USOO7256243B2
(12) United States Patent (10) Patent No.: US 7.256.243 B2 Oikawa et al. (45) Date of Patent: Aug. 14, 2007
(54) SILICON COMPOUND Shaped Organic/Inorganic Hybrid Polymers' authored by Fukuda et al and published in Macromolecules 2004, 37, 8517-8522.* (75) Inventors: Hisao Oikawa, Chiba (JP); Mikio Abstract for “Modified Cubic Spherosilicates as Macroinitiators for Yamahiro, Chiba (JP); Kazuhiro the Synthesis of Inorganic-Organic Starlike Polymers' authored by Holzinger et al. and published in the Journal of Polymer Science, Yoshida, Chiba (JP); Nobumasa Part A: Polymer Chemistry 2002, 40(21) 3858-3872.* Ootake, Chiba (JP); Kenichi 'Organic/Inorganic Nanocomposite star Polymers via Atom Trans Watanabe, Chiba (JP): Kohji Ohno, fer Radical Polymerization of Methyl Methacrylate Using Kyoto (JP); Yoshinobu Tsujii, Kyoto Octafunctional Silsesquioxane Cores' authored by Laine et al. and (JP); Takeshi Fukuda, Kyoto (JP) published in Macromolecules 2001, 34, 5398-5407.* Chunxin Zhang et al., “Hydrosilylation of Allyl Alcohol with (73) Assignee: Chisso Corporation, Osaka (JP) HSiMeOSiOls: Octa(3- hydroxypropyldimethylsiloxy)octasilsesquioxane and Its (*) Notice: Subject to any disclaimer, the term of this Octamethacrylate Derivative as Potential Precursors to Hybrid patent is extended or adjusted under 35 Nanocomposites”, J. Am. Chem. Soc., 122, 6979-6988, 2000. U.S.C. 154(b) by 266 days. Alan Sellinger et al., “Silsesquioxanes as Synthetic Platforms. 3. Photocurable, Liquid Epoxides as Inorganic/Organic Hybrid Pre (21) Appl. No.: 11/121,120 cursors”, Chem. Mater, vol. 8, No. 8, pp. 1592-1593, 1996. Alan Sellinger et al., “Silsesquioxanes as Synthetic Platforms. (22) Filed: May 4, 2005 Thermally Curable and Photocurable Inorganic/Organic Hybrids'. Macromolecules, 29, pp. 2327-2330, 1996. (65) Prior Publication Data Krzysztof Matyjaszewski et al., “Atom Transfer Radical Polymer US 2005/0250925 A1 Nov. 10, 2005 ization’, Chem. Rev., 101, 2921-2990, 2001. * cited by examiner (30) Foreign Application Priority Data Primary Examiner Marc S. Zimmer May 7, 2004 (JP) ...... 2004-138513 (74) Attorney, Agent, or Firm Wenderoth, Lind & Ponack, LLP. (51) Int. Cl. CSF 4/6 (2006.01) (57) ABSTRACT C08G 77/442 (2006.01) (52) U.S. Cl...... 526/126; 528/31:528/34; 525/100: 525/102: 525/106; 526/128; 526/129 The present invention provides a novel silicon compound (58) Field of Classification Search ...... 526/126, represented by Formula (1) having a living radical polymer 526/128, 129 ization initiating ability for addition-polymerizable mono See application file for complete search history. mers and a polymer obtained using the same. The above polymer can provide an organic-inorganic composite mate (56) References Cited rial having a distinct structure. U.S. PATENT DOCUMENTS 2002/0106513 A1* 8/2002 Matyjaszewski et al. ... 428/404 (1) 2005/0049381 A1 3f2005 Yamahiro et al...... 528.10 2005/0288468 A1* 12/2005 Ohno et al...... 526,317.1 2006, OO52623 A1 3, 2006 Yoshida et al. R! O-. -OS/ 2006/0094849 A1* 5/2006 Toyoda ...... 528.34 A-(R)(R2)Si VASi’ssi s-ossils-sicR)(R)-A 2006/0175684 A1* 8, 2006 Oikawa et al...... 257,632 No1 O V 2006/0287454 A1* 12/2006 Yamahiro et al...... 526,279 S. O - D3, D2&; 1Ns;-ry1O N O FOREIGN PATENT DOCUMENTS A-(R)(R4)Si Sir O No is, Si(R2)(R)-A EP 1 428 795 6, 2004 R -1R1 Nd R1 R1 OTHER PUBLICATIONS “Novel Inorganic-Organic Hybrid Block Copolymers as Pore Gen wherein R' is hydrogen, alkyl, aryl or arylalkyl; R and R' erators for Nanoporous Ultralow Dielectric Constant Films' are alkyl, phenyl or cyclohexyl, and A is a group having an authored by Yoon et al. and published in Macromolecules 2005, 38. 103.1-1034. ability to initiate polymerization of a monomer. “Living Radical Polymerization by Polyhedral Oligomeric Silsesquioxane-Holding Initiators: Precision Synthesis of Tadpole 54 Claims, No Drawings US 7,256.243 B2 1. 2 SILICON COMPOUND monomers of a wide range and which has a silsesquioxane skeleton of a double decker (a structure in which two corners FIELD OF THE INVENTION in a cage type structure of an octasilisesquioxane are broken) structure. Then, they have found that the above silicon The present invention relates to a novel silicon compound compound is effective for solving the problem described characterized by having a polymerization initiating ability above, and they have completed the present invention based for addition-polymerizable monomers, a production process on the above knowledge. That is, the present invention for the same and a polymer obtained using the same. comprises the following structures. BACKGROUND OF THE INVENTION 10 1 A silicon compound represented by Formula (1): Polymers have come to be used in various fields not only as a general purpose structure-forming material but also as (1) a value-added type material having functions and perfor mances of a high degree. This is followed by an increase in 15 R RI R1 the importance of producing high molecular materials under R O- - M precise design. Attentions are paid on silsesquioxane deriva VRS16SSS-Si(R)(R)-A A-(R)(R)Sint-SiO O Si V O tives of a cage type having a dimethylsiloxy group as an V O organic-inorganic composite material containing silsesqui - d. 3rd 2s; 1Ns;-ry1O Si n O oxane as an inorganic component. This is because they are A-(R)(R4)Si Sir O No sig YSi(R2)(R)-A expected to be applied to precursors of organic/inorganic R" yell- NG R1 hybrid materials, low dielectric materials, optical crystals R1 and materials forming liquid crystal display elements, and R1 the reason therefor resides in that the above silsesquioxane derivatives have a structure close to those of silica and 25 Zeolite. Cage type silsesquioxanes in which a hydroxyl wherein respective R's are groups independently selected group (J. Am. Chem. Soc., 122 (200), 6979-), an epoxy from hydrogen, alkyl having a carbon atom number of 1 to group (Chemistry of Materials, 8 (1996), 1592-) or a meth 45 in which optional hydrogen may be substituted with acryloyloxy group (Macromolecules, 29 (1996), 2327-) is fluorine and in which optional —CH2— may be substituted bonded to a dimethylsiloxy group are reported. So-called 30 with —O—, —CH=CH-, cycloalkylene or cycloalk organic-inorganic composite materials of organic polymers enylene, substituted or non-substituted aryl and arylalkyl and silsesquioxanes are prepared by making use of the above constituted from a substituted or non-substituted aryl group functional groups. The organic-inorganic composite mate and an alkylene group in which optional hydrogen may be rials can be obtained by radically polymerizing cage type substituted with fluorine and in which optional —CH2— silsesquioxanes having a methacryloyloxy group alone or 35 may be substituted with —O—, —CH=CH- or cycloalky under the coexistence of other acryl base monomers. lene; R and Rare groups independently selected from alkyl In order to optimize the functions of high molecular having a carbon atom number of 1 to 8, phenyl and cyclo materials according to purposes, the molecular properties of hexyl, and A is a group having a polymerization initiating a polymer and the properties thereof as a molecular aggre ability for a monomer. gate have to be precisely analyzed, and this makes it 40 necessary to use a polymer having a distinct structure. 2 The silicon compound as described in the item 1. However, conventional organic-inorganic composite mate wherein respective R's are groups independently selected rials do not contain polymers in which a structure is con from hydrogen, alkyl having a carbon atom number of 1 to trolled as an organic component including the composite 45 in which optional hydrogen may be substituted with materials described above. A large part of them is obtained 45 fluorine and in which optional —CH2— may be substituted by mechanically blending silsesquioxanes with organic with —O—, —CH=CH-, cycloalkylene or cycloalk polymers, and therefore it used to be very difficult to control enylene, substituted or non-substituted aryl and arylalkyl a structure thereof as a molecular aggregate of a composite constituted from a Substituted or non-substituted aryl group matter. Then, it has come to be tried to control a structure of and an alkylene group in which optional hydrogen may be a polymer by using a polymerization initiator. It is disclosed 50 substituted with fluorine and in which optional —CH2— in Chem. Rev., 101 (2001), 2921- that an O-haloester group may be substituted with —O—, —CH=CH- or cycloalky is a good polymerization initiator for styrene base monomers lene; R and Rare groups independently selected from alkyl and methacrylic acid base monomers in living polymeriza having a carbon atom number of 1 to 8, phenyl and cyclo tion, but silsesquioxane derivatives having an O-haloester hexyl, and A is a group having a living radical polymeriza group have not been known to date. 55 tion initiating ability for a monomer. DISCLOSURE OF THE INVENTION 3 The silicon compound as described in the item 1. wherein respective R's are groups independently selected An object of the present invention is to provide a novel from hydrogen, alkyl having a carbon atom number of 1 to silicon compound having a living radical polymerization 60 45 in which optional hydrogen may be substituted with initiating ability for addition-polymerizable monomers of a fluorine and in which optional —CH2— may be substituted wide range and a polymer obtained using the same to with —O—, —CH=CH-, cycloalkylene or cycloalk thereby solve the problems described above regarding con enylene, substituted or non-substituted aryl and arylalkyl ventional organic-inorganic composite materials. constituted from a Substituted or non-substituted aryl group The present inventors have found a silicon compound 65 and an alkylene group in which optional hydrogen may be which has a functional group having a living radical poly substituted with fluorine and in which optional —CH2— merization initiating ability for addition-polymerizable may be substituted with —O—, —CH=CH or cycloalky US 7,256.243 B2 3 4 lene; R and Rare groups independently selected from alkyl having a carbon atom number of 1 to 8, phenyl and cyclo hexyl, and A is a group represented by any of Formula (2-1), (R) (2-4) Formula (2-2), Formula (2-3) and Formula (2-4); 3. 5
(2-1) --().- z-s--N V O R. R9 —zi-o-c--x 10 wherein R and Rare independently alkyl having a carbon atom number of 1 to 12, cycloalkyl having a carbon atom number of 5 to 10 or aryl having a carbon atom number of wherein Z' is alkylene having a carbon atom number of 2 to 15 6 to 10, and RandR may be combined with each other to 20 or alkenylene having a carbon atom number of 3 to 8, and form a ring together with N. Z is alkylene which has a optional —CH2— in these alkylene and alkenylene may be carbon atom number of 1 to 3 and in which optional substituted with —O : R is hydrogen, alkyl having a —CH2— may be substituted with —O : Z” is alkylene carbon atom number of 1 to 20, aryl having a carbon atom which has a carbon atom number of 2 to 10 and in which number of 6 to 20 or arylalkyl having a carbon atom number optional —CH2— may be substituted with —O—, of 7 to 20; R is alkyl having a carbon atom number of 1 to —COO or —OCO : R is alkyl having a carbon atom 20, aryl having a carbon atom number of 6 to 20 or arylalkyl number of 1 to 3; a is an integer of 0 to 2; and a bonding having a carbon atom number of 7 to 20; and X is halogen; position of Z on the benzene ring is a metaposition or a para 25 position to a bonding position of Z’, and a bonding position of R is an optional position excluding the respective bond (2-2) (R), ing positions of Z and Z'. 4 The silicon compound as described in the item 3. 30 wherein respective R's are groups independently selected --(). from hydrogen and alkyl having a carbon atom number of 1 to 30 in which optional hydrogen may be substituted with O fluorine and in which optional —CH2— may be substituted with —O— or cycloalkylene. 35 wherein Z is alkylene having a carbon atom number of 2 to 5. The silicon compound as described in the item 3. 10, and optional —CH2— in this alkylene may be substi wherein respective R's are groups independently selected tuted with —O— or -COO. : R is alkyl having a carbon from alkenyl having a carbon atom number of 2 to 20 in atom number of 1 to 3; a is an integer of 0 to 2: X is which optional hydrogen may be substituted with fluorine halogen; and a bonding position of-SOX on the benzene 40 and in which optional —CH2— may be substituted with ring is an ortho position, a meta position or a para position —O— or cycloalkylene and alkyl having a carbon atom to a bonding position of Z, and a bonding position of R is number of 1 to 20 in which optional hydrogen may be an optional position excluding the respective bonding posi substituted with fluorine and in which at least one —CH2— tions of Z and -SOX: 45 is substituted with cycloalkenylene. 6. The silicon compound as described in the item 3. wherein respective R's are groups independently selected (2-3) from phenyl in which optional hydrogen may be substituted (R), 50 with halogen or alkyl having a carbon atom number of 1 to 10 and non-substituted naphthyl; in alkyl which is a sub stituent of the phenyl, optional hydrogen may be substituted with fluorine, and optional —CH2— may be substituted with —O—, —CH=CH cycloalkylene or phenylene; 55 and when the phenyl has plural substituents, the substituents wherein Z is alkylene which has a carbon atom number of may be the same group or different groups. 1 to 3 and in which optional —CH2— may be substituted 7. The silicon compound as described in the item 3. with —O ; Z” is alkylene which has a carbonatom number wherein respective R's are groups independently selected of 2 to 10 and in which optional —CH2— may be substi from phenylalkyl constituted from a phenyl group in which tuted with —O , —COO or —OCO : R is alkyl 60 optional hydrogen may be substituted with halogen or alkyl having a carbon atom number of 1 to 3; a is an integer of 0 having a carbon atom number of 1 to 12 and an alkylene to 2: X is halogen; and a bonding position of Z on the group having a carbon atom number of 1 to 12 in which benzene ring is a meta position or a para position to a optional hydrogen may be substituted with fluorine and in bonding position of Z’, and a bonding position of R is an 65 which optional —CH2— may be substituted with —O—, optional position excluding the respective bonding positions —CH=CH or cycloalkylene; in alkyl which is a sub of Z and Z7; stituent of the phenyl group, optional hydrogen may be US 7,256.243 B2 5 substituted with fluorine, and optional —CH2— may be substituted with —O , —CH=CH cycloalkylene or phenylene; and when the phenyl group has plural Substitu (2-1) ents, the Substituents may be the same group or different O R. groups. - ZI-O-C-C-XI 8. The silicon compound as described in the item 3. wherein respective R's are groups independently selected from alkyl having a carbon atom number of 1 to 8 in which optional hydrogen may be substituted with fluorine and in 10 which optional —CH2— may be substituted with —O , —CH=CH cycloalkylene or cycloalkenylene, phenyl in wherein Z' is alkylene having a carbon atom number of 2 to which optional hydrogen may be substituted with halogen, 20 or alkenylene having a carbon atom number of 3 to 8, and optional —CH2— in these alkylene and alkenylene may be methyl or methoxy, non-substituted naphthyl and phenyla 15 lkyl constituted from a phenyl group in which optional substituted with —O : R is hydrogen, alkyl having a hydrogen may be substituted with fluorine, alkyl having a carbon atom number of 1 to 20, aryl having a carbon atom carbon atom number of 1 to 4, vinyl or methoxy and an number of 6 to 20 or arylalkyl having a carbon atom number alkylene group which has a carbon atom number of 1 to 8 of 7 to 20; R is alkyl having a carbon atom number of 1 to and in which optional —CH2— may be substituted with 20, aryl having a carbon atom number of 6 to 20 or arylalkyl —O , —CH=CH or cycloalkylene; and when the phe having a carbon atom number of 7 to 20; and X is halogen. nyl or a phenyl group in the phenylalkyl has plural Substitu 13. The silicon compound as described in the item 3. ents, the Substituents may be the same group or different wherein all R's are phenyl: A is the group represented by groups. 25 Formula (2-1); and Z' in Formula (2-1) is alkylene which 9. The silicon compound as described in the item 3. has a carbon atom number of 2 to 10 and in which optional wherein all R's are the same group selected from alkyl —CH2— may be substituted with —O—. having a carbon atom number of 1 to 8 in which optional 14 The silicon compound as described in the item 3. hydrogen may be substituted with fluorine and in which wherein all R's are phenyl; R and Rare methyl: A is the optional —CH2— may be substituted with —O—, 30 group represented by Formula (2-1); in Formula (2-1), Z' is —CH=CH-, cycloalkylene or cycloalkenylene, phenyl in C.H. , —CH - or -CH, O C.H. : R* and R' which optional hydrogen may be substituted with halogen, are methyl; and X is bromine. methyl or methoxy, non-substituted naphthyl and phenyla lkyl constituted from a phenyl group in which optional 35 15 The silicon compound as described in the item 3. hydrogen may be substituted with fluorine, alkyl having a wherein all R's are the same group selected from alkyl carbon atom number of 1 to 4, vinyl or methoxy and an having a carbon atom number of 1 to 8 in which optional alkylene group which has a carbon atom number of 1 to 8 hydrogen may be substituted with fluorine and in which and in which optional —CH2— may be substituted with optional —CH2— may be substituted with —O—, —O , —CH=CH or cycloalkylene; and when the phe 40 —CH=CH cycloalkylene or cycloalkenylene, phenyl in nyl or a phenyl group in the phenylalkyl has plural Substitu which optional hydrogen may be substituted with halogen, ents, the Substituents may be the same group or different methyl or methoxy, non-Substituted naphthyl and phenyla groups. lkyl constituted from a phenyl group in which optional hydrogen may be substituted with fluorine, alkyl having a 10. The silicon compound as described in the item 3. 45 wherein all R's are phenyl. carbon atom number of 1 to 4, vinyl or methoxy and an alkylene group which has a carbon atom number of 1 to 8 11 The silicon compound as described in the item 3. and in which optional —CH2— may be substituted with wherein all R's are phenyl, and R and R are methyl. —O—, —CH=CH or cycloalkylene; when the phenyl or 12. The silicon compound as described in the item 3. 50 a phenyl group in the phenylalkyl has plural Substituents, the wherein all R's are the same group selected from alkyl Substituents may be the same group or different groups; and having a carbon atom number of 1 to 8 in which optional A is the group represented by Formula (2-2): hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH cycloalkylene or cycloalkenylene, phenyl in 55 (2-2) which optional hydrogen may be substituted with halogen, (R), methyl or methoxy, non-substituted naphthyl and phenyla lkyl constituted from a phenyl group in which optional --(y hydrogen may be substituted with fluorine, alkyl having a 60 carbon atom number of 1 to 4, vinyl or methoxy and an alkylene group which has a carbon atom number of 1 to 8 O and in which optional —CH2— may be substituted with —O , —CH=CH or cycloalkylene; when the phenyl or a phenyl group in the phenylalkyl has plural Substituents, the 65 wherein Z is alkylene having a carbon atom number of 2 to Substituents may be the same group or different groups; and 10, and optional —CH2— in this alkylene may be substi A is the group represented by Formula (2-1): tuted with —O— or -COO : R is alkyl having a carbon US 7,256.243 B2 7 8 atom number of 1 to 3; a is an integer of 0 to 2: X is group represented by Formula (2-3); in Formula (2-3), Z is halogen; and a bonding position of-SOX on the benzene —CH2—, Z is —C.H. : X is chlorine or bromine; and a ring is an ortho position, a meta position or a para position is 0. to a bonding position of Z, and a bonding position of R is 21. The silicon compound as described in the item 3. an optional position excluding the respective bonding posi wherein all R's are the same group selected from alkyl tions of Z and -SOX. having a carbon atom number of 1 to 8 in which optional 16. The silicon compound as described in the item 3. hydrogen may be substituted with fluorine and in which wherein all R's are phenyl: A is the group represented by optional —CH2— may be substituted with —O—, Formula (2-2); Z in Formula (2-2) is —CH Z; and Z 10 —CH=CH cycloalkylene or cycloalkenylene, phenyl in is a single bond or alkylene which has a carbonatom number which optional hydrogen may be substituted with halogen, of 1 to 8 and in which optional —CH2—may be substituted methyl or methoxy, non-Substituted naphthyl and phenyla with —O— or —COO—. lkyl constituted from a phenyl group in which optional 17. The silicon compound as described in the item 3. 15 hydrogen may be substituted with fluorine, alkyl having a wherein all R's are phenyl; R and Rare methyl: A is the carbon atom number of 1 to 4, vinyl or methoxy and an group represented by Formula (2-2); in Formula (2-2), Z is alkylene group which has a carbon atom number of 1 to 8 —CRH. : X is chlorine or bromine; and a is 0. and in which optional —CH2— may be substituted with —O—, —CH=CH or cycloalkylene; when the phenyl or 18. The silicon compound as described in the item 3. wherein all R's are the same group selected from alkyl a phenyl group in the phenylalkyl has plural Substituents, the having a carbon atom number of 1 to 8 in which optional Substituents may be the same group or different groups; and hydrogen may be substituted with fluorine and in which A is the group represented by Formula (2-4): optional —CH2— may be substituted with —O—, —CH=CH cycloalkylene or cycloalkenylene, phenyl in 25 (2-4) which optional hydrogen may be substituted with halogen, (R), methyl or methoxy, non-substituted naphthyl and phenyla lkyl constituted from a phenyl group in which optional hydrogen may be substituted with fluorine, alkyl having a carbon atom number of 1 to 4, vinyl or methoxy and an 30 = 7 z-s--( alkylene group which has a carbon atom number of 1 to 8 and in which optional —CH2— may be substituted with —O , —CH=CH or cycloalkylene; when the phenyl or a phenyl group in the phenylalkyl has plural Substituents, the wherein RandR are independently hydrogen, alkyl having Substituents may be the same group or different groups; and 35 a carbonatom number of 1 to 12, cycloalkyl having a carbon A is the group represented by Formula (2-3): atom number of 5 to 10 or aryl having a carbonatom number of 6 to 10, and RandR may be combined with each other to form a ring together with N; Z is alkylene which has a (2-3) 40 carbon atom number of 1 to 3 and in which optional (R), —CH2— may be substituted with —O : Z” is alkylene which has a carbon atom number of 2 to 10 and in which optional —CH2— may be substituted with —O—, —COO or —OCO : R is alkyl having a carbon atom 45 number of 1 to 3; a is an integer of 0 to 2; and a bonding position of Z on the benzene ring is a metaposition or a para wherein Z is alkylene which has a carbon atom number of position to a bonding position of Z’, and a bonding position 1 to 3 and in which optional —CH2— may be substituted with —O ; Z” is alkylene which has a carbonatom number of R is an optional position excluding the respective bond of 2 to 10 and in which optional —CH2— may be substi 50 ing positions of Z and Z'. tuted with —O , —COO or —OCO : R is alkyl 22 The silicon compound as described in the item 3. having a carbon atom number of 1 to 3; a is an integer of 0 wherein all R's are phenyl: A is the group represented by to 2: X is halogen; and a bonding position of Z on the Formula (2-4); and in Formula (2-4), Z7 is C.H. Z'. benzene ring is a meta position or a para position to a and Z' is a single bond or alkylene which has a carbon atom bonding position of Z, and a bonding position of R is an 55 number of 1 to 8 and in which optional —CH2— may be optional position excluding the respective bonding positions substituted with —O—, —COO— or —OCO-. of Z and Z7. 23 The silicon compound as described in the item 3. 19. The silicon compound as described in the item 3. wherein all R's are phenyl; R and Rare methyl; A is the wherein all R's are phenyl: A is the group represented by 60 group represented by Formula (2-4); in Formula (2-4), R Formula (2-3); Z” in Formula (2-3) is C.H. Z'; and Z' and Rare ethyl; Z is —CH2—, Z” is —CH ; and a is is a single bond or alkylene which has a carbonatom number O. of 1 to 8 and in which optional —CH2— may be substituted 24. A production process for a silicon compound repre with —O—, —COO— or —OCO-. 65 sented by Formula (1-1) characterized by obtaining a com 20. The silicon compound as described in the item 3. pound represented by Formula (5) by a step (a) and carrying wherein all R's are phenyl; R and Rare methyl: A is the out a step (b) and then a step (c): US 7,256.243 B2 10
10 o-1 Si N/ R1 wherein respective R's are groups independently selected 15 from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk enylene, substituted or non-substituted aryl and arylalkyl constituted from a Substituted or non-substituted aryl group and an alkylene group in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH- or cycloalky lene; R and Rare groups independently selected from alkyl 25 having a carbon atom number of 1 to 8, phenyl and cyclo hexyl; and A' is a group represented by Formula (2-1-1):
(2-1-1) 30 O R. —ch-z-o-c-f-x 35 wherein Z is a single bond or alkylene having a carbon atom wherein in the above formulas, R', RandR have the same number of 1 to 18 or alkenylene having a carbon atom number of 2 to 6, and optional —CH2— in these alkylene meanings as those of these codes in Formula (1-1), and M and alkenylene may be substituted with —O : R is hydro 40 is a monovalent alkali metal atom; gen, alkyl having a carbon atom number of 1 to 20, aryl
(6)
(7)
RI US 7,256.243 B2 11 12 wherein Z in the above formulas has the same meaning as and an alkylene group in which optional hydrogen may be that of Z in Formula (2-1-1), and R', RandR in Formula substituted with fluorine and in which optional —CH2— (7) have the same meanings as those of these codes in may be substituted with —O—, —CH=CH- or cycloalky Formula (1-1); lene; R and Rare groups independently selected from alkyl having a carbon atom number of 1 to 8, phenyl and cyclo
(8) O R —ch-z-o-c-f-x
x-c--x 15 wherein Z is a single bond or alkylene having a carbon atom number of 1 to 18 or alkenylene having a carbon atom wherein R, R and X" have the same meanings as those of number of 2 to 6, and optional —CH2— in these alkylene these codes in Formula (2-1-1); and X is halogen. and alkenylene may be substituted with —O : R is hydro gen, alkyl having a carbon atom number of 1 to 20, aryl 25. The production process as described in the item 24, having a carbon atom number of 6 to 20 or arylalkyl having wherein all R's are the same group selected from alkyl a carbonatom number of 7 to 20; R is alkyl having a carbon having a carbon atom number of 1 to 8 in which optional atom number of 1 to 20, aryl having a carbon atom number hydrogen may be substituted with fluorine and in which of 6 to 20 or arylalkyl having a carbon atom number of 7 to optional —CH2— may be substituted with —O—, 25 20; and X is halogen; —CH=CH cycloalkylene or cycloalkenylene, phenyl in which optional hydrogen may be substituted with halogen,
60 wherein R, R and R in the above formulas have the same wherein respective R's are groups independently selected meanings as those of these codes in Formula (1-1); from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with
(6) CH=CH-Z2-OH (7) 1 D1 R1 R R1 2 3y to 2\c: yOSs:- Ns.( HO-Z-CH-(R)(R sis-s-sO No1 v O HO-Z2-CH,-(R3)(R2)Si1 O orSin N O Si R Y-R1 No R1 R1 wherein Z in the above formulas has the same meaning as 30 A production process for a silicon compound repre that of Z in Formula (2-1-1), and R', RandR in Formula sented by Formula (1-3) characterized by carrying out a step (7) have the same meanings as those of these codes in (e) and then a step (f): Formula (1-1); (1-3)
(8) 30 O R
X---x wherein respective R's are groups independently selected 35 from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with wherein R, R and X have the same meanings as those of fluorine and in which optional —CH may be substituted these codes in Formula (2-1-1); and X is halogen. with —O—, —CH=CH-, cycloalkylene or cycloalk enylene, substituted or non-substituted aryl and arylalkyl 40 constituted from a Substituted or non-substituted aryl group and an alkylene group in which optional hydrogen may be 28. The production process as described in the item 27, substituted with fluorine and in which optional —CH2— wherein all R's are the same group selected from alkyl may be substituted with —O—, —CH=CH- or cycloalky having a carbon atom number of 1 to 8 in which optional 45 lene; R and Rare groups independently selected from alkyl hydrogen may be substituted with fluorine and in which having a carbon atom number of 1 to 8, phenyl and cyclo optional —CH2— may be substituted with —O—, hexyl; and A is a group represented by Formula (2-3-1): —CH=CH cycloalkylene or cycloalkenylene, phenyl in which optional hydrogen may be substituted with halogen, (2-3-1) methyl or methoxy, non-substituted naphthyl and phenyla 50 (R'), lkyl constituted from a phenyl group in which optional hydrogen may be substituted with fluorine, alkyl having a carbon atom number of 1 to 4, vinyl or methoxy and an alkylene group which has a carbon atom number of 1 to 8 and in which optional —CH2— may be substituted with 55 —O , —CH=CH or cycloalkylene; when the phenyl or wherein Z is alkylene which has a carbon atom number of a phenyl group in the phenylalkyl has plural Substituents, the 1 to 3 and in which optional —CH may be substituted Substituents may be the same group or different groups; and with —O ; Z is a single bond or alkylene which has a R° and R are groups independently selected from alkyl 60 carbon atom number of 1 to 8 and in which optional having a carbon atom number of 1 to 8, phenyl and cyclo —CH2— may be substituted with —O , —COO or hexyl. —OCO : R is alkyl having a carbon atom number of 1 to 3; a is an integer of 0 to 2: X is halogen; and a bonding position of Z on the benzene ring is a metaposition or a para 65 position to a bonding position of Z, and a bonding position 29. The production process as described in the item 27, of R is an optional position excluding the respective bond wherein all R's are phenyl, and R and R are methyl. ing positions of Z and Z: US 7,256.243 B2 15 16
(1-4)
30
(5)
RI Oss- - O R 35
On. wherein respective R's are groups independently selected 40 from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk wherein R, R and R in the above formulas have the same enylene, substituted or non-substituted aryl and arylalkyl meanings as those of these codes in Formula (1-3), and M 45 constituted from a Substituted or non-substituted aryl group is a monovalent alkali metal atom; and an alkylene group in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH- or cycloalky a step in which the compound represented by Formula (5) is lene; R and Rare groups independently selected from alkyl reacted with a compound represented by Formula (2-3-2) to 50 having a carbon atom number of 1 to 8, phenyl and cyclo obtain the silicon compound represented by Formula (1-3): hexyl; and A' is a group represented by Formula (2-4-1):
(2-3-2) (2-4-1) (R), 55 (R'), -et--(y- z-s--N V 60 R9 wherein Z, Z, R', a and X have the same meanings as those of these codes in Formula (2-3-1); and the bonding positions of Z and R7 on the benzene ring are the same as wherein Z is alkylene which has a carbon atom number of the bonding positions thereof in Formula (2-3-1). 1 to 3 and in which optional —CH2— may be substituted 65 with —O ; Z is a single bond or alkylene which has a 31 The production process as described in the item 30, carbon atom number of 1 to 8 and in which optional wherein all R's are the same group selected from alkyl —CH2— may be substituted with —O , —COO or US 7,256.243 B2 17 18 —OCO : R and R are independently hydrogen, alkyl —O—, —CH=CH or cycloalkylene; when the phenyl or having a carbon atom number of 1 to 12, cycloalkyl having a phenyl group in the phenylalkyl has plural Substituents, the a carbon atom number of 5 to 10 or aryl having a carbon Substituents may be the same group or different groups; and atom number of 6 to 10, and R and R may be combined R° and R are groups independently selected from alkyl with each other to form a ring together with N. R7 is alkyl having a carbon atom number of 1 to 8, phenyl and cyclo having a carbon atom number of 1 to 3; a is an integer of 0 to 2; and a bonding position of Z on the benzene ring is a hexyl. meta position or a para position to a bonding position of Z. 35. The production process as described in the item 33. and a bonding position of R is an optional position exclud wherein all R's are phenyl, and R and Rare methyl. ing the respective bonding positions of Z and Z: 10 36 A production process for a silicon compound repre sented by Formula (1-1) characterized by carrying out a step (1-3) (g) and then a step (h):
15 (1-1)
Al-(R)(R2)Si Si Si V No1 O V y, O -NotR1 Y. O R1 Al-(R)(R4)SiI-R (Rs.1"Sso1's Sir O No sig O Si(R2)(R)-A R l RI No R1 wherein R, R and R have the same meanings as those of 25 RI these codes in Formula (1-4), and A is a group represented by Formula (2-3-1): wherein respective R's are groups independently selected from hydrogen, alkyl having a carbon atom number of 1 to (2-3-1) 30 (R), 45 in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk enylene, substituted or non-substituted aryl and arylalkyl 35 constituted from a Substituted or non-substituted aryl group and an alkylene group in which optional hydrogen may be wherein Z, Z, R7 and a have the same meanings as those substituted with fluorine and in which optional —CH2— of these codes in Formula (2-4-1); X is halogen; and the may be substituted with —O—, —CH=CH- or cycloalky bonding positions of Z and R7 on the benzene ring are the lene; R and Rare groups independently selected from alkyl same as the bonding positions thereof in Formula (2-4-1); 40 having a carbon atom number of 1 to 8, phenyl and cyclo hexyl; and A' is a group represented by Formula (2-1-1):
(9) S R8 (2-1-1) | / 45 O R. MI S-C-N V —ch-z-o-c-f-x wherein RandR have the same meanings as those of these 50 codes in Formula (2-4-1); M' is a metal element of the first wherein Z is a single bond or alkylene having a carbon atom group or the second group in the periodic table; and p is the number of 1 to 18 or alkenylene having a carbon atom same value as a valence of M'. number of 2 to 6, and optional —CH2— in these alkylene and alkenylene may be substituted with —O : R is hydro 34. The production process as described in the item 33. 55 wherein all R's are the same group selected from alkyl gen, alkyl having a carbon atom number of 1 to 20, aryl having a carbon atom number of 1 to 8 in which optional having a carbon atom number of 6 to 20 or arylalkyl having hydrogen may be substituted with fluorine and in which a carbonatom number of 7 to 20; R is alkyl having a carbon optional —CH2— may be substituted with —O—, atom number of 1 to 20, aryl having a carbon atom number —CH=CH cycloalkylene or cycloalkenylene, phenyl in 60 of 6 to 20 or arylalkyl having a carbon atom number of 7 to which optional hydrogen may be substituted with halogen, 20; and X" is halogen; methyl or methoxy, non-substituted naphthyl and phenyla lkyl constituted from a phenyl group in which optional hydrogen may be substituted with fluorine, alkyl having a a step in which a compound represented by Formula (4) is carbon atom number of 1 to 4, vinyl or methoxy and an 65 reacted with a compound represented by Formula (2-1-2) in alkylene group which has a carbon atom number of 1 to 8 the presence of a transition metal catalyst to obtain a silicon and in which optional —CH2— may be substituted with compound represented by Formula (2-1-3): US 7,256.243 B2 19 20 and in which optional —CH2— may be substituted with —O—, —CH=CH or cycloalkylene; when the phenyl or R2 (4) a phenyl group in the phenylalkyl has plural Substituents, the Substituents may be the same group or different groups; and C1-S-H R° and R are groups independently selected from alkyl having a carbon atom number of 1 to 8, phenyl and cyclo hexyl. (2-1-2) O R. 38. The production process as described in the item 36, CH=CH-Z4-O-C-C-X----vi 10 wherein all R's are phenyl, and R and Rare methyl. 39 A production process for a silicon compound repre (2-1-3) sented by Formula (1-2) characterized by carrying out a step R2 O R (i) and then a step ():
15 ci-s-ch-z-o-c-f-x (1-2) R RI R voss- -O J. 2 3 2 wherein R and R in the above formulas have the same SS-O- -O-sis-SiR )(R)-A meanings as those of these codes in Formula (1-1), and Z. A2-(R)(R2)Si-O O R, R and X" have the same meanings as those of these V O O Si codes in Formula (2-1-1); A2-(R3)(R2)Si1(R) R's yi-Osis T 1 in s Q sig1Oa. Si(R2)(R)-A2 RI O O RI 25 RI a step in which the compound represented by Formula R1 (2-1-3) is reacted with a compound represented by Formula (3-1) or a compound represented by Formula (3-2) to thereby obtain the compound represented by Formula (1-1): wherein respective R's are groups independently selected 30 from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with (3-1) fluorine and in which optional —CH2— may be substituted RI with —O—, —CH=CH-, cycloalkylene or cycloalk R! O-l-I-O-N enylene, substituted or non-substituted aryl and arylalkyl VRSSi’ssi 36ssis O O Y O V 35 constituted from a Substituted or non-substituted aryl group S. O e4M and an alkylene group in which optional hydrogen may be O n substituted with fluorine and in which optional —CH2— Asis O-SiNO1 lso-s- V may be substituted with —O—, —CH=CH- or cycloalky RI R1 O RI lene; R and Rare groups independently selected from alkyl RI 40 having a carbon atom number of 1 to 8, phenyl and cyclo (3-2) hexyl; and A is a group represented by Formula (2-2-1): R1 R R1 R -O-N (2-2-1) 1. 2,2's Si -O-ssis OH HO O 45 (R), y O Onslo-SinSin syo-si1. OH o- V R1 RI O RI R1 50 wherein R' in the above formulas has the same meaning as that of R' in Formula (1-1), and M is a monovalent alkali wherein Z is a single bond or alkylene having a carbon atom metal atom. number of 1 to 8, and optional —CH in the above 55 alkylene may be substituted with —O— or -COO : R is 37. The production process as described in the item 36, alkyl having a carbon atom number of 1 to 3; a is an integer wherein all R's are the same group selected from alkyl of 0 to 2: X is halogen; and a bonding position of SOX having a carbon atom number of 1 to 8 in which optional on the benzene ring is an ortho position, a meta position or hydrogen may be substituted with fluorine and in which a para position to a bonding position of Z, and a bonding optional —CH2— may be substituted with —O—, 60 position of R is an optional position excluding the respec —CH=CH cycloalkylene or cycloalkenylene, phenyl in tive bonding positions of Z and SOX: which optional hydrogen may be substituted with halogen, methyl or methoxy, non-substituted naphthyl and phenyla
In Formula (2-1-4), Z is a single bond or alkylene having a 60 carbon atom number of 1 to 8, and optional —CH2—in this alkylene may be substituted with —O—. That is, the preferred example of Z' is alkylene which has a carbon atom number of 2 to 10 and in which optional —CH2— may be substituted with —O—. The examples of 65 Such alkylene are CH . C.H. , CHs , C5Ho , CH, O—CH and CH, O US 7,256.243 B2 39 40 R", R and R in Formula (1-2) have the same meanings as tion having haloalkylphenyl has an excellent polymerization those of these codes in Formula (1), and A is a group initiating ability in the presence of a transition metal catalyst represented by Formula (2-2): and can continue to maintain a living polymerizability. It can initiate polymerization for all radically polymerizable monomers. In particular, it can reveal an excellent living (2-2) (R6) polymerizability to styrene base derivatives. Ahaloalkylphenyl has a strong electrophilicity, and there fore an amino group, a hydroxyl group and a mercapto group 10 can be introduced into the silicon compound of the present --(). invention having haloalkylphenyl by making use of various O electrophilic reagents. That is, this silicon compound can efficiently be used as a useful intermediate. The preferred examples of the silicon compound of the In Formula (2-2), X is halogen, and the examples thereof 15 present invention having haloalkylphenyl is a compound are chlorine, bromine and iodine. Chlorine and bromine are most preferred as an initiating group for atom transfer represented by Formula (1-3): radical polymerization. Z is alkylene having a carbon atom number of 2 to 10, and optional —CH2— in this alkylene (1-3) may be substituted with —O— or —COO . A bonding position of -SOX on the benzene ring is an ortho posi tion, a meta position or a para position to a bonding position of Z. R is alkyl having a carbon atom number of 1 to 3. The code of a showing the number of R is 0, 1 or 2, and Zero is 25 most preferred. A bonding position of R is an optional position excluding the respective bonding positions of Z. and SOX. Z in Formula (2-2) is preferably a group represented by 30 —CH Z as is the case with Formula (2-1). That is, the preferred example of Formula (2-2) is Formula (2-2-4): R", R and R in Formula (1-3) have the same meanings as those of these codes in Formula (1), and A is a group (2-2-4) represented by (R), 35
(2-3) (R),
40 O
In Formula (2-2-4), Z is a single bond or alkylene having a 45 X in Formula (2-3) is halogen such as chlorine, bromine carbon atom number of 1 to 3. and iodine. Chlorine and bromine are more preferred as an That is, the preferred example of Z is alkylene having a initiating group in atom transfer radical polymerization. Z. carbon atom number of 2 to 5. The examples of such is alkylene having a carbon atom number of 1 to 3. The alkylene are —CH , —CH , —CHs and —Cs examples of Z are methylene, 1.2-ethylene, 1,1-ethylene, Ho-. The most preferred example of Z is —CH-. 50 1,3-trimethylene, ethylmethylene, 1-methyl-1,2-ethylene However, the selected range of Z shall not be restricted to and 2-methyl-1,2-ethylene. The preferred example of Z is them. In Formula (2-2-4), the codes other than Z have the methylene. same meanings as those of the codes in Formula (2-2), and Z” is alkylene having a carbon atom number of 2 to 10. In the bonding positions of the halogenated Sulfonyl group and this alkylene, one —CH2— may be substituted with —O—. R to Z on the benzene ring are the same as these bonding 55 A bonding position of Z on the benzene ring is a meta positions to Z in Formula (2-2). position or a para position to a bonding position of Z. R is Anatom transfer radical polymerization method is known as a polymerization method using haloalkylpheny as a group alkyl having a carbon atom number of 1 to 3. The examples for initiating radical polymerization. In this method, a metal of R7 are methyl, ethyl, propyl and isopropyl. Preferred R' complex comprising an 8th group, 9th group, 10th group or 60 is methyl. The term a showing the number of R is 0, 1 or 11th group element in the periodic table as a central metal 2, and a is preferably 0. A bonding position of R7 on the is used as a catalyst. In this atom transfer radical polymer benzene ring is an optional position excluding the bonding ization, it is known that haloalkylphenyl has an excellent positions of Z and Z7. polymerization initiating ability. Further, it is well known as 65 Z7 in Formula (2-3) is preferably a group represented by well that this polymerization is similar to living polymer —C.H. Z' as is the case with Formula (2-1). That is, the ization. That is, the silicon compound of the present inven preferred example of Formula (2-3) is Formula (2-3-4): US 7,256.243 B2 41 42
(2-3-4) (R) (2-4) (R), 3. 5 --().= z*-s--N V R9 Z' in Formula (2-3-4). is a single bond or alkylene which 10 has a carbon atom number of 1 to 8 and in which one Z, Z7, Randa in Formula (2-4) have the same meanings as those of these codes in Formula (2-3), and the bonding —CH2— may be substituted with —O—. positions of Z and R7 on the benzene ring are the same That is, the preferred example of Z7 in Formula (2-1) is positions in Formula (2-3). R and R are independently alkylene which has a carbon atom number of 2 to 10 and in 15 hydrogen, alkyl having a carbon atom number of 1 to 12, which one —CH2— may be substituted with —O—. The cycloalkyl having a carbon atom number of 5 to 10 or aryl examples of such Zare —CH , —CH , —OC.H. , having a carbon atom number of 6 to 10. The examples of —OCH , —CH2OCH , —CH2OCH , R or R other than hydrogen are methyl, ethyl, propyl, —CHOCH - and —CHOCH-. However, the isopropyl, butyl, isobutyl, pentyl, 2-methylbutyl, hexyl, selected range of Z shall not be restricted to them. In 2-methylpentyl, heptyl, 2-methylhexyl, octyl, 2-methylhep Formula (2-3-4), the codes other than Z'have the same tyl, 2-ethylhexyl, decyl, phenyl, cyclopentyl and cyclohexyl. meanings as those of the codes in Formula (2-3), and the Both of R and R may be one of these groups or one may bonding positions of Zand R7 to Z" on the benzene ring are be one of these groups, and the other may be hydrogen. the same as these bonding positions to Z” in Formula (2-3). RandR may be combined with each other to form a ring A photo initiator-transfer agent-terminator polymerization 25 together with N. In this case, the examples of a dithiocar bamate group are N-cyclotrimethylenedithiocarbamate, method is known as a photopolymerization method using a N-cyclotetramethylenedithiocarbamate, N-cyclopentameth dithiocarbamate group as a polymerization initiating group. ylenedithiocarbamate, N-cyclohexamethylenedithiocar In this photo initiator-transfer agent-terminator polymeriza bamate, N-cycloheptamethylenedithiocarbamate and N-cy tion, it is well known that a dithiocarbamate group is 30 clooctamethylenedithiocarbamate. The preferred radically dissociated by virtue of light and that it has an dithiocarbamate groups are N,N-dimethyldithiocarbamate, excellent polymerization initiating ability and sensitizing N,N-diethyldithiocarbamate, N-methyldithiocarbamate and ability. It is well known as well that this photopolymeriza N-ethyldithiocarbamate. N,N-diethyldithiocarbamate is tion is similar to living polymerization. Accordingly, the most preferred. silicon compound of the present invention having a dithio 35 Z7 in Formula (2-4) is preferably a group represented by carbamate group can continue to maintain a living polymer —C.H. Z' as is the case with Formula (2-1). That is, the izability as long as it is irradiated with light, and it has a preferred example of Formula (2-4) is Formula (2-4-3): photopolymerization initiating ability for all radically poly merizable monomers. In particular, it can reveal an excellent living polymerizability to (meth)acrylic acid derivatives. A 40 (2-4-3) dithiocarbamate group has a radiation resistance, a pharma (R'), cological activity Such as a weeding effect, a complex forming ability and a hydrophilicity in addition to the characteristics as a photopolymerization initiating group, -et-z-( = ) z*-s--Ni , and therefore it is possible to efficiently use these charac 45 V teristics. R9 The preferred example of the silicon compound of the present invention having a dithiocarbamate group is a com In Formula (2-4-3), Z'has the same meaning as that of Z' pound represented by Formula (1-4): 50 in Formula (2-3-4), and the codes other than Z'have the same meanings as those of the codes in Formula (2-4). The bonding positions of Zand R to that of Z' on the benzene (1-4) ring are the same as the bond positions thereof to Z” in Formula (2-4). 55 Rolosa O---N-At 3 / : flo2\ flo3y - A 4 Next, a part of the specific examples of the compound isos-o sin-SiR )(R)-A (1-1), the compound (1-2), the compound (1-3) and the A*-(R3)(R2)Si-O O V compound (1-4) among the silicon compounds of the present y O O i invention shall be shown in Tables 2 to 4 using codes shown 4- D3v d2s; 1Ns;-ry1 N O in Table 1. These examples are the examples of cases where A*-(R)(R4)Si ; V No sig YSi(R2)(R)-A 60 in the following Formula (1-1-1), Formula (1-2-1), Formula R - No R1 (1-3-1) and Formula (1-4-1), R' is phenyl: Z' is —CH , C. Hs , —CHo- or —CH-O-CH ; Z is a single bond, —CH2—, —CH - or -CH ; and Z is a single bond, —CH2—, —CH - or a group in which one R", R and R in Formula (1-4) have the same meanings as 65 —CH2— in the above alkylenes is substituted with those of these codes in Formula (1), and A' is a group —COO . The above examples are the preferred examples represented by Formula (2-4): of the silicon compound of the present invention.
US 7,256.243 B2 47 48
-continued (2-1) (5) O R. R1 R R O-ll-O R1 —zi-o-c--x H-(R3)(R2)Si YS 6ss.( Si(R)(R)-H No1 O Si V O M O - D3, D2&; 1Ns;-ry1O Si n O In Formula (2-1), Z' is alkylene having a carbon atom 10 H-(R)(R4)Si Siro No-S1 Ysi(R2)(R)-H number of 2 to 20 or alkenylene having a carbon atom R1 o-1 N O VR1 number of 3 to 8, and optional —CH2— in these alkylene R1 and alkenylene may be substituted with —O : R is hydro R1 gen, alkyl having a carbon atom number of 1 to 20, aryl having a carbon atom number of 6 to 20 or arylalkyl having 15 a carbon atom number of 7 to 20; R is alkyl having a carbon R", RandR in these formulas have the same meanings as atom number of 1 to 20, aryl having a carbon atom number those of these codes in Formula (1). of 6 to 20 or arylalkyl having a carbon atom number of 7 to A method making use of nucleophilic displacement can be 20; and X" is halogen. adopted in order to react the compound (3-1) with the compound (4) to synthesize the compound (5). This method The preferred raw material used in the present invention is described in, for example, J. Am. Chem. Soc., 112 (1990), is a compound (3-1): 1931-. Conditions for selecting a solvent used for this nucleophilic displacement reaction are that it is not reacted with the compound (3-1) and the compound (4) and that it (3-1) is sufficiently dehydrated. The examples of the solvent are 25 tetrahydrofuran, toluene and dimethylforamide. The most preferred solvent is well dehydrated tetrahydrofuran. A preferred use amount of the compound (4) is 3 to 15 times in terms of an equivalent ratio based on the compound (3-1). In this reaction, triethylamine may be used as a catalytic role 30 for allowing the reaction to quickly proceed. When using triethylamine, an amount thereof is preferably 3 to 15 times in terms of an equivalent ratio based on the compound (3-1). The reaction temperature shall not specifically be restricted as long as side reactions do not take place at the 35 same time and a quantitative nucleophilic reaction goes on. In Formula (3-1), R' has the same meaning as that of R' in In charging the raw materials, however, the reaction may be Formula (1), and M is a monovalent alkali metal atom. The carried out under a low temperature condition, for example, preferred examples of the alkali metal are sodium and in an ice bath. The Subsequent reaction may be carried out potassium. The most preferred example is sodium. under a room temperature condition or a heating condition. The compound (3-1) can be obtained by hydrolyzing and 40 To be specific, the reaction temperature falls in a range of 0 condensing a silane compound having a trifunctional hydro to 150° C., more preferably in a range of 0 to 50° C. The ly Zable group in the presence of an organic solvent, water reaction time shall not specifically be restricted as long as it and alkali metal hydroxide. The compound (3-1) can be is time enough for a quantitative nucleophilic reaction to go produced for short time at a high yield by the above method on. Usually, the intended silicon compound can be obtained (refer to, for example, WO03/024870 pamphlet). In produc 45 in 1 to 15 hours. ing the compound (3-1), the compound (3-1) in which eight Further, the compound (3-1) has —ONa as a reactive R's are constituted from at least two different groups can be group, and therefore hydrogen chloride is not produced obtained by using at least two silane compounds having a when chlorosilanes are used for synthetic reaction of the trifunctional hydrolyzable group. Since the compound (3-1) derivatives. Accordingly, the reaction operation can be shows a high reactivity, use of this compound as a raw 50 material makes it possible to readily synthesize the deriva facilitated, and the reaction can completely carried out. tive thereof at a high yield. For example, an Si-H func Another preferred raw material used in the present inven tional silsesquioxane derivative can be produced by reacting tion is a compound (3-2): the compound (3-1) with Si-H functional diorganochlo rosilane. 55 (3-2) The Si-H functional diorganochlorosilane is represented by Formula (4). The preferred example of Formula (4) is R filo.- O ' dimethylchlorosilane. A compound (5) is obtained by react V/Ns.Si-O.J. 1 Gs n ing the compound (3-1) with the compound (4): HO s OH 60 V O HO Si n (4) sis or No. 1" R1 O-Isin- VRI 65 US 7,256.243 B2 49 50 R" in Formula (3-2) has the same meaning as that of R' in apparatus and the form of the product or the by-products, Formula (1). Such compound is readily obtained by reacting and therefore the range of the above reaction time does not the compound (3-1) with an acid. In this case, an organic mean to restrict the present invention. Solvent can be used, if necessary, in reacting with the acid. The compound (5) can be synthesized by reacting the Capable of being used is a method in which the compound 5 compound (3-2) with the compound (4) making use of (3-1) is mixed with the organic solvent and in which the acid nucleophilic displacement as is the case with the compound is dropwise added to this mixture to thereby allow the (3-1). A preferred use amount of the compound (4) is 3 to 15 reaction to proceed. times in terms of an equivalent ratio based on the compound (3-2) when it is reacted with the whole Si-OH (silanol) The organic solvent shall not specifically be restricted as 10 groups of the compound (3-2). In this reaction, hydrogen of long as it does not hinder the progress of the reaction. It silanol is reacted with chlorine of chlorosilane to thereby includes, for example, aliphatic hydrocarbons such as hex generate hydrogen chloride, and therefore this hydrogen ane and heptane, aromatic hydrocarbons such as benzene, chloride has to be removed from the reaction system. A toluene and xylene, ethers such as diethyl ether, tetrahydro method for removing hydrogen chloride shall not be furan and dioxane, halogenated hydrocarbons such as meth 15 restricted, and triethylamine is most preferably used. A ylene chloride and carbon tetrachloride and acetates Such as preferred use amount of triethylamine is 3 to 15 times in methyl acetate, ethyl acetate and butyl acetate, and tetrahy terms of an equivalent ratio based on the compound (3-2). A drofuran and ethyl acetate are preferred. preferred solvent used in the reaction is the same as those in A preferred proportion of the compound (3-1) mixed with the reaction using the compound (3-1). The preferred reac the organic solvent is 0.05 to 50% by weight based on the tion temperature is temperature at which side reactions do weight of the solvent. If it is less than 50% by weight, a not take place at the same time and a quantitative nucleo concentration of the by-produced salts can be reduced, and philic reaction can be allowed to go on. In charging the raw it is advantageous for allowing the reaction to proceed. On materials, the reaction is most preferably carried out under the other hand, if it is 0.05% by weight or more, the volume a low temperature condition, for example, in an ice bath, and efficiency is good, and it is preferred in terms of the cost. The 25 then it may be carried out at room temperature. The reaction more preferred proportion is 1 to 10% by weight. time shall not specifically be restricted as long as it is time The acid used in the above reaction shall not specifically enough for allowing a quantitative nucleophilic reaction to be restricted as long as it is a proton donor (Brinsted acid) go on. Usually, the intended silicon compound can be and is a compound which can be reacted with the compound obtained in 1 to 15 hours. (3-1) to obtain the compound (3-2). Capable of being given 30 In synthesizing the silicon compound of the present as the examples thereof are, for example, cyanic acid, invention, a hydrosilylation reaction method using the com isocyanic acid, thiocyanic acid, isothiocyanic acid, nitric pound (5) described above is preferably used. That is, it is acid, nitrous acid, Sulfuric acid, Sulfurous acid, carbonic the reaction of the compound (5) with a compound (6) in the acid, hydrochloric acid, hydrobromic acid, phosphoric acid, presence of a transition metal catalyst: 35 boric acid, formic acid, acetic acid, propionic acid, butyric CH=CH-Z’ OH (6) acid, Stearic acid, oxalic acid, malonic acid, Succinic acid, adipic acid, acrylic acid, methacrylic acid, oleic acid, maleic Z in Formula (6) is a single bond or alkylene having a acid, chloroformic acid, chloroacetic acid, trifluoroacetic carbon atom number of 1 to 18 or alkenylene having a acid, cyclohexanecarboxylic acid, pivalic acid, benzoic acid, 40 carbon atom number of 2 to 6, and optional —CH2— in toluic acid, naphthoic acid, phthalic acid, cinnamic acid, these alkylene and alkenylene may be substituted with nicotinic acid, thiophenecarboxylic acid, S-thioacetic acid, —O—. dithioacetic acid, S-thiobenzoic acid, dithiobenzoic acid, thiocarbonic acid, trithiocarbonic acid, Xanthic acid, meth The examples of the transition metal catalyst used are anesulfonic acid, benzenesulfonic acid, p-toluenesulfonic platinum, rhodium, iridium, ruthenium, palladium, molyb 45 denum, iron, cobalt, nickel and manganese. Among them, a acid, phenylphosphonic acid and diphenylphosphinic acid. It platinum catalyst is more preferred. The above catalysts can is preferably an organic acid, more preferably a carboxylic be used in the form of a homogeneous catalyst in which they acid and most preferably acetic acid. are dissolved in a solvent or a solid catalyst in which they are In respect to a use proportion when using the above acids, carried on carbon or silica. They may be used in a form in use of 4 times mole or more based on the compound (3-1) 50 which phosphine, amine and potassium acetate are allowed makes it possible to complete the reaction. If the above use to be coexistent. A preferred use amount of the transition proportion falls in the above range, undesirable side reac metal catalyst is 1x10 to 1x10 mole per mole of an tions are less likely to be brought about, and an amount of Si-H group in the compound (5) in terms of a transition a neutralizing agent used at an after-treating step is Small, so metal catalyst atom. that it is efficient. The above use proportion is preferably 4 55 A use amount of the compound (6) is preferably 1 to 5 times mole or more and 10 times mole or less, more times in terms of an equivalent ratio based on an Si-H preferably 4 times mole or more and 5 times mole or less group in the compound (5). Hydrosilylation reaction is based on the compound. reaction which almost quantitatively proceeds, and therefore The reaction temperature may be room temperature, and it is not meaningful so much to increase the above equivalent heating may be carried out, if necessary, in order to accel 60 ratio. However, the effect of shortening the reaction time can erate the reaction. Or, cooling may be carried out, if neces be expected, and therefore an adverse effect brought about sary, in order to control heat generated by the reaction or by using the compound (6) in a large amount is only the cost undesirable reactions. efficiency. On the other hand, when intending to allow a part The reaction time is 0.5 to 8 hours. In general, however, of the Si-H group to remain as it remains unreacted, it is the reaction time is influenced by, in addition to the reac 65 enough to make the equivalent ratio described above lower tivity of the raw material, the raw material concentration, the than 1. Thus, a compound represented by Formula (7) is reaction temperature, the shape (stirring efficiency) of the obtained: US 7,256.243 B2 52
(7) R RI RI O R HO-Z2-CH-H-(R)( (R)(R2)Si Sin-si N.'s s: 1 O O y O HO-Z2-CH,-(R)(R)s. 1 O sy or in s O Si R o-1R ind R1
15 R", R and R in Formula (7) have the same meanings as derived into the compound (7) having a hydroxyl group at those of the respective codes in Formula (1), and Z has the room temperature or under a slightly heating (40° C.) same meaning as that of Z in Formula (6). condition by alcoholysis using large excess methanol.
(6-T) CH=CH-Z2-O-TMS (7-T) i R1 RI \ -O-- e O ... 1 e -SS Si(R2)(R)-CH-Z2-O-TMS isoslo SinO O V V O Si Ns:-1 O Sir O SiSt. YSi(R2)(R)-CH-Z2-O-TMS R -1R1 No RI R1
35 A preferred reaction temperature in the hydrosilylation Z in the above formulas has the same meaning as that of Zf reaction is not higher than a boiling point of the solvent used. in Formula (6): Z, R, R and R have the same meanings The compound (6) is a compound having a polymerizable as those of these codes in Formula (7); and TMS represents unsaturated bond. The preferred reaction temperature for a trimethylsilyl group. preventing this compound from being spontaneously poly 40 Then, the compound (7) is reacted with a compound (8) merized during the hydrosilylation reaction is 20 to 80° C. in which halogen is bonded to carbon of an a position, A polymerization inhibitor Such as phenol derivatives, phe whereby the compound (1-1) is obtained: nothiazine derivatives or N-nitrosophenylamine salt deriva tives may be used for the purpose of inhibiting the above 45 (8) polymerization reaction. The most preferred polymerization O R. inhibitor is 4-tert-butylpyrocatechol. A preferred use amount thereof is 1 to 100,000 ppm based the whole weight of the reaction liquid. The more preferred range of the use amount x-c--x thereof is 100 to 20,000 ppm. An organic solvent used for the above hydrosilylation 50 reaction shall not specifically be restricted as long as it R, R and X" in Formula (8) have the same meanings as readily dissolves the raw materials without reacting with those of these codes in Formula (2-1), and X is halogen. The them. examples of this halogen are chlorine, bromine and iodine, The preferred examples of the organic solvent are ali 55 and chlorine and bromine are preferred. X may be the same phatic hydrocarbons (examples: hexane and heptane), aro as or different from X. matic hydrocarbons (examples: toluene and Xylene) and Hydrogen chloride by-produced in the above reaction cyclic ethers (examples: tetrahydrofuran and dioxane). Con induces side reactions such as dehydration and addition to a sidering a solubility of the compound (5), toluene is most double bond part, and therefore the reaction is carried out in preferred. Alcohols such as 2-propanol may be added for the 60 the coexistence of an organic base in order to remove it. The purpose of controlling the activity of the catalyst. examples of the organic base are pyridine, dimethylaniline, The compound (7) can be produced as well by the triethylamine and tetramethylurea. Other organic bases may following method. First, the compound (5) and a compound be used as long as they can inhibit the side reactions and (6-T) having an alkenyl group protected by a trimethylsilyl allow the reaction to quickly proceed. The most preferred group are Subjected to hydrosilylation reaction in toluene in 65 example of the organic base is triethylamine. This reaction the presence of a platinum-divinyltetramethylsiloxane com is a nucleophilic displacement reaction which proceeds plex to thereby produce a compound (7-T). Then, it is quantitatively, and a use amount of the compound (8) is US 7,256.243 B2 53 54 preferably 1 to 10 times in terms of an equivalent ratio based Formula (1-1); and X', RandR have the same meanings on the compound (7). An increase in a use amount of the as those of these codes in Formula (2-1). compound (8) makes it possible to react the whole com The reaction of the compound (6) with the compound (8) pound (7) and makes it possible to shorten the reaction time. can be carried out in the same manner as that of the reaction Usually, the above reaction is carried out in the environ of the compound (7) with the compound (8). The hydrosi ment of inert gas such as argon gas and nitrogen gas in the lylation reaction of the compound (2-1-2) with the com presence of a dried organic solvent which is inert to the raw pound (4) can be carried out in the same manner as that of materials. The examples of the organic solvent are cyclic the reaction of the compound (6) with the compound (5). ethers (THF, dioxane and the like), aromatic hydrocarbons 10 The reaction of the compound (2-1-3) with the compound (toluene, Xylene and the like), halogenated hydrocarbons (3-1) or the compound (3-2) can be carried out in the same (methylene chloride, chloroform and the like) and carbon manner as that of the reaction of the compound (4) with the tetrachloride. The preferred example of the organic solvent compound (3-1) or the compound (3-2). is methylene chloride. The reaction temperature shall not In the following explanations, a general term of “impu specifically be restricted. However, the above reaction 15 quickly goes on while generating heat, and therefore usually rities' shall be given to the unreacted raw material com it is carried out preferably under a low temperature condi pounds and the solvent. If a distillation method is applied in tion. The preferred reaction temperature is 100° C. or lower, order to remove the impurities, the liquid is maintained and the most preferred reaction temperature is 35° C. or under a high temperature condition for long time, and lower. As a matter of fact, the reaction may be carried out therefore the intended compound is likely to be decom while irregularly controlling the reaction temperature. For posed. Accordingly, refining is preferably carried out by example, the reaction may be carried out while cooling the reprecipitation operation in order to efficiently remove the reaction system using a dry ice-methanol bath or an ice bath impurities without damaging a purity of the compound in an initial stage, and then the temperature may be elevated (1-1). This refining method is carried out in the following to the vicinity of room temperature to continue the reaction. 25 The reaction time shall not specifically be restricted, and manner. First, the reaction liquid is dissolved in a solvent usually the intended silicon compound can be obtained in 1 dissolving both of the compound (1-1) and the impurities. In to 10 hours. this case, a preferred concentration of the compound (1-1) is, roughly speaking, 1 to 15% by weight. Next, a solvent which The compound (1-1) can be produced as well by a method 30 does not dissolve the compound (1-1) but dissolve the in which a reaction step of the compound (6) and the impurities, a so-called precipitant is added to the above compound (8) is carried out in advance. First, the compound solution to precipitate only the compound (1-1). A preferred (6) is reacted with the compound (8) to synthesize a com use amount of the precipitant is 20 to 50 times based on the pound represented by Formula (2-1-2): weight of the solvent used for dissolving both of the com 35 pound (1-1) and the impurities. The above use range is a rough standard, and as is the case with the foregoing (2-1-2) concentration rage of the compound (1-1), it does not O R4 necessarily have to fall in the above range. 40 The preferred solvent used for dissolving the compound ch=CH-7-0---x (1-1) is a solvent having a large dissolving power and a relatively low boiling point. The preferred precipitant is a Z in Formula (2-1-2) has the same meaning as that of Z in solvent which is compatible with the solvent for dissolving Formula (6), and X', RandR have the same meanings as 45 the compound (1-1) and does not dissolve the compound those of these codes in Formula (2-1). (1-1) at all and which dissolves only the impurities and has a relatively low boiling point. The example of the preferred Then, the compound (2-1-2) and the compound (4) are precipitant is lower alcohols. The particularly preferred Subjected to hydrosilylation reaction to synthesize a com precipitant is methanol. A repeating frequency of the repre pound represented by Formula (2-1-3), and it is further 50 cipitation operation is advisably raised in order to further reacted with the compound (3-1) or the compound (3-2) to elevate the refining degree. synthesize the compound (1-1). A method for synthesizing A column chromatographic method is preferably applied the compound (2-1-3) is described in, for example, Macro in order to further refine the compound (1-1) after removing mol. Rapid Commu.., 23 (2002), 612-. 55 the polymerizable unreacted products. An adsorbent used in this case is silica gel and the like. A preferred developing Solvent is hexane, cyclohexane, toluene, chloroform, ethyl acetate and acetone. More preferred developing solvent is a (2-1-3) mixed solvent of hexane and ethyl acetate. A mixing pro R2 O R 60 portion of the solvents shall not specifically be restricted, and it is controlled so that a migration rate (Rf value) of the ci-s-ch-z-o-c-f-x intended compound to the developing solvent falls in a range of 0.1 to 0.7. 65 Next, a production process of the compound (1-2) out of Z in Formula (2-1-3) has the same meaning as that of Z in the silicon compounds of the present invention shall be Formula (6); R and R have the same meanings as those in explained: US 7,256.243 B2 56 this alkylene may be substituted with —O— or COO : R. X and a have the same meanings as those of these codes in Formula (2-2); a bonding position of SO, X on the benzene ring is an ortho position, a meta position or a para position to a bonding position of halogenated Z, and a bonding position of R is an optional position excluding the respective bonding positions of Z' and SOX ; and R' and R have the same meanings as those of these codes in Formula (1-2). 10 Then, the compound (2-2-3) is reacted with the compound (3-1) or the compound (3-2) each described above to syn thesize the silicon compound represented by Formula (1-2). The hydrosilylation reaction of the compound represented by Formula (4) with the compound represented by Formula R", R and R in Formula (1-2) have the same meanings as 15 (2-2-2) can be carried out in the same manner as that of the those of these codes in Formula (1), and A is a group reaction of the compound (5) with the compound (6). The represented by Formula (2-2): reaction of the compound (2-2-3) with the compound (3-1) or the compound (3-2) can be carried out in the same manner as that of the reaction of the compound (4) with the (2-2) compound (3-1) or the compound (3-2). (R), The refining method by reprecipitation operation and/or the column chromatographic method each described above can be used for refining the compound (1-2) contained in the reaction mixture. --(). 25 Next, the production processes of the compound (1-3) and O the compound (1-4) out of the silicon compounds of the present invention shall be explained: In Formula (2-2), Z is alkylene having a carbon atom number of 2 to 10, and optional —CH2— in this alkylene 30 (1-3) may be substituted 15 with —O— or -COO : R is alkyl RI RI having a carbon atom number of 1 to 3; a is an integer of 0 to 2: X is halogen; and a bonding position of -SOX on the benzene ring is an ortho position, a meta position or a para position to a bonding position of Z, and a bonding 35 position of R is an optional position excluding the respec tive bonding positions of Z and -SO.X . First, a compound represented by Formula (4) and a compound represented by Formula (2-2-2) are subjected to hydrosilylation reaction to synthesize a compound repre 40 sented by Formula (2-2-3):
(4) R2 45 c-i-
(2-2-2) (R6) 50 R", RandR in the above formulas have the same meanings c-en-z-()= \, x: as those of these codes in Formula (1); and A is a group 55 represented by Formula (2-3); and A' is a group represented O by Formula (2-4): (2-2-3) (R), (2-3) (R), c----(y 60 R3 ->- O
65 In the above formulas, Z is a single bond or alkylene having In Formula (2-3), Z is alkylene which has a carbon atom a carbon atom number of 1 to 8, and optional —CH2— in number of 1 to 3 and in which optional —CH2— may be US 7,256.243 B2 57 58 substituted with —O : Z” is alkylene which has a carbon The silicon compound represented by Formula (1-4) can atom number of 2 to 10 and in which optional —CH2—may be obtained by reacting the compound (1-3) obtained at the be substituted with —O , —COO or —OCO : R is hydrosilylation reaction step described above with a dithio alkyl having a carbon atom number of 1 to 3; a is an integer carbamic acid metal salt represented by Formula (9): of 0 to 2: X is halogen; and a bonding position of Z on the 5 benzene ring is a meta position or a para position to a bonding position of Z’, and a bonding position of R is an (9) optional position excluding the respective bonding positions S R8 / of Z and Z7; M S-C-N 10 V (R) (2-4) 3.
15 RandR in Formula (9) have the same meanings as those --().—7 z*-s--N of these codes in Formula (2-4); M' is a metal element of the V 1st or the 2nd group in the periodic table; and p is the same R9 value as a valence of M'. The examples of M" are Li, Na, K, Cu, Mg, Ca and Zn, and the preferred examples of M" are Na and K. In Formula (2-4), R and Rare independently alkyl having a carbon atom number of 1 to 12, cycloalkyl having a carbon The reaction of the compound (1-3) with the compound atom number of 5 to 10 or aryl having a carbonatom number (9) is a quantitative nucleophilic displacement reaction, and of 6 to 10, and R and R may be combined with each other side reactions do not take place. However, a preferred use to form a ring together with N; Z is alkylene which has a 25 amount of dithiocarbamate is 1 to 5 times in terms of an carbon atom number of 1 to 3 and in which optional equivalent ratio based on a halogen content in the compound —CH2— may be substituted with —O : Z” is alkylene (1-3). Use of a large amount of this salt makes it possible to which has a carbon atom number of 2 to 10 and in which shorten the reaction time. The reaction is usually carried out optional —CH2— may be substituted with —O—, in an inert gas atmosphere Such as nitrogen in a dried organic —COO or —OCO : R is alkyl having a carbon atom 30 solvent which is inert to the raw materials. The examples of number of 1 to 3; a is an integer of 0 to 2; and a bonding position of Zion the benzene ring is a metaposition or a para the organic solvent are lower alcohols (example: methanol), position to a bonding position of Z’, and a bonding position cyclic ethers (examples: tetrahydrofuran and dioxane) and of R is an optional position excluding the respective bond aromatic hydrocarbons (examples: toluene and Xylene). The ing positions of Z and Z'. 35 preferred examples of the organic solvent are tetrahydrofu A preferred production process for the compound (1-3) is ran and methanol. The preferred reaction temperature is the hydrosilylation reaction of a compound represented by 120° C. or lower considering the possibility that dithiocar Formula (2-3-2) with the compound (5) obtained by the bamate is thermally decomposed. The more preferred tem reaction of the compound (3-1) or the compound (3-2) with perature is 100° C. or lower. The reaction time shall not the compound (4): 40 specifically be restricted, and the intended silicon compound can be obtained usually in 1 to 10 hours. Capable of being used, if necessary, for the reaction is a phase transfer catalyst (2-3-2) (R), Such as benzyltrimethylammonium chloride, tetramethylam monium chloride, tetrabutylammonium bromide, triocty 45 lammonium chloride, dioctylmethylammonium chloride, triethylamine or dimethylaniline. The compound (1-4) contained in the reaction mixture is refined by a refining method carried out by the reprecipita In Formula (2-3-2), Z is a single bond or alkylene which has 50 tion operation and/or the column chromatographic method a carbon atom number of 1 to 8 and in which optional each described above. The reaction of dithiocarbamate with —CH2— may be substituted with —O , —COO or the compound (1-3) and refining of the compound (1-4) have —OCO : Z, R. X and a have the same meanings as to be carried out under a fluorescent lump in which a UV ray those of these codes in Formula (2-3); and a bonding 55 is cut and in a draft in which a UV-cut film is applied. The position of Z on the benzene ring is a metaposition or a para compound (1-4) has dithiocarbamate which is a photosen position to a bonding position of Z, and a bonding position sitive group, and therefore it has to be stored in a light of R is an optional position excluding the respective bond shielded vessel charged with inert gas such as nitrogen and ing positions of Z and Z. argon in a cold and dark place under non-aqueous environ The hydrosilylation reaction of the compound (5) with the 60 ment. compound (2-3-2) can be carried out in the same manner as that of the reaction of the compound (5) with the compound The compound (1-4) can be obtained as well by a process (6). in which a reacting step of a dithiocarbamic acid metal salt The refining method by reprecipitation operation and/or with a halogenated alkyl group is carried out in advance. the column chromatographic method each described above 65 This production process is a process in which the compound can be used for refining the compound (1-3) contained in the (2-3-2) is first reacted with the compound (9) to prepare a reaction mixture. compound represented by Formula (2-4-2): US 7,256.243 B2 59 60 Next, an addition-polymerizable monomer which can initiate polymerization using the compound (1) shall be (2-4-2) explained. This addition-polymerizable monomer is a mono R", merhaving at least one addition-polymerizable double bond. One of the examples of a monomer having one addition polymerizable double bond is a (meth)acrylic acid deriva c-en-z-()= z*-s--Ni , tive. The specific examples thereof are (meth)acrylic acid, V methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl R9 (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth) 10 acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, In Formula (2-4-2), Z is a single bond or alkylene which n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl has a carbon atom number of 1 to 8 and in which optional (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acry —CH2— may be substituted with —O , —COO or late, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, —OCO-; the other codes have the same meanings as those decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth) of the codes in Formula (2-4); and a bonding position of Z. 15 acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, on the benzene ring is a meta position or a para position to 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth) a bonding position of Z, and a bonding position of R is an acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl optional position excluding the respective bonding positions (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Stearyl of Z and Z. (meth)acrylate, glycidyl (meth)acrylate, 3-ethyl-3-(meth) This reaction itself is fundamentally the same as the acryloyloxymethyloxetane, 2-(meth)acryloyloxyethylisocy reaction of the compound (1-3) with the compound (9) each anate, 2-aminoethyl (meth)acrylate, 2-(2-bromopropanoyly described above, and it can be carried out in the same loxy)ethyl (meth)acrylate, 2-(2-bromoisobutyryloxy)ethyl manner as in the case of the above reaction. However, the (meth)acrylate, 1-(meth)acryloxy-2-phenyl-2-(2.2.6.6-tet same caution as in the reaction of the compound (5) with the ramethyl-1-piperidinyloxy)ethane, (1-(4-(4-(meth)acry compound (2-3-2) in the production process described above 25 loxy)ethoxyethyl)phenylethoxy)piperidine, Y-(methacryloy is required in terms of handling the compound having a loxypropyl)trimethoxysilane, 3-(3,5,7,9,11,13,15 polymerizable group. That is, the reaction temperature has to heptaethylpentacyclo-9.5.1.1.1.17 octasiloxane-1- be controlled to a considerably low temperature of 20 to 80° yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisobutyl C., and a polymerization inhibitor has to be used. Further, a pentacyclo[9.5.1.1.1.17 octasiloxane-1-yl)propyl UV ray has to be cut off as much as possible not only in the 30 (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo reaction and the refining step but also in storing the product. 9.5.1.1.1.17'-octasiloxane-1-yl)propyl (meth)acry The compound (1-4) can be obtained by the hydrosilylation late, 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo reaction of the compound (5) with the compound (2-4-2) 9.5.1.1.1.17'-octasiloxane-1-yl)propyl (meth) each described above. This hydrosilylation reaction can be acrylate, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo carried out in the same manner as that of the reaction of the 35 9.5.1.1.1.17'-octasiloxane-1-yl)propyl (meth) compound (5) with the compound (2-3-2). acrylate, 3-(3,5,7,9,11,13,15-heptaethylpentacyclo The compound (1-3) can be produced as well by a 9.5.1.1.1.17 octasiloxane-1-yloxy)dimethylsilyl production process in which reaction using the compound propyl (meth)acrylate, 3-(3,5,7,9,11,13,15 (3-1) or the compound (3-2) is a final reaction step. First, the heptaisobutylpentacyclo-9.5.1.1.1.17 octasiloxane compound (4) and the compound (2-3-2) are subjected to 40 1-yloxy)dimethylsilylpropyl (meth)acrylate, 3-(3,5,7,9,11, hydrosilylation reaction to produce a compound represented 13,15-heptaisooctylpentacyclo-9.5.1.1.1". 17' by Formula (2-3-3): octasiloxane-1-yloxy)dimethylsilylpropyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-9. 5.1.1.1.17 octasiloxane-1-yloxy)dimethylsilylpro (2-3-3) 45 pyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaphenylpenta (R'), cyclo-9.5.1.1.1.17 octasiloxane-1-yloxy)dimethyl silylpropyl (meth)acrylate, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl 50 (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, trifluorom In Formula (2-3-3), R and Rhave the same meanings as ethyl (meth)acrylate, diperfluoromethylmethyl (meth)acry those of these codes in Formula (4), and the other codes have late, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acry the same meanings as those of these codes in Formula late, 2-perfluorohexylethyl (meth)acrylate, (2-3-2). The bonding positions of Zand R7 on the benzene 55 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexade ring are the same as the bond positions thereof in Formula cylethyl (meth)acrylate and 2-(meth)acryloyloxyethylphos (2-3-2). phorylcholine. Then, the compound (2-3-3) is reacted with the compound Another example of the monomer having one addition (3-1) or the compound (3-2) to produce the compound (1-3). polymerizable double bond is a styrene base monomer. The The hydrosilylation reaction of the compound (4) with the 60 specific examples thereof are styrene, vinyltoluene, C.-me compound (2-3-2) can be carried out in the same manner as thylstyrene, p-chlorostyrene, p-chloromethylstyrene, that of the hydrosilylation reaction of the compound (5) with m-chloromethylstyrene, o-aminostyrene, p-styrenechloro the compound (2-3-2). The reaction of the compound (2-3-3) Sulfonic acid, styrenesulfonic acid and salts thereof, with the compound (3-1) or the compound (3-2) can be vinylphenylmethyl dithiocarbamate, 2-(2-bromopropanony carried out in the same manner as that of the reaction of the 65 loxy)styrene, 2-(2-bromo-isobutyryloxy)styrene, 1-(2-((4- compound (4) with the compound (3-1) or the compound vinylphenyl)methoxy)-1-phenylethoxy)-2.2.6.6-tetram (3-2). ethyl-piperidine, 1-(4-vinylphenyl)-3,5,7,9,11,13,15 US 7,256.243 B2 61 62 heptaethylpentacyclo9.5.1.1.1.17'-octasiloxane, (meth)acryloxypolyethoxybisphenol A, 1.3-bis(hydroxy 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutylpentacyclo ethyl) 5,5-dimethylhydantoin, 3-methylpentanediol 9.5.1.1.1.17'-octasiloxane, 1-(4-vinylphenyl)-3.5, di (meth)acrylate, di(meth)acrylates of hydroxypivalic acid 7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1.1.17'- ester neopentylglycol derivatives and bis(meth)acryloylox octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15 ypropyltetramethyldisiloxane. Further, given as well are heptacyclopentylpentacyclo[9.5.1.1.1.17'- macromonomers which have two polymerizable double octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15 bonds in a molecule and in which a principal chain is a heptaphenylpentacyclo[9.5.1.1.1.17'-octasiloxane, macromer of Styrene, (meth)acrylic acid ester, diorganosi 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1.1". loxane or alkylene glycol. 17 octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15 10 The examples of a monomer having three or more addi heptaisobutylpentacyclo[9.5.1.1.1.17'-octasiloxane tion-polymerizable double bonds are trimethylolpropane tri 1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisooctylpenta (meth)acrylate, pentaerythritol tri(meth)acrylate, pen cyclo[9.5.1.1.1.17'-octasiloxane-1-yl)ethylstyrene, taerythritol tetra(meth)acrylate, dipentaerythritol 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo9.5.1. monohydroxypenta(meth)acrylate, tris(2-hydroxyethyliso 1.1.17'-octasiloxane-1-yl)ethylstyrene, 3-(3.5.7.9, 15 cyanate) tri(meth)acrylate, tris(diethylene glycol)trimelate 11,13,15-heptaphenylpentacyclo[9.5.1.1.1.17'-octa tri(meth)acrylate, 3,7,14-tris(((meth)acryloyloxypropyl) siloxane-1-yl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethyl dimethylsiloxy) 1,3,5,7,9,11,14-heptaethyltricyclo pentacyclo[9.5.1.1.1.17 octasiloxane-1-yloxy) 7.3.3.1'']heptasiloxane, 3,7,14-tris(((meth)acryloylox dimethylsilylethylstyrene, 3-((3,5,7,9,11,13,15 ypropyl)dimethylsiloxy)-1,3,5,7,9,11,14 heptaisobutylpentacyclo-9.5.1.1.1.17 octasiloxane heptaisobutyltricyclo[7.3.3.1'-heptasiloxane, 3,7,14-tris 1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15 (((meth)acryloyloxy-propyl)dimethylsiloxy)-1,3,5,7,9,11, heptaisooctylpentacyclo-9.5.1.1.1.17 octasiloxane 14-heptaisooctyltricyclo[7.3.3.1']heptasiloxane, 3.7, 14 1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15 tris(((meth)acryloyloxypropyl)dimethylsiloxy)-1,3,5,7,9. heptacyclopentylpentacyclo[9.5.1.1.1.17'- 11,14-heptacyclopentyl-tricyclo[7.3.3.1']heptasiloxane, octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene and 3-((3. 25 3,7,14-tris(((meth)acryloyloxypropyl)dimethylsiloxy)-1,3, 5,7,9,11,13,15-heptaphenylpentacyclo-9.5.1.1.1.17 5,7,9,11,14-heptaphenyltricyclo[7.3.3.1'-heptasiloxane, 13 octasiloxane-1-yloxy)dimethylsilylethylstyrene. octakis(3-(meth)acryloyloxypropyldimethylsiloxy)octasils The other examples of the monomer having one addition esquioxane and octakis(3-(meth)acryloyloxypropyl)octa polymerizable double bond are fluorine-containing vinyl silsesquioxane. Further, given as well are macromonomers OOCS (perfluoroethylene, perfluoropropylene, 30 which have three or more polymerizable double bonds in a vinylidene fluoride and the like), silicon-containing vinyl molecule and in which a principal chain is a macromer of base monomers (vinyltrimethoxysilane, vinyltriethoxysilane styrene, (meth)acrylic acid ester, diorganosiloxane or alky and the like), maleic anhydride, maleic acid, monoalkyl lene glycol. esters and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid, male 35 The monomers described above may be used alone or a imide base monomers (maleimide, methylmaleimide, ethyl plurality thereof may be copolymerized. When copolymer maleimide, propylmaleimide, butylmaleimide, hexylmale ized, they may be random-copolymerized or block-copoly imide, octylmaleimide, dodecylmaleimide, merized. The preferred monomers used in the present inven Stearylmaleimide, phenylmaleimide and cyclohexylmaleim tion are the (meth)acrylic acid derivatives and the styrene ide), monomers having a nitrile group (acrylonitrile, meth 40 derivatives. The more preferred monomers are the (meth) acrylonitrile and the like), monomers having an amide group acrylic acid derivatives. The plural (meth)acrylic acid (acrylamide, methacrylamide and the like), vinyl ester base derivatives may be copolymerized, and the plural styrene monomers (vinyl acetate, vinyl propionate, vinyl pivalate, derivatives may be copolymerized. At least one (meth) vinyl benzoate, vinyl cinnamate and the like), olefins (eth acrylic acid derivative may be copolymerized with at least ylene, propylene and the like), conjugated diene base mono 45 one styrene derivative. mers (butadiene, isoprene and the like), halogenated vinyls Next, a method for subjecting an addition-polymerizable (vinyl chloride and the like), halogenated vinylidenes (vi monomer to atom transfer radical polymerization using the nylidene chloride and the like), halogenated allyls (allyl compound (1-1) or the compound (1-2) or the compound chloride and the like), allyl alcohol, vinylpyrrolidone, (1-3) as an initiator and using a transition metal complex as vinylpyridine, N-vinylcarbazole, methyl vinyl ketone and 50 a catalyst shall be explained. An atom transfer radical vinylisocyanate. Further, given as well are macromonomers polymerization method in the present invention is one of which have one polymerizable double bond in a molecule living radical polymerization methods. The examples of and in which a principal chain is a macromer of styrene, documents in which the living radical polymerization (meth)acrylic acid ester, diorganosiloxane or alkylene gly method is described are J. Am. Chem. Soc., 117 (1995), col. 55 5614 Macromolecules, 28 (1995), 7901- and Science, The examples of a monomer having two addition-poly 272 (1996), 866-. merizable double bonds are divinylbenzene and di(meth) The preferred examples of a transition metal complex acrylate base monomers. The examples of the di(meth) used as a polymerizing catalyst are metal complexes in acrylate base monomers are 1,3-butanediol di(meth) which a 7th, 8th, 9th, 10th or 11th group element in the acrylate, 1,4-butanediol di(meth)acrylate, 1.6-hexanediol 60 periodic table is used as central metal. The more preferred di (meth)acrylate, polyethylene glycol di(meth)acrylate, catalysts are a complex of Zero-valent copper, a complex of diethylene glycol di(meth)acrylate, neopentyl glycol monovalent copper, a complex of divalent ruthenium, a di (meth)acrylate, triethylene glycol di(meth)acrylate, tripro complex of divalent iron and a complex of divalent nickel. pylene glycol di(meth)acrylate, hydroxypivalic acid ester Among them, the complexes of copper are preferred. The neopentyl glycol di(meth)acrylate, trimethylolpropane 65 examples of a monovalent copper compound are cuprous di(meth)acrylate, bis(meth)acryloyloxyethoxybisphenol chloride, cuprous bromide, cuprous iodide, cuprous cyanide, A, bis(meth)acryloyloxyethoxytetrabromobisphenol A, bis cuprous oxide and cuprous perchlorate. When using the US 7,256.243 B2 63 64 copper compounds, 2,2'-bipyridyl or derivatives thereof, The polymerization temperature falls in a range of 0 to 200° 1,10-phenanthroline or derivatives thereof, pyridylmethane C., and the preferred polymerization temperature falls in a imines (N-(n-propyl)-2-pyridylmethaneimine and the like), range of room temperature to 150° C. polyamines (tetramethylethylenediamine, pentamethyldi When using a compound (1-1-2) as an initiator, a polymer ethylene-triamine, hexamethyltris(2-aminoethyl)amine and obtained by the method described above is represented by the like) or polycyclic alkaloid such as L-(-)-sparteine are Formula (P-1). In the following explanations, the polymer added as a ligand in order to enhance the catalyst activity. A represented by Formula (P-1) is shown as the polymer (P-1): tristriphenylphosphine complex (RuCl(PPh.),) of divalent ruthenium chloride is also suited as the catalyst. When the ruthenium compound is used as the catalyst, aluminum 10 (1-1-2) alkoxides are added as an activating agent. The examples of R11 the Suited catalysts other than the above compounds are a R Eo R11 bistriphenylphosphine complex (FeCl (PPh3)) of divalent y"O-s:Ras-liss, 1 no-1 si(R)(R)-A iron, a bistriphenylphosphine complex (NiC1 (PPh)) of 15 Al-(R)(R2)Si-O O V divalent nickel and a bistributylphosphine complex (NiBr. y O (PBus.),) of divalent nickel. 1- D3v D2 s; 1Ns;--r1O i n O A solvent may be used for the polymerization reaction. Al-(R)(R4)Si Sir O Losi, Si(R2)(R)-A The examples of the solvent used are hydrocarbons (ex R -1. No R11 amples: benzene, toluene and the like), ethers (examples: R R11 diethyl ether, THF, diphenyl ether, anisole, dimethoxyben Zene and the like), halogenated hydrocarbons (examples: methylene chloride, chloroform, chlorobenzene and the In Formula (1-1-2), all R's are the same group selected like), ketones (examples: acetone, methyl ethyl ketone, from alkyl having a carbon atom number of 1 to 8 in which methyl isobutyl ketone and the like), alcohols (examples: 25 optional hydrogen may be substituted with fluorine and in methanol, ethanol, propanol, isopropanol, n-butyl alcohol, which optional —CH2— may be substituted with —O—, tert-butyl alcohol and the like), nitriles (examples: acetoni —CH=CH cycloalkylene or cycloalkenylene, phenyl in trile, propionitrile, benzonitrile and the like), esters (ex which optional hydrogen may be substituted with halogen, amples: ethyl acetate, butyl acetate and the like), carbonate methyl or methoxy, non-Substituted naphthyl and phenyla base solvents (examples: ethylene carbonate, propylene car 30 lkyl constituted from a phenyl group in which optional bonate and the like), amide base solvents (examples: N.N- hydrogen may be substituted with fluorine, alkyl having a dimethylformamide, N,N-dimethylacetamide and the like), carbon atom number of 1 to 4, vinyl or methoxy and an hydrochlorofluorocarbon base solvents (examples: HCFC alkylene group which has a carbon atom number of 1 to 8 141b, HCFC-225 and the like), hydrofluorocarbon base and in which optional —CH2— may be substituted with solvents (examples: HFCs and the like), perfluorocarbon 35 —O—; when the phenyl or a phenyl group in the phenyla base solvents (examples: perfluoropentane, perfluorohexane lkyl has plural substituents, the substituents may be the same and the like), alicyclic hydrofluorocarbon base solvents group or different groups; R and R are groups indepen (examples: fluorocyclopentane, fluorocyclobutane and the dently selected from alkyl having a carbon atom number of like), oxygen-containing fluorine base solvents (examples: 1 to 8, phenyl and cyclohexyl; and A' is a group represented fluoroether, fluoropolyether, fluoroketone, fluoroalcohol and 40 by Formula (2-1): the like) and water. The compounds given above in paren theses are the preferred examples of the respective solvents. They may be used alone or in combination of two or more (2-1) kinds thereof. The polymerization can be carried out as well O R4 in an emulsion system or a system in which a Supercritical 45 fluid CO, is used as a medium. The solvent which can be used shall not be restricted to the above examples. The atom transfer radical polymerization can be carried out under reduced pressure, atmospheric pressure or applied pressure according to the kind of the addition-polymerizable 50 In Formula (2-1), Z' is alkylene having a carbon atom monomer and the kind of the solvent. The polymerizing number of 2 to 20 or alkenylene having a carbon atom catalyst or a radical produced is likely to be deactivated number of 3 to 8, and optional —CH2— in these alkylene when brought into contact with oxygen. In Such case, the and alkenylene may be substituted with —O : R is hydro polymerizing speed is reduced, and the good living polymer gen, alkyl having a carbon atom number of 1 to 20, aryl is not obtained. Accordingly, it is important to carry out the 55 having a carbon atom number of 6 to 20 or arylalkyl having polymerization under inert gas environment of nitrogen or a carbonatom number of 7 to 20; R is alkyl having a carbon argon. In this reaction, oxygen dissolved in the polymeriza atom number of 1 to 20, aryl having a carbon atom number tion system has to be removed in advance under reduced of 6 to 20 or arylalkyl having a carbon atom number of 7 to pressure. Then, it is possible to shift to a polymerization step 20; and X" is halogen. as it is under reduced pressure after finishing the step of 60 In introducing A' as a polymerization initiator into a removing dissolved oxygen. A conventional method can be silsesquioxane derivative, a representative method for adopted for the atom transfer radical polymerization, and it obtaining the derivative which is not hydrolyzed includes a shall not specifically be restricted by the polymerization method in which a Grignard reagent is reacted with Si method. Capable of being adopted is, for example, a bulk halogen and a method in which a compound having an polymerization method, a solution polymerization method, a 65 aliphatic unsaturated bond is reacted with Si-H. Usually, Suspension polymerization method, an emulsion polymer the latter is called a hydrosilylation reaction method. In the ization method or a bulk-Suspension polymerization method. present invention, the hydrosilylation reaction method is US 7,256.243 B2 65 66 rather liable to be applied in terms of an easiness in In Formula (2-2), Z is alkylene having a carbon atom obtaining the raw material, but it shall not be restricted number of 2 to 10, and optional —CH2— in this alkylene thereto. may be substituted with —O— or -COO : R is alkyl having a carbon atom number of 1 to 3; a is an integer of 0 to 2: X is halogen; and a bonding position of SOX on (P-1) the benzene ring is an ortho position, a meta position or a R11 para position to a bonding position of Z, and a bonding R11 R11 R11 position of R is an optional position excluding the respec V Oss- -ON/ tive bonding positions of Z and SOX. Also when Sisoglosin O Si(R)(R)-Bl 10 introducing A as a polymerization initiator into a silsesqui Bl-(R)(R2)Si-O O V oxane derivative, a method in which a Grignard reagent is v O O Si reacted with Si-halogen and a method in which a compound -(RyRs1's-oris O having an aliphatic unsaturated bond is reacted with Si-H Bl-(R)(R4)Si Sir O No sig Si(R2)(R)-Bl can be used similarly to the case of obtaining the compound R -1R11 No R11 15 R11
R'', RandR in Formula (P-1) have the same meanings as those of these codes in Formula (1-1-2), and B is a group represented by Formula (2-1-P):
(2-1-P) O R. 25
30 R'', RandR in Formula (P-2) have the same meanings as In Formula (2-1-P), P' is a chain of a structural unit obtained those of these codes in Formula (1-2-2), and B is a group by polymerizing an addition-polymerizable monomer, and represented by Formula (2-2-P): the other codes have the same meaning as those of the codes in Formula (2-1). When using a compound (1-2-2) as an initiator, a polymer 35 (2-2-P) obtained by the method described above is represented by (R), Formula (P-2). In the following explanations, the polymer represented by Formula (P-2) is shown as the polymer (P-2): -- "y 40 (1-2-2) O R11 R Elo R11 O In Formula (2-2-P), P’ is a chain of a structural unit obtained A2-(R)(R2)Si-O isos v26ss',Si(R)(R)-A 45 by polymerizing an addition-polymerizable monomer; the y other codes have the same meanings as those of the codes in O Formula (2-2); and the bonding positions of -SOX and A--(R)(R4)Si:-(RyRs. 1's-oris\ Loc's O R (R)-A R on the benzene ring are the same as the bonding positions R -Nd R11 in Formula (2-2). R R11 50 When using a compound (1-3-2) as an initiator, a polymer obtained by the method described above is represented by Formula (P-3). In the following explanations, the polymer R'', R and R in Formula (1-2-2) have the same mean ings as those of these codes in Formula (1-1-2); A is a group represented by Formula (P-3) is shown as the polymer (P-3): represented by Formula (2-2); and B is a group represented 55 (1-3-2) by Formula (2-2-P):
(2-2) --().(R), 60 O 65 US 7,256.243 B2 67 68 R'', R and R in Formula (1-3-2) have the same meanings bonded is obtained. If adopted is a method in which the as those of these codes in Formula (1-1-2); A is a group monomers are successively added, for example, a method in represented by Formula (2-3): which the second monomer is added after finishing the polymerization of the first monomer to complete the poly merization, silsesquioxane to which the block copolymer is (2-3) bonded is obtained. Repeating of the above staged polymer (R), ization using plural monomers makes it possible to obtain silsesquioxane to which the multiblock copolymer is bonded. Coexistence of, if necessary, a multifunctional 10 monomer makes it possible as well to prepare a cross-linked polymer having a three-dimensional network structure. When polymerizing a conventional addition-polymeriz In Formula (2-3), Z is alkylene which has a carbon atom able monomer, combined use of a compound having a number of 1 to 3 and in which optional —CH2— may be polymerizable functional group together with a function of substituted with —O : Z” is alkylene which has a carbon 15 an initiator makes it possible to obtain silsesquioxane to atom number of 2 to 10 and in which optional —CH2—may which the high branched type polymer is bonded. The be substituted with —O-, -COO or —OCO : R is examples of Such compound are 2-(2-bromopropanoyloxy) alkyl having a carbon atom number of 1 to 3; a is an integer ethyl (meth)acrylate, 2-(2-bromoisobutyryloxy)ethyl (meth) of 0 to 2: X is halogen; and a bonding position of Z on the acrylate, 2-(2-bromopropanoyloxy)styrene and 2-(2-bro benzene ring is a meta position or a para position to a moisobutyryloxy)styrene. Combined use of a silicon bonding position of Z, and a bonding position of R is an compound having a (meth)acryl group or a styryl group optional position excluding the respective bonding positions makes it possible to introduce a structural unit containing a of Zand Z7. Also when introducing A as a polymerization silicon atom into the structure of the polymer. The examples initiator into a silsesquioxane derivative, a method in which of the above silicon compound are trialkoxysilane, polydim a Grignard reagent is reacted with Si-halogen and a method 25 ethylsiloxane and silsesquioxane. After copolymerized with in which a compound having an aliphatic unsaturated bond an addition-polymerizable monomer having an initiating is reacted with Si-H can be used similarly to the case of group which does not take part in atom transfer radical obtaining the compound (1-1-2). polymerization, the addition-polymerizable monomer is fur ther polymerized in the other polymerization mode (for 30 example, nitroxyl polymerization and photo initiator-trans (P-3) fer agent-terminator polymerization) using the resulting polymer as an initiator, whereby a graft copolymer can be formed. The examples of the addition-polymerizable mono mer having an initiating group which does not take part in 35 atom transfer radical polymerization are 1-(2-(4-vinylphe nylmethoxy)-1-phenylethoxy-2.2.6.6-tetramethylpyridine, 1-(meth)acryloxy-2-phenyl-2-(2.2.6,6-tetramethyl-1-pip eridinyloxy)ethane, (1-(4-(4-(meth)acryloxyethoxyethyl) phenylethoxy)piperidine and vinylphenylmethyldithiocar 40 bamate. After copolymerized with a monomer having a glycidyl group (example: glycidyl (meth)acrylate), a monomer hav ing an oxetanyl group(example: 3-ethyl-3-(meth)acryloy R'', RandR in Formula (P-3) have the same meanings as loxymethyloxetane) or a monomer having dioxolane(ex those of these codes in Formula (1-3-2), and B is a group 45 ample: 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3- represented by Formula (2-3-P): dioxolane), an aliphatic Sulfonium salt, an aromatic Sulfonium salt or an aromatic iodonium salt is added as a thermally latent or optically latent cationic polymerization (2-3-P) initiator to the resulting polymer, whereby a cross-linked (R), 50 polymer having a three-dimensional network structure can be prepared by cationic polymerization. The examples of the aliphatic sulfonium salt which is the thermally latent cat ionic polymerization initiator are 3-methyl-2-butenyltetram ethylenesulfonium hexafluoroantimonate and 2-butenyltet 55 ramethylenesulfonium hexafluoroantimonate, and they are In Formula (2-3-P), P is a chain of a structural unit obtained marketed from Asahi Denka Co., Ltd. Many products of the by polymerizing an addition-polymerizable monomer; the aromatic sulfonium salt which is the thermally latent or other codes have the same meaning as those of these codes optically latent cationic polymerization initiator are mar in Formula (2-3); and the bonding positions of Zand Ron keted from Sanshin Chemical Industry Co., Ltd. and Asahi the benzene ring are the same as the respective bonding 60 Denka Co., Ltd. Diphenyl-4-thiophenoxyphenylsulfonium positions in Formula (2-3). hexafluoroantimonate also is the example of the aromatic Suitable selection of the kind of the monomer used makes Sulfonium salt. The example of the aromatic iodonium salt it possible to control the structure of the polymer (P-1). For is (4-pentadecyloxyphenyl)phenyliodonium hexafluoroanti example, if the monomer is homopolymerized, silsesquiox monate. When carrying out optically latent cationic poly ane to which the homopolymer is bonded is obtained. If the 65 merization, a photosensitizer, for example, Adeka Optomer plural monomers are added at the same time and polymer SP-100 (manufactured by Asahi Denka Co., Ltd.) may be ized, silsesquioxane to which the random copolymer is used in combination. Also, when obtaining a cross-linked US 7,256.243 B2 69 70 polymer having a three-dimensional network structure by and aluminum silicate. The examples of the basic adsorbents cationic polymerization, a monofunctional or multifunc are activated alumina, the Zeolite base adsorbents and the tional glycidyl base cross-linking agent or a monofunctional hydrotalcites compounds each described above. These or multifunctional oxetane base cross-linking agent may be adsorbents may be used alone or in a mixture of two or more allowed to coexist. kinds thereof. The polymer (P-1) produced by the atom Next, a refining method for the polymer (P-1) shall be transfer radical polymerization can be refined by bringing explained. This compound is isolated and refined by effi into contact with activated alumina. A commercial product ciently removing the unreacted vinyl base monomer. Various available from Aldrich Co., Ltd. can be used as activated methods are available, and a refining method carried out by alumina. When adsorbing treatment is carried out by using reprecipitation operation is preferred. This refining method 10 is carried out in the following manner. First, a solvent which activated alumina in combination with the other adsorbent, does not dissolve the polymer (P-1) but dissolves the unre the adsorbents can be mixed and brought into contact with acted monomer, a so-called precipitant is added to the the compound, but they may be brought into contact at the polymerization reaction liquid containing the polymer (P-1) separate steps respectively. When brought into contact with and the unreacted monomer to precipitate only the polymer 15 the adsorbent, the reaction liquid may be used as it is or may (P-1). A preferred use amount of the precipitant is 20 to 50 be diluted with a solvent. The diluent may be selected from times based on the weight of the polymerization reaction usual solvents only on the condition that it is not a poor liquid described above. solvent for the polymer. A temperature for treating with the The preferred precipitant is a solvent which is compatible adsorbent shall not specifically be restricted. The treatment with the polymerization solvent used in polymerization and may be carried out usually at 0 to 200° C. The preferred which does not dissolve the polymer (P-1) at all but dis temperature range is room temperature to 180° C. A use Solves only the unreacted monomer and has a relatively low amount of the absorbent falls in a range of 0.1 to 500% by boiling point. The examples of the preferred precipitant are weight based on the weight of the polymer (P-1). Consid lower alcohols and aliphatic hydrocarbons. The particularly ering the economical efficiency and the operability, the preferred precipitant is methanol and hexane. A repeating 25 preferred range is 0.5 to 10% by weight. frequency of the reprecipitation operation is advisably A method of a batch system in which stirring-mixing and increased in order to further raise a removing efficiency of Solid-liquid separation are carried out by batch operation can the unreacted monomer. This method makes it possible to be used for solid-liquid contact of the absorbent and the deposit only the polymer (P-1) in a poor solvent, and the polymer liquid. In addition thereto, capable of being used is polymer can readily be separated from the unreacted mono 30 a method of a continuous system such as a fixed layer system mer by filtering operation. in which the polymer liquid is allowed to pass through a The transition metal complex which is the polymerizing vessel charged with the adsorbent, a moving layer system in catalyst remains in the compound (P-1) isolated by the which the liquid is allowed to pass through a moving layer method described above, and therefore problems such as of the adsorbent and a fluidized layer system in which the coloring of the polymer, influence on the physical properties 35 adsorbent is fluidized by a liquid to carry out adsorption. and environmental safety are brought about in a certain case. Further, a mixing and dispersing operation carried out by Accordingly, this catalyst residue has to be removed in stirring can be combined, if necessary, with operation for finishing the polymerization reaction. The catalyst residue elevating the dispersing efficiency, Such as shaking of the can be removed by adsorbing treatment using activated vessel and use of a SuperSonic wave. After the polymer carbon. The examples of adsorbents other than activated 40 liquid is brought into contact with the absorbent, the absor carbon are ion exchange resins (acid, basic or chelate form) bent is removed by a method such as filtering, centrifugal and inorganic adsorbents. The inorganic adsorbents have a separation and settling separation, and washing treatment is character of a solid acid, a solid base or neutrality. They are carried out if necessary to obtain the refined polymer liquid. particles having a porous structure and therefore have a very Treatment by the absorbent may be carried out for the high adsorbing ability. It is also one of the characteristics of 45 polymer (P-1) which is the final product, and it may be the inorganic adsorbents that they can be used in a wide carried out for an intermediate product used for producing temperature range extending from a low temperature to a this polymer. For example, in the respective polymerizing high temperature. steps of the block copolymer obtained by the atom transfer The examples of the inorganic adsorbents are silicon radical polymerization, this polymer can be isolated and dioxide, magnesium oxide, silica alumina, aluminum sili 50 subjected to adsorbing treatment. The polymer (P-1) sub cate, activated alumina, clay base adsorbents such as acid jected to treatment by the adsorbent may be separated by clay and activated clay, Zeolite base adsorbents, dawsonites depositing in a poor solvent or distilling off volatile com compounds and hydrotalcites compounds. Zeolite includes ponents such as the solvent under reduced pressure. natural products and synthetic products, and either can be The catalyst residue can be removed by carrying out used. Kinds Such as a crystal form, an amorphous form, a 55 refining treatment using a non-water soluble solvent and a noncrystal form, a glass form, a synthetic product and a complexing agent aqueous solution or using a non-water natural product are available for silicon dioxide, and silicon soluble solvent and a complexing agent aqueous solution dioxide of a powder form can be used in the present further containing an electrolytic component. That is, after invention regardless of the kind. The examples of natural the polymer (P-1) is dissolved in a non-water soluble aluminum silicate are pumice, fly ash, kaoline, bentonite, 60 Solvent, a complexing agent aqueous solution or a complex activated clay and diatomaceous earth. Synthetic aluminum ing agent aqueous solution further containing an electrolytic silicate has a large specific Surface area and a high adsorbing component is added to the above solution of the polymer ability. The hydrotalcites compound is carbonate hydrate of (P-1) and stirred and mixed to convert the transition metal aluminum-magnesium hydroxide. component to a complex with the complexing agent, fol The acid adsorbents and the basic adsorbents are prefer 65 lowed by extracting it in the aqueous layer, whereby a ably used in combination with activated carbon. The concentration of the catalyst component remaining in the examples of the acid adsorbents are acid clay, activated clay polymer (P-1) can notably be reduced. US 7,256.243 B2 71 72 The polymerization reaction liquid may be a target for the centrifugal separators can be used. When an inorganic refining treatment. When the polymerization reaction liquid adsorbent is used in combination, a decanter of a three phase has a high Viscosity, a non-water soluble solvent may be separation type is used since solid matters such as sludge are added thereto to control the viscosity to a suited solution contained, but also in Such case, other centrifugal separators Viscosity, and then the refining treatment may be carried out. can naturally be used. The polymer treated at the steps That is, after the polymerization reaction liquid containing described above can be isolated by depositing in a poor the polymer (P-1) is diluted by a prescribed amount of a Solvent and distilling off volatile components such as the non-water soluble solvent in finishing the polymerization solvent and the like under reduced pressure. reaction, a complexing agent aqueous solution or a com The frequency of mixing and contacting of the polymer plexing agent aqueous solution further containing an elec 10 (P-1) solution with the complexing agent aqueous solution trolytic component is added to the above solution and stirred or the complexing agent aqueous solution further containing and mixed to convert the transition metal component to a an electrolytic component and the oil-water separation step complex salt, which is transferred into the aqueous solution shall not specifically be restricted as long as a concentration described above, and then the non-water soluble solvent of the catalyst component remaining in the polymer (P-1) containing the polymer (P-1) is separated from the aqueous 15 can notably be reduced. That is, assuming that a mixing/ Solution described above by physical operation Such as contacting and oil-water separation step is one step, the centrifugal separation and static separation. Such refining transition metal component contained in the polymer (P-1) treatment makes it possible to notably reduce a concentra is analyzed every one step, whereby the frequency of the tion of the catalyst component remaining in the polymer steps is determined at the step at which-the transition metal (P-1). component has been reduced to the targeted content. The operational procedure of the above refining treatment In general, an addition proportion of the complexing may not necessarily be carried out in the manner described agent to the transition metal component contained in the above. For example, a complexing agent or a complexing polymer (P-1) is preferably 1 to 1000 equivalents in terms of and an electrolytic component may be added to the polymer a mole ratio of the complexing agent based on the transition (P-1) or the polymerization reaction liquid containing the 25 metal component. A content of the transition metal con polymer (P-1), and then a non-water soluble solvent may be tained in the polymer (P-1) can beforecasted in advance by added thereto, followed by further adding water. The refin calculation in charging the polymerization reaction liquid, ing treatment, even if it is carried out by any operational and therefore an amount of the complexing agent described procedure, leads finally to the same extraction treatment as above can be determined by a content of the transition metal the case of the operational procedure explained at the 30 contained in the polymer (P-1) to be treated. A concentration beginning, and the same effect is obtained. of the complexing agent contained in the complexing agent In this case, a solution obtained by dissolving the polymer aqueous solution falls preferably in a range of 0.001 to 20% (P-1) in a non-water soluble solvent, the polymerization by weight. reaction liquid or a solution obtained by diluting the poly Further, in the complexing agent aqueous Solution con merization reaction liquid by a non-water Soluble solvent 35 taining an electrolytic component, a use amount thereof shall be called a polymer (P-1) solution. The polymer (P-1) shall not specifically be restricted as long as a rise in the solution is preferably mixed and brought into contact with oil-water separation efficiency by increasing a specific grav the complexing agent aqueous solution or the complexing ity of the aqueous Solution is a principal object and time agent aqueous Solution further containing an electrolytic required for the separation is shortened. In general, it can be component by Stirring in a bath type treating bath of a batch 40 used in a Saturated or half-saturated State. type equipped with a stirrer. A bath type treating bath of a Such step is carried out for the polymer (P-1) which is the shaking type may be used. A concentration of the polymer final product, but it may be carried out for an intermediate contained in the polymer (P-1) solution makes it a condition product used for producing the above polymer. It is possible that the solution is homogeneous and that it has a viscosity as well, for example, to isolate the above polymer in the which enables stirring and mixing with the complexing 45 respective polymerization stages of the block copolymer agent aqueous Solution, and it is preferably 40% by weight obtained by the atom transfer radical polymerization and or less. When a concentration of the polymer contained in then carry out the above treatment. the polymer (P-1) solution is raised, the problems of the The examples of the non-water soluble solvent used at the deposition of the polymer and an increase in the Viscosity are above refining step are anisole, benzene, carbon tetrachlo brought about in a certain case, and in Such case, it is 50 ride, chlorobenzene, chloroform, 1-chloronaphthalene, advisable to carry out treatment under heating in a treating dibenzylnaphthalene, o-dichlorobenzene, m-dichloroben bath equipped with a heating device Such as a steam coil or Zene, 1,1-dichloroethane, 1,2-dichloroethane, dichlo a steam jacket by which heating can be carried out at 70 to romethane, diisopropyl ether, N,N-dimethylaniline, diphe 100° C. If the polymer contained in the polymer (P-1) nyl ether, ethyl acetate, mesitylene, methyl acetate, isoamyl Solution has a low concentration and the solution is homo 55 acetate, cyclohexanone, cyclopentanone, nitrobenzene, geneous at room temperature, the solution can be stirred and nitromethane, tetrachloroethylene, tetralin, toluene, trichlo contacted at room temperature. roethylene and xylene. More preferred examples are chlo Centrifugal separation or static separation in which a roform, ethyl acetate and toluene. difference in a specific gravity is utilized and electrostatic The complexing agent aqueous Solution used is an aque deoiling making use of a difference in electric properties can 60 ous solution of at least one compound selected from ali be utilized for oil-water separation of the polymer (P-1) phatic carboxylic acids, aromatic carboxylic acids, ammo Solution from the complexing agent aqueous solution or the nia, amines, aminocarboxylic acids, amino acids, complexing agent aqueous solution further containing an phosphoric acids, phosphonic acids and inorganic Sulfur electrolytic component. In the present invention, oil-water compounds. The compounds other than the inorganic Sulfur separation of two phases is required, and therefore a 65 compounds among the above compounds can be used, if decanter of a two phase separation type is most Suitably necessary, in the form of salts, for example, the salts of used, but it is a matter of course in this case that other alkaline metals such as Sodium, potassium and lithium, the US 7,256.243 B2 73 74 salts of alkaline earth metals such as calcium and barium, the ramethylenediaminetetraacetic acid, pentamethylenedi salts of heavy metals such as iron (III) and Vanadium, aminetetraacetic acid, hexamethylenediaminetetraacetic hydrochlorides, ammonium salts, amine salts, salts partially acid, octamethylenediaminetetraacetic acid, 1.2-cyclopenta neutralized by equivalent or more or less of metals and basic diaminetetraacetic acid, trans-cyclohexane-1,2-diaminetet Substances based on carboxyl groups and the mixtures of the raacetic acid, cyclohexane-1,4-diaminetetraacetic acid, 1.3, above salts. 5-triaminocyclohexaacetic acid, The examples of the aliphatic carboxylic acids are formic o-phenylenediaminetetraacetic acid, 2-hydroxytrimethyl acid, acetic acid, propionic acid, butyric acid, isobutyric enediaminetetraacetic acid, ethyletherdiaminetetraacetic acid, Valeric acid, isovaleric acid, oxalic acid, malonic acid, acid, hydantoic acid, (S,S)-ethylenediaminedisuccinic acid, Succinic acid, glutaric acid, maleic acid, adipic acid, fumaric 10 (S,S)-ethylenediaminediglutaric acid, (S,S)-asparagic acid acid, citraconic acid, itaconic acid, tricarbazylic acid, pro N,N-diacetic acid, (S,S)-iminodisuccinic acid, (S)-glutamic pane-1,1,2,3-tetracarboxylic acid, butane-1-glycolic acid, acid-N,N-diacetic acid, (S)-O-alanine-N,N-diacetic acid and lactic acid, B-hydroxypropionic acid, malic acid, tartaric taurine-N,N-diacetic acid. acid, citric acid, alloisocitric acid, gluconic acid, pyruvic The examples of the amino acids are glycine, sarcosine, acid, oxaric acid, diglycolic acid and thiodiglycolic acid. 15 glycine methyl ester, Valine, alanine, B-alanine, norleucine, The examples of the aromatic carboxylic acid are benzoic leucine, isoleucine, phenylalanine, tyrosine, cysteine, acid, phthalic acid, isophthalic acid, mandelic acid, Salicylic methionine, serine, threonine, asparagine, glutamine, lysine, acid, 5-sulfosalicylic acid, C-carboxy-o-anisic acid and e-polylysine, histidine, arginine, glutamic acid, poly o-(carboxymethylthio)benzoic acid. glutamic acid, asparagic acid, 1,2-diaminopropionic acid, The examples of the amines are diethylamine, methy proline, triptophan and N-ethylglycine. lamine, ethylamine, propylamine, triethylamine, morpho The examples of the phosphoric acids are hexametaphos line, piperidine, ethylenediamine, N-methylethylenedi phoric acid, tetrametaphosphoric acid and condensed phos amine, N-ethylethylenediamine, N-n- phoric acid. The examples of the phosphonic acids are propylethylenediamine, N-isopropylethylenediamine, N-(2- ethylidenephosphonic acid, diethylenetriaminepenta(meth hydroxyethyl)ethylenediamine, N,N- 25 ylenephosphonic acid), methyldiphosphonic acid, nitrilotris dimethylethylenediamine, N,N-diethylethylenediamine, (methylenephosphonic acid), ethylenediaminetetrakis-(me N-N'dimethylethylenediamine, N,N'-diethylethylenedi thylenephosphonic acid) and 1.2-propylenediaminetetra amine, N,N'-di-n-propylethylenediamine, N,N-di(2-hy (methylenephosphonic acid). droxyethyl)ethylenediamine, N.N.N',N'-tetramethylethyl The examples of the inorganic Sulfur compounds are enediamine, 1,2-diaminopropane, meso-2,3-diaminobutane, 30 thiosulfates (examples: Sodium thiosulfate), polythionates rac-2,3-diaminobutane, trimethylenediamine, tetramethyl (examples: SO (S), SO (n=1 to 4)), dithionites (ex enediamine, pentamethylenediamine, triethylenediamine, amples: sodium dithionite), sulfites (examples: sodium diethylenetriamine, 3,3'-diaminodipropylamine, triethylene Sulfite) and dithionates (examples: sodium dithionate). tetraamine, 2-hydroxyethylamine, 2-methoxyethylamine, There are no selecting conditions for water used other 2,2'-dihydroxydiethyleneamine and polyamideamine. 35 than considering to prevent the polymer from being con The examples of the aminocarboxylic acids are iminodi taminated. Water allowed to pass through a filter of 50 um acetic acid, iminodipropionic acid, N-methyliminodiacetic or less is preferred, and purified water which is treated with acid, N-(3,3'-dimethylbutyl)iminodiacetic acid, phenylimi an ion-exchange resin is more preferred. nodiacetic acid, hydroxyethyliminodiacetic acid, hydroxy The examples of the electrolytic component are sodium ethyliminopropionic acid, hydroxypropyliminodiacetic acid, 40 chloride, ammonium chloride, Sodium acetate, sodium phos 2-hydroxycyclohexyliminodiacetic acid, methoxyethylimi phate, sodium citrate, sodium tartarate, sodium benzoate, nodiacetic acid, 2-hydroxybenzyliminodiacetic acid, N-(o- Sodium Sorbate, Sodium phthalate and sodium metabisulfate, carboxyphenyl)iminodiacetic acid, N-(m-carboxyphenyl) and they may be potassium salts. The compounds which can iminodiacetic acid, N-(p-carboxylphenyl)iminodiacetic be used as the electrolytic component are included in the acid, N-(carbamoylmethyl)iminodiacetic acid, cyanometh 45 compounds which are used for the complexing agent aque yliminodiacetic acid, aminoethyliminodiacetic acid, ous solution described above. When using the electrolytic 2-ethoxycabonylaminoethyliminodiacetic acid, phospho component, at least one of them is added to the complexing nomethyliminodiacetic acid, phosphonoethyliminodiacetic agent aqueous Solution. acid, Sulfoethyliminodiacetic acid, o-sulfophenyliminodi Adsorbing treatment using activated carbon may be used acetic acid, m-Sulfophenyliminodiacetic acid, nitrilotriacetic 50 in combination with the method described above in order to acid, carboxyethyliminodiacetic acid, carboxymethylimino remove the residual catalyst. When solid-liquid contact of an dipropionic acid, nitrilotripropionic acid, N,N'-ethylenedi ion exchange resin and an inorganic adsorbent with the amine, ethylenediamine-N,N'-dipropionic acid, N,N'-dichy polymer Solution is used in combination, a method of a batch droxyethyl)ethylenediamine diacetic acid, N-n- type in which stirring/mixing and solid-liquid separation are butylethylenediaminetriacetic acid, 55 carried out by batch operation can be utilized. In addition N-cyclohexylethylenediaminetriacetic acid, N'-hydroxy thereto, capable of being utilized as well are a fixed bed ethyl-N,N,N'-triacetic acid, benzylethylenediaminetriacetic system in which the polymer Solution is allowed to pass acid, ethylenediaminetetraacetic acid, ethylenediaminetet through a vessel filled with an adsorbent, a moving bed raacetic acid-zinc, ethylenediaminetetraacetic acid-diso system in which the solution is allowed to pass through a dium, ethylenediaminetetraacetic acid-calcium, ethylenedi 60 moving bed of an adsorbent and a continuous system such aminetetraacetic acid-magnesium, as a fluidized bed system in which adsorption is carried out ethylenediaminetetraacetic acid-dipotassium, ethylenedi with an adsorbent fluidized by a liquid. Further, mixing and amine-N,N'-diacetic acid N,N'-dipropionic acid, ethylenedi dispersing operation can be combined, if necessary, with amine-N,N'-dic2-propionic acid), ethylenediamine-N,N'- operation for elevating a dispersing efficiency Such as shak disuccinic acid, ethylenediamine-N,N'-diglutaric acid, 65 ing of a vessel and utilizing of a SuperSonic wave. After the ethylenediaminetetrapropionic acid, 1,2-propylenediamine polymer Solution is brought into contact with the adsorbent, tetraacetic acid, trimethylenediaminetetraacetic acid, tet the adsorbent is removed by a method such as filtration, US 7,256.243 B2 75 76 centrifugal separation and settling separation, and washing be predicted from a mole ratio of the vinyl base monomer/ treatment with water is carried out if necessary, whereby the C-haloester group and a consumption rate of the monomer refining degree can further be raised. using the following calculation equation: The analytical methods of a molecular weight and a molecular weight distribution of the polymer (P-1) shall be Mn=(consumption rate (mole %) of monomer 100)x explained. Usually, a molecular weight of an addition poly MW x(mole ratio of vinyl base monomer to mer can be measured by gel permeation chromatography C-haloester group)+MW, (GPC) using a calibration curve in which a linear polymer In the above calculation equation, Mn is a theoretical Such as polystyrene and poly (methyl methacrylate) is used number average molecular weight; MW is a molecular as a standard sample. However, the polymer (P-1) belongs to 10 a polymer of a vinyl base monomer originating in Silses weight of the vinyl base monomer; and MW, is a molecular quioxane, that is, a branched type high molecular com weight of the C-haloester group. When intending to obtain pound. Accordingly, in determining a molecular weight of a polymer having the number average molecular weight the polymer (P-1) having the above structure, it is consid range described above, a mole ratio of the vinyl base ered that use of a calibration curve in which a linear polymer 15 monomer/C-haloester group can be selected from a range of Such as polystyrene and poly (methyl methacrylate) is used about 2/1 to about 40000/1, preferably about 10/1 to about as a standard sample brings about a problem on an accuracy 5000/1. The above number average molecular weight can be in molecular weight analysis. However, the polymer (P-1) controlled as well by changing the polymerization time. has silsesquioxane at an end part thereof, and therefore it can A theoretical molecular weight of the polymer (P-1) itself readily be decomposed under an acid condition or a basic can be predicted as well from a mole ratio of the vinyl base condition. That is, an accuracy in molecular weight analysis monomer/the compound (1-1-2) and a consumption rate of of the polymer part can further be enhanced by cutting off the monomer using the following calculation equation: the addition polymer from Silsesquioxane and then measur ing a molecular weight thereof. Hydrofluoric acid is pref Mn=(consumption rate (mole %) of monomer 100)x erably used when decomposing the polymer (P-1) under an 25 MW x(mole ratio of vinyl base monomer to acid condition. Potassium hydroxide is preferably used compound (1-1-2))+MW when decomposing the polymer (P-1) under a basic condi tion. The polymer (P-1) can be decomposed in both of a In the above calculation equation, Mn is a theoretical homogeneous system and a heterogeneous system. For number average molecular weight: MW is a molecular example, the Silsesquioxane part of the polymer (P-1) can be 30 weight of the vinyl base monomer; and MW, is a molecular cut off in a homogeneous mixed system of an organic weight of the compound (1-1-2). solvent (THF, acetonitrile and the like) which can dissolve Any method of GPC, 'H-NMR and gas chromatography the polymer (P-1) and hydrofluoric acid. The silsesquioxane can be adopted as a method for determining a consumption part can be decomposed as well in a heterogeneous mixed rate (hereinafter referred to as “a conversion rate') of the system of toluene and hydrofluoric acid. In this case, a phase 35 OOC. transfer catalyst is preferably used in combination. The The explanations described above regarding the polymer examples of the phase transfer catalyst are benzyltrimethy lammonium chloride, tetramethylammonium chloride, tet (P-1) can be applied to the polymer (P-2) and the polymer rabutylammonium bromide, trioctylammonium chloride, (P-3). dioctylmethylammonium chloride, triethylamine and dim 40 Next, a method for photopolymerizing the vinyl base ethylaniline. When using potassium hydroxide, decomposi monomer using the compound (1-4) as the initiator, a tion can be carried out as well in a mixed solvent of THF, so-called photo initiator-transfer agent-terminator polymer ethanol and water. izing method shall be explained. It is well known that in this The addition polymer cut off by the above methods is photo initiator-transfer agent-terminator polymerization, a measured by GPC, whereby a molecular weight of an 45 dithiocarbamate group is radically dissociated by light and addition polymer part in the polymer (P-1), a molecular has an excellent polymerization initiating ability and a weight of a so-called graft chain can be determined. It is sensitizing ability. It is well known as well that photopoly possible as well to determine a molecular weight of the merization in this case is radical polymerization and that it polymer (P-1) itself by using a universal calibration curve is similar to living polymerization. These informations are obtained from the viscosity and the GPC data. An absolute 50 disclosed in, for example, Polymer Bulletin, 11 (1984), 135 molecular weight of the polymer (P-1) can be determined as and Macromolecules, 19 (1986), 287-. Accordingly, the well by an end group determination method, a membrane silicon compound of the present invention having a dithio osmotic pressure method, a ultracentrifugal method and a carbamate group can continue to maintain a polymerization light scattering method. initiating ability as long as irradiated with light, and it has a A preferred molecular weight of the graft chain in the 55 photopolymerization initiating ability for all radically poly polymer (P-1) falls in a range of 500 to 1,000,000 for a merizable monomers. number average molecular weight in terms of poly (methyl It is known as well that a dithiocarbamate group has the methacrylate). The more preferred range is 1,000 to 100, respective functions of a polymerization initiator, a chain 000. However, the upper limit value and the lower limit transfer agent and a photopolymerization terminator all value in this range do not necessarily have a specific 60 together in photopolymerization, and the reaction mecha meaning. The molecular weight distribution falls preferably nism thereof has already become clear. The compound (1-4) in a range of 1.01 to 2.0 in terms of a dispersion degree of the present invention having a dithiocarbamate group is (Mw/Mn). dissociated into a radical on an alkylphenyl group bonded to The molecular weight of the graft chain can be controlled the silicon compound and a dithiocarbamate radical by by a proportion of the vinyl base monomer to an O-haloester 65 irradiating with light. Then, the radical on the alkylphenyl group which is an initiating group. That is, a theoretical group takes part in the initiation of the reaction, and the molecular weight of the graft chain in the polymer (P-1) can dithiocarbamate radical takes part in the termination of the US 7,256.243 B2 77 78 reaction. When irradiation with light is stopped or the monomer is exhausted, the dithiocarbamate radical is added to the growing end as a terminator to form again a dithio (R) (2-4) carbamate group. Accordingly, the polymer thus formed can 3. also be used as a polymer photoinitiator having a photopo 5 lymerization initiating ability. The silicon compound of the present invention having a dithiocarbamate group can ini --().= z*-s--N V tiate photopolymerization of a vinyl base monomer coex R9 isting therewith by being decomposed by irradiating with a 10 UV ray having a wavelength of 250 to 500 nm, preferably 300 to 400 nm having energy required for radically disso In Formula (2-4), R and R are independently hydrogen, alkyl having a carbon atom number of 1 to 12, cycloalkyl ciating the dithiocarbamate group. having a carbon atom number of 5 to 10 or aryl having a The form of carrying out the polymerization reaction can carbon atom number of 6 to 10, and R and R may be suitably be selected from bulk polymerization, solution 15 combined with each other to form a ring together with N. Z polymerization, Suspension polymerization, emulsion poly is alkylene which has a carbon atom number of 1 to 3 and merization and bulk-Suspension polymerization. A solvent in which optional —CH may be substituted with —O : used when producing by Solution polymerization is prefer Z” is alkylene which has a carbon atom number of 2 to 10 ably a solvent which has a small chain transfer constant and and in which optional —CH2— may be substituted with which can dissolve a vinyl base monomer and a polymer —O ,-COO or —OCO : R is alkyl having a carbon atom number of 1 to 3; a is an integer of 0 to 2; and a thereof. The examples of such preferred solvent are benzene, bonding position of Z on the benzene ring is a metaposition toluene, Xylene, ethylbenzene, acetone, methyl ethyl ketone, or a para position to a bonding position of Z, and a bonding methyl isobutyl ketone, ethyl acetate, methyl cellosolve, position of R is an optional position excluding the respec ethyl cellosolve, dimethylformamide, isopropyl alcohol, 25 tive bonding positions of Zand Z. Also when introducing butanol, hexane and heptane. A solvent having no charac A" as a polymerization initiator into a silsesquioxane deriva teristic absorption in a UV ray area of 250 to 500 nm is tive, a method in which a Grignard reagent is reacted with rather preferred. The polymerization temperature falls in a Si-halogen and a method in which a compound having an range of 0 to 200° C., preferably room temperature to 150° 30 aliphatic unsaturated bond is reacted with Si-H can be used C., but it shall not specifically be restricted. similarly to the case of obtaining the compound (1-1-2). The photo initiator-transfer agent-terminator polymeriza tion can be carried out under reduced pressure, atmospheric pressure or applied pressure according to the kind of the vinyl base monomer and the kind of the solvent. It is 35 important to carry out the polymerization usually under environment of inert gas Such as nitrogen and argon, for example, under flowing of inert gas. Oxygen dissolved in the polymerization system has to be removed in advance under 40 reduced pressure, and therefore it is possible as well to transfer to a polymerization step as it is under reduced pressure after finishing the step of removing dissolved OXygen. When using a compound (1-4-2) as an initiator, a polymer 45 obtained by the method described above is represented by R'', RandR in Formula (P-4) have the same meanings as Formula (P-4). In the following explanations, the polymer those of these codes in Formula (1-4-2), and B" is a group represented by Formula (P-4) is shown as the polymer (P-4): represented by Formula (2-4-P): 50 (2-4-P) (1-4-2) (R), R11 R11SignsCissé,Si(R)(R)-A R11 R11 --(y,= 7 z-p-s--X A*-(R3)(R2)Si-O. O V O , O A-(R3)(R2)S 1 SS-O1 so-, "see 60 In Formula (2-4-P), P is a group comprising the polymer of R11 -Nd R11 the vinyl base monomer, and the other codes have the same R" meanings as those of the codes in Formula (2-4). The bonding positions of Zand R7 on the benzene ring are the same as the bond positions thereof in Formula (2-4). In Formula (1-4-2), R', RandR have the same meanings 65 The structure of the polymer (P-4) can be controlled by as those of these codes in Formula (1-1-2), and A' is a group the same method as in obtaining the polymer (P-1) by the represented by Formula (2-4): atom transfer radical polymerization method. Silsesquiox US 7,256.243 B2 79 80 ane to which a high branched type polymer is bonded can be to 100,000. However, the upper limit value and the lower obtained by using an initiator monomer, for example, N.N- limit value in this range do not have a specific meaning. A diethyldithiocarbamoylmetylstyrene or N-ethyldithiocar molecular weight distribution of the graft chain falls pref bamoylmetylstyrene in combination in polymerizing a con erably in a range of 1.01 to 3.0 in terms of a dispersion ventional vinyl base monomer. After copolymerized with a vinyl base monomer having an initiating group which does degree. It is possible as well to determine a molecular weight not take part in photo initiator-transfer agent-terminator of the polymer (P-4) by using a universal calibration curve polymerization, the vinyl base monomer is further polymer obtained from the viscosity and the GPC data. An absolute ized in the other polymerization mode (for example, an atom molecular weight of the polymer (P-4) can be determined as transfer radical polymerization method) using the resulting 10 well by an end group determination method, a membrane polymer as an initiator, whereby a graft copolymer can be osmotic pressure method, a ultracentrifugal method and a formed. The examples of the vinyl base monomer having an light scattering method. A molecular weight of the graft initiating group which does not take part in the photo chain in the polymer (P-4) can be controlled in the same initiator-transfer agent-terminator polymerization are 1-(2- manner as in the case of the polymer (P-1). ((4-ethenylphenyl)methoxy)-1-phenylethoxy-2.2.6.6-tet 15 ramethylpyridine, 1-(meth)acryloxy-2-phenyl-2-(2.2.6.6- tetramethyl-1-piperidinyloxy)ethane, (1-(4-(4-(meth) EXAMPLES acryloxy)ethoxyethyl)phenylethoxy)piperidine, 2-(2- bromopropanoyloxy)ethyl (meth)acrylate, 2-(2- The present invention shall more specifically be explained bromoisobutyryloxy)ethyl (meth)acrylate, with reference to examples, but the present invention shall p-chloromethylstyrene, 2-(2-bromopropanoyloxy)Styrene not be restricted to the following examples. and 2-(2-bromoisobutyryloxy)styrene. Codes used in the examples have the following meanings. After finishing the photo initiator-transfer agent-termina tor polymerization, the end dithiocarbamate group thereof is Ph: phenyl treated, whereby the polymer (P-4) can be deactivated 25 against a UV ray. The examples of a deactivating method are TMS: trimethylsilyl a method in which the polymer (P-4) is treated in an acid Mn: number average molecular weight Solution or a basic Solution, a method in which the polymer is treated at a high temperature of 250° C. or higher, a Mw: weight average molecular weight method in which the polymer is irradiated with an electro 30 magnetic beam of high energy having a wavelength of 220 EDTA2Na: disodium ethylenediaminetetraacetate nm or less, a method in which a monomer having a UV dihydrate ray-absorbing group is added and then photopolymerized All the data of molecular weights in the examples were and a method in which a UV ray-absorbing agent is merely polystyrene-reduced values determined by GPC (gel perme added. It is possible as well to substitute the end dithiocar 35 ation chromatography). The measuring conditions of GPC bamate group by adding a reagent having a large chain are shown below. transfer constant (thiol derivatives, thiuram, Xanthates and nitroxides) while irradiating the polymer (P-4) obtained with Apparatus: JASCO GULLIVER1500 (intelligent differen a UV ray. tial refractometer RI-1530), manufactured by A method for isolating and refining the polymer (P-4) 40 shall be explained. This compound is isolated and refined by JASCO Corp. efficiently removing the unreacted vinyl base monomer. Solvent: tetrahydrofuran (THF) Various methods are available, and a refining method carried out by the reprecipitating operation described above is Flow velocity: 1 ml/minute preferred. This method makes it possible to precipitate only 45 the polymer (P-4) in a poor solvent and readily separate the Column temperature: 40° C. polymer from the unreacted monomer by filtering operation. Columns used: the following columns (used connecting in The polymer may be isolated by distilling off volatile series) manufactured by Tosoh Co., Ltd. components such as the solvent and the unreacted monomer TSKguardcolumn HXL-L (GUARDCOLUMN) under a condition of reduced pressure. A preferred solvent 50 for dissolving the polymer (P-4) is a solvent having a large TSKgel G1000HXL (excluded critical molecular weight dissolving power and a relatively low boiling point. A (polystyrene): 1,000) preferred precipitant is a solvent which is compatible with TSKgel G2000HXL (excluded critical molecular weight the solvent for the polymer (P-4) and does not dissolve at all (polystyrene): 10,000) the polymer (P-4) and which dissolves only the impurities or 55 the unreacted monomer and has a relatively low boiling Standard sample for calibration curve: Polymer Standards point. The examples of the preferred precipitant are lower (PL), Polystyrene, manufactured by Polymer Laboratories alcohols and aliphatic hydrocarbons. The particularly pre Co., Ltd. ferred precipitant is methanol or hexane. It is advisable to increase the repeating frequency of the reprecipitating 60 In Examples 6 to 19, Shodex KF-G (GUARDCOLUMN) operation in order to further raise the refining degree. and 2 columns of Shodex KF-804L (excluded critical A molecular weight and a molecular weight distribution molecular weight (polystyrene): 400,000) manufactured by of the polymer (P-4) can be analyzed by the same method as Showa Denko K. K. were used connecting in series, and explained in the polymer (P-1). The polymer of the vinyl Shodex STANDARD M-75 (polymethyl methacrylate) base monomer bonded to silsesquioxane, a so-called graft 65 manufactured by Showa Denko K. K. was used as a standard chain has a number average molecular weight falling in a sample for a calibration curve. The other conditions are the range of 500 to 1,000,000. The more preferred range is 1,000 same as described above. US 7,256.243 B2 81 82 Example 1 structure is a term showing a partial structure in which three oxygen atoms are bonded to one silicon atom, that is,
A four neck flask of 50 ml equipped with a reflux condenser was charged with the compound (A-1) (1.2 g), Example 3 tetrahydrofuran (10 g) and triethylamine (1.6 g) and sealed 40 with dry nitrogen. Trimethylchlorosilane (2.2 g) was drop
(7-1) Ph Ph Ph \Si3S1Ns. is -O Ph HOS-1a O 1N1SMeSi-O - / OS-1S1 V s O-SiMe.1N1\ 1N1 OH 1N1 O n-1N MeSi-OV Sin O 9 SiMe3-N-O Sir Si Yo-si N-1 No p? o-1N?Ph \ Ph
Example 4 Example 5 (1-1-3) Ph Me Ph Ph Ph Br O <- Ns/ Me Br Me N1\o1 N1,Ns c/ isk Y sign 1.1\-" Me O - M O O Me O-n-O O-N-N-3 O sire 1 Si n so- O-SiMe. n1N1 O n-N,O Me Br p/ 'o-N/ Y, Br Me Ph Me Ph Example 6 was cut off by hydrolysis brought about by hydrofluoric acid treatment and that all terminating ends in the polymerization 6 8. 5,300 7,200 1.12 Example 20 55 (5-1) Ph Ph Synthesis of a Compound (3-2-1): Phenylsilsesquioxane Ph Ph having Silanol Obtained by using the Compound (3-1-1) as H-MeSi y/Oss-Si- - - SSs/ 60 no-'-O-s- \ . a Raw Materiald Q V O-SiMe-H A reactor having a Volume content of 100 ml equipped H-Me-Si-O -S; O O-SiMe-H with a dropping funnel and a thermometer was charged with S-ON Si s O-S the compound (3-1-1) (6 g) obtained in Example 1 and Ph O- No.M VPh tetrahydrofuran (50 ml), and it was sealed with dry nitrogen. 65 Ph Then, glacial acetic acid (2.4 g) was dropwise added thereto Ph in about 10 seconds while stirring to maintain a solution US 7,256.243 B2 91 92 Example 22 (7-2) Example 23 (1-1-4) US 7,256.243 B2 93 94 Example 24 Example 25 40 (10) (1-1-4) Me M Me 9N-1Nc Sin O-SiMe Me Br Sis-O1 O Br is Si Yo-si N-1- Me Ph o- No/ Me O Ph Ph O Ph 15 Example 28 Example 30 (1-1-3) Ph Ph Ph Me V O - O Ph M Br O SCsi- 6Ns/ Br Me N1\o1N1,Ns c; isk1. Y sign-1-o-1a1" Me O V O O O MeSi-O Sis O-SiMe. Me u-n- n-1N1 Sir so- n-1N1 O n-N,O Me Br p/ 'o-N/Si Y, Br Me Ph Me Ph Example 32 60 (11-2) 55 (2-1-1) wherein in the above formulas, R', RandR have the same O R. meanings as those of these codes in Formula (1-1), and M is a monovalent alkali metal atom; 60 (6) CH=CH-Z2-OH R RI (7) R1 O-. Elo , HO-Z2-CH,-(R)(R)SiN O Saos Si 6ss, O Si(R')(R)-CH-Z'-OH O V S. O HO-Z2-CH,-(R3)(R2)Si1 O v n he k"see-ch-z-oh R -1R1 No R1 R1 wherein Z in the above formulas has the same meaning as that of Z in Formula (2-1-1), and R', RandR in Formula (7) have the same meanings as those of these codes in (1-1) Formula (1-1); 2O R RI R1 R ps- ass,-S1 Si(R2)(R)-A Al-(R)(R)sils s1 No1 (8) 30 O R X---x wherein respective R's are groups independently selected from hydrogen, alkyl having a carbon atom number of 1 to R5 45 in which optional hydrogen may be substituted with 35 fluorine and in which optional —CH2— may be substituted wherein R, R and X" have the same meanings as those of with -O-, -CH=CH-, cycloalkylene or cycloalk h des in F la (2-1-1); and X is hal enylene, substituted or non-substituted aryl and arylalkyl these codes in Formula (2-1-1); an 1S nalogen. constituted from a Substituted or non-substituted aryl group and an alkylene group in which optional hydrogen may be 25. The production process as described in claim 24, 40 substituted with fluorine and in which optional —CH2— wherein all R's are the same group selected from alkyl may be substituted with —O—, —CH=CH- or cycloalky having a carbon atom number of 1 to 8 in which optional lene; RandR are groups independently selected from alkyl hydrogen may be substituted with fluorine and in which having a carbon atom number of 1 to 8, phenyl and cyclo optional —CH2— may be substituted with —O—, 45 hexyl, and A' is a group represented by Formula (2-1-1): —CH=CH cycloalkylene or cycloalkenylene, phenyl in which optional hydrogen may be substituted with halogen, (2-1-1) methyl or methoxy, non-substituted naphthyl and phenyla- O R. lkyl constituted from a phenyl group in which optional 2 | hydrogen may be substituted with fluorine, alkyl having a 50 -CH-Z2-O-C-C-X carbon atom number of 1 to 4, vinyl or methoxy and an alkylene group which has a carbon atom number of 1 to 8 and in which optional —CH2— may be substituted with wherein Z is a single bond or alkylene having a carbon atom —O , —CH=CH or cycloalkylene; when the phenyl or number of 1 to 18 or alkenylene having a carbon atom a phenyl group in the phenylalkyl has plural Substituents, the 55 number of 2 to 6, and optional —CH2— in these alkylene Substituents may be the same group or different groups; and and alkenylene may be substituted with —O : R is hydro R° and R are groups independently selected from alkyl gen, alkyl having a carbon atom number of 1 to 20, aryl having a carbon atom number of 1 to 8, phenyl and cyclo having a carbon atom number of 6 to 20 or arylalkyl having hexyl. 60 a carbonatom number of 7 to 20; R is alkyl having a carbon atom number of 1 to 20, aryl having a carbon atom number 26. The production process as described in claim 24, of 6 to 20 or arylalkyl having a carbon atom number of 7 to wherein all R's are phenyl, and R and R are methyl. 20; and X is halogen; 27. A production process for a silicon compound repre (6) (7) R RI R1 R O- - -9N HO-Z2-CH-(R)(R2)S. Si2OS-OSSS 2 ( )( Sin-si Rs. O O Si R1 wherein Z in the above formulas has the same meaning as that of Z in Formula (2-1-1), and R', RandR in Formula (7) have the same meanings as those of these codes in Formula (1-1); (8) O R4 X-C-C-X 65 wherein respective R's are groups independently selected from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with US 7,256.243 B2 111 112 fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk -continued enylene, substituted or non-substituted aryl and arylalkyl (5) constituted from a Substituted or non-substituted aryl group and an alkylene group in which optional hydrogen may be 5 R1 R substituted with fluorine and in which optional —CH2— "yes-l's J. : To 2y to 3 may be substituted with —O—, —CH=CH- or cycloalky H - (R)?ld 3v ?ld2\s:R' sis-si - O-s:1Y - O-SS No1 Si(R4)(R)-H lene; R and Rare groups independently selected from alkyl Oy VO having a carbon atom number of 1 to 8, phenyl and cyclo 1n.O 1 iin O hexyl; and A is a group represented by Formula (2-3-1): 10 H-(R)(R2)Si Sir O Iso- YSi(R2)(R)-H O V R RI R1 RI (2-3-1) (R), wherein R, R and R in the above formulas have the same meanings as those of these codes in Formula (1-3), and M wherein Z is alkylene which has a carbon atom number of is a monovalent alkali metal atom; 1 to 3 and in which optional —CH2— may be substituted with —O ; Z is a single bond or alkylene which has a a step in which the compound represented by Formula (5) is carbon atom number of 1 to 8 and in which optional reacted with a compound represented by Formula (2-3-2) to —CH2— may be substituted with —O , —COO or obtain the silicon compound represented by Formula (1-3): —OCO : R is alkyl having a carbon atom number of 1 to 3; a is an integer of 0 to 2: X is halogen; and a bonding 25 position of Z on the benzene ring is a metaposition or a para (2-3-2) position to a bonding position of Z, and a bonding position (R'), of R is an optional position excluding the respective bond ing positions of Z and Z: 30 5 (2-3-1) (R'), 10 wherein Z, Z, R” and a have the same meanings as those of these codes in Formula (2-4-1); X is halogen; and the wherein respective R's are groups independently selected 15 bonding positions of Zand R7 on the benzene ring are the from hydrogen, alkyl having a carbon atom number of 1 to same as the bonding positions thereof in Formula (2-4-1); 45 in which optional hydrogen may be substituted with fluorine and in which optional —CH may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk (9) S R8 enylene, substituted or non-substituted aryl and arylalkyl / constituted from a Substituted or non-substituted aryl group MI S-C-N and an alkylene group in which optional hydrogen may be V substituted with fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH- or cycloalky lene; R and Rare groups independently selected from alkyl 25 wherein RandR have the same meanings as those of these having a carbon atom number of 1 to 8, phenyl and cyclo codes in Formula (2-4-1); M' is a metal element of the first hexyl; and A is a group represented by Formula (2-4-1): group or the second group in the periodic table; and p is the same value as a valence of M'. 30 34. The production process as described in claim 33, (2-4-1) wherein all R's are the same group selected from alkyl (R), having a carbon atom number of 1 to 8 in which optional hydrogen may be substituted with fluorine and in which optional —CH2— may be substituted with —O—, -call--()—7 Z'-s -C-Ni 35 —CH=CH cycloalkylene or cycloalkenylene, phenyl in V which optional hydrogen may be substituted with halogen, R9 methyl or methoxy, non-Substituted naphthyl and phenyla lkyl constituted from a phenyl group in which optional wherein Z is alkylene which has a carbon atom number of hydrogen may be substituted with fluorine, alkyl having a 1 to 3 and in which optional —CH2— may be substituted 40 carbon atom number of 1 to 4, vinyl or methoxy and an with —O ; Z is a single bond or alkylene which has a alkylene group which has a carbon atom number of 1 to 8 carbon atom number of 1 to 8 and in which optional and in which optional —CH2— may be substituted with —CH2— may be substituted with —O , —COO or —O—, —CH=CH or cycloalkylene; when the phenyl or —OCO : R and R are independently hydrogen, alkyl a phenyl group in the phenylalkyl has plural Substituents, the having a carbon atom number of 1 to 12, cycloalkyl having 45 Substituents may be the same group or different groups; and a carbon atom number of 5 to 10 or aryl having a carbon R° and R are groups independently selected from alkyl atom number of 6 to 10, and R and R may be combined having a carbon atom number of 1 to 8, phenyl and cyclo with each other to form a ring together with N; R is alkyl hexyl. having a carbon atom number of 1 to 3; a is an integer of 0 35. The production process as described in claim 33, to 2; and a bonding position of Z on the benzene ring is a 50 wherein all R's are phenyl, and R and R are methyl. meta position or a para position to a bonding position of Z. 36. A production process for a silicon compound repre and a bonding position of R is an optional position exclud sented by Formula (1-1) characterized by carrying out a step ing the respective bonding positions of Z and Z: (g) and then a step (h): 55 (1-1) R1 ps- -O /R' 60 Al-(R3)(R2)Si Y-O-O-Sino- Si(R2)(R)-A No1 O V y O O Al-(R)(R2)Si 1n.Sis O1Y n in : 1cs:O D2, D3, Al RIA Yo-hsin,O-Si Y, S(R4)(R4)(R) (R)-A R1 R 65 R1 US 7,256.243 B2 115 116 wherein respective R's are groups independently selected from hydrogen, alkyl having a carbon atom number of 1 to 45 in which optional hydrogen may be substituted with (3-1) fluorine and in which optional —CH2— may be substituted with —O—, —CH=CH-, cycloalkylene or cycloalk 5 si- - - O enylene, substituted or non-substituted aryl and arylalkyl O1 O V constituted from a Substituted or non-substituted aryl group O S. e4M and an alkylene group in which optional hydrogen may be ns;Sir 1Nsyo-si1. O substituted with fluorine and in which optional —CH2— 10 R O NyO \R1 may be substituted with —O—, —CH=CH- or cycloalky RI lene; R and Rare groups independently selected from alkyl RI (3-2) having a carbon atom number of 1 to 8, phenyl and cyclo RI R' RI hexyl; and A' is a group represented by Formula (2-1-1): R -O 15 S2's i- tiss's -S Ois: V OH (2-1-1) y O O R. "sis-orills,( o-sin s-oilV —ch-z-o-c--x R R O RI R1 wherein Z is a single bond or alkylene having a carbon atom wherein R' in the above formulas has the same meaning as number of 1 to 18 or alkenylene having a carbon atom 25 that of R' in Formula (1-1), and M is a monovalent alkali number of 2 to 6, and optional —CH2— in these alkylene metal atom. and alkenylene may be substituted with —O : R is hydro 37. The production process as described in claim 36, gen, alkyl having a carbon atom number of 1 to 20, aryl wherein all R's are the same group selected from alkyl having a carbon atom number of 6 to 20 or arylalkyl having having a carbon atom number of 1 to 8 in which optional 30 hydrogen may be substituted with fluorine and in which a carbon atom number of 7 to 20; R is alkyl having a carbon optional —CH2— may be substituted with —O—, atom number of 1 to 20, aryl having a carbon atom number —CH=CH-, cycloalkylene or cycloalkenylene, phenyl in of 6 to 20 or arylalkyl having a carbon atom number of 7 to which optional hydrogen may be substituted with halogen, 20; and X" is halogen; methyl or methoxy, non-Substituted naphthyl and phenyla (R) (2-4-P) wherein Z is alkylene which has a carbon atom number of 10 1 to 3 and in which optional —CH2— may be substituted with —O : Z7 is alkylene which has a carbon atom number --(y,- 7 zi-p-s--N of 2 to 10 and in which optional —CH2— may be substi V tuted with —O , —COO or —OCO : R is alkyl R9 having a carbon atom number of 1 to 3; a is an integer of 0 15 to 2: X is halogen; a bonding position of Z on the benzene wherein Z is alkylene which has a carbon atom number of ring is a meta position or a para position to a bonding 1 to 3 and in which optional —CH2— may be substituted position of Z', and a bonding position of R is an optional with —O : Z7 is alkylene which has a carbon atom number position excluding the respective bonding positions of Z. of 2 to 10 and in which optional —CH2— may be substi and Z'; and P is a chain of a structural unit obtained by tuted with -O-, -COO– or - OCO ; R and R are polymerizing an addition-polymerizable monomer. independently hydrogen, alkyl having a carbon atom num 50. A polymer represented by Formula (P-4): ber of 1 to 12, cycloalkyl having a carbon atom number of 5 to 10 or aryl having a carbon atom number of 6 to 10, and Rand R may be combined with each other to form a ring 25 together with N; R is alkyl having a carbon atom number of 1 to 3; a is an integer of 0 to 2: a bonding position of Zon the benzene ring is a meta position or a para position to a bonding position of Z’, and a bonding position of R is an optional position excluding the respective bonding positions 30 of Z and Z'; and P' is a chain of a structural unit obtained by polymerizing an addition-polymerizable monomer. 51. The polymer as described in claim 47, wherein the addition-polymerizable monomer is at least one selected from the group of (meth)acrylic acid derivatives and the 35 group of Styrene derivatives. 52. The polymer as described in claim 48, wherein the wherein all R's are the same group selected from alkyl addition-polymerizable monomer is at least one selected having a carbon atom number of 1 to 8 in which optional from the group of (meth)acrylic acid derivatives and the hydrogen may be substituted with fluorine and in which group of Styrene derivatives. optional —CH2— may be substituted with —O—, 40 53. The polymer as described in claim 49, wherein the —CH=CH cycloalkylene or cycloalkenylene, phenyl in addition-polymerizable monomer is at least one selected which optional hydrogen may be substituted with halogen, from the group of (meth)acrylic acid derivatives and the methyl or methoxy, non-substituted naphthyl and phenyla group of Styrene derivatives. lkyl constituted from a phenyl group in which optional 54. The polymer as described in claim 50, wherein the hydrogen may be substituted with fluorine, alkyl having a 45 addition-polymerizable monomer is at least one selected carbon atom number of 1 to 4, vinyl or methoxy and an from the group of (meth)acrylic acid derivatives and the alkylene group which has a carbon atom number of 1 to 8 group of Styrene derivatives. and in which optional —CH2— may be substituted with —O , —CH=CH or cycloalkylene; when the phenyl or k k k k k