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(12) United States Patent (10) Patent No.: US 7.256.243 B2 Oikawa Et Al

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(12) United States Patent (10) Patent No.: US 7.256.243 B2 Oikawa Et Al 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
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