Isobutylene Polymer Having Unsaturated Group and Preparation

Europaisches Patentamt European Patent Office

Office europeen des brevets (11) EP 0 452 875 B2

(12) NEW EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) |nt CI.6: C08F 10/10, C08F 2/42 of the opposition decision: 18.08.1999 Bulletin 1999/33

(45) Mention of the grant of the patent: 09.08.1995 Bulletin 1995/32

(21) Application number: 91106042.4

(22) Date of filing: 16.04.1991

(54) Isobutylene polymer having unsaturated group and preparation thereof Isobutylenpolymer mit ungesattigter Gruppe und seine Herstellung Polymere de I'isobutylene ayant un groupe insature et sa preparation

(84) Designated Contracting States: (74) Representative: BE CH DE ES FR GB IT LI NL SE Hansen, Bernd, Dr. Dipl.-Chem. et al Hoffmann Eitle, (30) Priority: 16.04.1990 JP 10102990 Patent- und Rechtsanwalte, 29.11.1990 JP 33636490 Postfach 81 04 20 81904 Miinchen (DE) (43) Date of publication of application: 23.10.1991 Bulletin 1991/43 (56) References cited: EP-A- 0 265 053 EP-B- 0 322 241 (73) Proprietor: Kanegafuchi Chemical Industry Co., CA-A- 467 049 GB-A- 1 059 580 Ltd. US-A- 4 31 6 973 US-A- 4 327 201 Kita-ku Osaka-shi Osaka-fu (JP) US- A- 4 524 1 88 US-A- 4 758 63 1 US-A- 4 929 683 (72) Inventors: • Noda, Koji Remarks: Kobe-shi, Hyogo-ken (JP) The file contains technical information submitted • Fujisawa, Hiroshi after the application was filed and not included in this Kobe-shi, Hyogo-ken (JP) specification • Yonezawa, Kazuya Kobe-shi, Hyogo-ken (JP)

CM DO 10 Is- 00 CM IO ^- o a. LU

Printed by Jouve, 75001 PARIS (FR) EP 0 452 875 B2

Description

[0001] The present invention relates to an isobutylene polymer having an unsaturated group and a process for preparing the same. 5 [0002] An isobutylene polymer having more than one unsaturated group per molecule on the average is cross linked and cured to produce a rubbery cured material. Such polymer can be modified by introducing a cross-linkable silicon group to form a moisture-curable polymer as disclosed in U.S. Patent No. 4,904,732 and Japanese Patent Kokai Publication No. 6041/1988. [0003] The isobutylene polymer having more than one unsaturated group per molecule on the average is disclosed 10 in U.S. Patent Nos. 3,644,315 and 4,524,187 and it is prepared by copolymerizing isobutylene and a compound having a conjugated double bond, so that it has double bonds in polymer chains and is poor in weather resistance, chemical resistance and reactivity. [0004] U.S. Patent Nos. 4,31 6,973 and 4,758,631 and Japanese Patent Kokai Publication No. 105005/1 988 disclose polymers having an unsaturated group at a chain end. The polymer of U.S. Patent Nos. 4,316,973 and 4,758,631 is is prepared by an Inifer method comprising cationically polymerizing isobutylene in the presence of 1 ,4-bis(a-chloroiso- propyl)benzene as a polymerization initiating and chain transfer agent and BCI3 as a catalyst and further reacting a formed polymer having a chlorine atom at a chain end. [0005] A polymer disclosed in Japanese Patent Kokai Publication No. 105005/1988 is prepared by synthesizing an isobutylene polymer having chlorine atoms at both chain ends by the Inifer method and, just after synthesis or purifi- 20 cation, reacting the isobutylene polymer with allyltrimethylsilane to obtain a polymer having allyl groups at both chain ends. [0006] However, the polymers disclosed in U.S. Patent No. 4,316,973 and Japanese Patent Kokai Publication No. 105005/1988 require multiple steps for the production and/or expensive raw materials. [0007] CA-467 049 discloses a copolymer of isoolefins (in particular isobutylene) with non-conjugated diolefins of 25 the formula CH2=CR-Cn-H2n.x wherin R is an alkyl group (preferably methyl), n is any whole number greater than 2 and x is any uneven number. The number of these unconjugated diene units is according to the examples in the order of 4.7 to 6.5. [0008] EP-B-0 322 241 relates to viscous polybutenes, having a number average molecular weight of 500 to 5000 and a total terminal double bond content of at least 40% based on the total theoretic unsaturation of the polybutene. 30 "Terminal" means terminal disubstituted or terminal trisubstituted. The polybutene product obtained is further characterized by the proportionate distribution of terminal disubstituted double bonds and tetrasubstituted double bonds present therein. Normally one does not detect the presence of monosubstituted double bonds in polybutene molecules like that of EP-B-0 322 241.

35 SUMMARY OF THE INVENTION

[0009] One object of the present invention is to provide a novel isobutylene polymer having an unsaturated group. [0010] Another object of the present invention is to provide a process for easily preparing such isobutylene polymer at a low cost. 40 [0011] According to a first aspect of the present invention, there is provided an isobutylene polymer comprising 1,1 to 5 units per molecule on the average of the formula

CH2 - ChHj- 45

Q (I)

50 HC=CH2

wherein Q is a C-|-C30 divalent organic group and which has the unit of formula (I) at the polymer chain end(s). [0012] According to a second aspect of the present invention, there is provided a process for preparing the isobuty- 55 lene polymer having an unsaturated group as defined above, which comprises polymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated diene in the presence of a Lewis acid and a polymerization initiating and chain transfer agent of formula (III) as defined below. [0013] According to a third aspect of the present invention, there is provided a process for prepanng the isobutylene

2 EP 0 452 875 B2

polymer having an unsaturated group as defined above which comprises polymerizing a cationically polymerizable monomer containing isobutylene in the presence of a Lewis acid and a polymerization initiating and chain transfer agent of formula (III) as defined below, and reacting the resulting polymer with a non-conjugated diene.

5 Figs. 1 and 2 are the I R spectrum and the 1H-NMR spectrum of the polymer prepared in Example 1 , respectively and Figs. 3 and 4 are the I R spectrum and the 1H-NMR spectrum of the polymer prepared in Example 8, respectively.

[0014] The group Q may be a straight or branched divalent organic group and preferably a straight or branched alkylene group such as a hexylene group. 10 [0015] The isobutylene polymer of the present invention is characterized in that it comprises the unit of the formula (I). The isobutylene polymer of the present invention usually has a number average molecular weight of from 500 to 500,000, preferably from 1000 to 50,000 and comprises at least 1.1 and not more than 5 units of the formula (I) on the average per molecule. [0016] The unit of the formula (I) is present at the end(s) of the polymer chain. Preferably, the isobutylene polymer is of the present invention has no unsaturated group in the polymer chain in view of properties of the polymer such as weather resistance. [0017] Typically, the isobutylene polymer of the present invention can be prepared by the following two processes.

Process 1 20 [0018] A cationically polymerizable monomer containing isobutylene and a non-conjugated diene are polymerized in the presence of a Lewis acid and a polymerization and chain transfer agent of formula (III) as defined below.

Process 2 25 [0019] A cationically polymerizable monomer containing isobutylene is polymerized in the presence of a Lewis acid and a polymerization and chain transfer agent of formula (III) as defined below, and then the resulting polymer is reacted with a non-conjugated diene. [0020] The "cationically polymerizable monomer" herein used is intended to include not only a pure isobutylene 30 monomer but also a monomer mixture comprising 50 % by weight or more of isobutylene and 50 % by weight or less of at least one other cationically polymerizable monomer which is copolymerizable with isobutylene. [0021] The other cationically polymerizable monomer copolymerizable with isobutylene includes C3-C12 olefins, conjugated dienes, vinyl ethers, aromatic vinyl compounds, vinylsilanes. Among them, the C3-C12 olefins and conjugated dienes are preferred. In view of weather resistance of the polymer, the olefins other than the conjugated dienes are 35 preferred. [0022] Specific examples of the other cationically polymerizable monomers copolymerizable with isobutylene are propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, vinylcy- clohexane, butadiene, isoprene, cyclopentadiene, methylvinylether, ethylvinylether, isobutylvinylether, styrene, a- methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, p-pinene, indene, vinyltrichlorosilane, vinylmeth- 40 yldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, di- vinyldimethoxysilane, divinyldimethylsilane, 1 ,3-divinyl-1 ,1 ,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsi- lane, y-methacryloyloxypropyltrimethoxysilane, y-methacryloyloxypropylmethyldimethoxysilane. Among them, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene and cyclopentadiene are preferred. They may be used independently or as a mixture of two or more of them. 45 [0023] The non-conjugated diene to be used in the present invention is a diene of the formula:

CH2=CH-Q-CH=CH2 (II)

wherein Q, is the same as defined above. [0024] As the non-conjugated diene, any of the compounds of the formula (II) can be used. Examples of the non- conjugated diene are 1 ,4-pentadiene, 1 ,5-hexadiene, 1 ,6-heptadiene, 1 ,7-octadiene, 1 ,8-nonadiene, 1 ,9-decadiene, 1,19-dodecadiene, 1 ,5,9-decatriene. Among them, a,co-dienes such as 1 ,4-pentadiene, 1 ,5-hexadiene, 1,6-heptadiene, 1 ,7-octadiene, 1 ,8-nonadiene, 1 ,9-decadiene and 1 ,19-dodecadiene are preferred in view of activity of the functional groups contained in the prepared polymer. [0025] The Lewis acid is used as a polymerization catalyst in the process 1 and as a polymerization catalyst and also as a reactant in the process 2 and includes a compound of the formula:

3 EP 0 452 875 B2

MX'p

wherein M is a metal atom, X' is a halogen atom, and p is a valency of the metal M (e.g. AICI3, SnCI4, TiCI4, VCI5, 5 FeCI3, BF3) and organic aluminum compounds (e.g. (C2H5)2AICI, C2H5AICI2). Among them, SnCI4, TiCI4, (C2H5)2AICI and C2H5AICI2 are preferred. [0026] In the process 1, the amount of the Lewis acid is from 0.1 to 10 times, more preferably from 0.2 to 5 times the weight of the non-conjugated diene to be polymerized with isobutylene. [0027] In the process 2, the amount of the Lewis acid is from 0.001 to 0.1 time the weight of isobutylene, and 0.01 10 to 5 times the weight of the non-conjugated diene. [0028] In either of the processes 1 and 2, a polymerization initiator is present in a polymerization system. As the polymerization initiator, water contained in the system in atrace amount is effectively used. In addition, a polymerization initiating and chain transfer agent is used. [0029] An example of the polymerization initiating and chain transfer agent is an organic compound of the formula: 15

R6-C-X (III) 20 is

wherein X is a halogen atom or a group of the formula: RCOO-or RO- in which R is a monovalent organic group, R4, 25 and R5 are the same or different and each a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R6 is a polyvalent aromatic group or a substituted or unsubstituted polyvalent hydrocarbon group, provided that when R6 is a polyvalent hydrocarbon group, at least one of R4 and R5 is not a hydrogen atom. More concretely, the organic compound (III) includes a compound of the formula:

30 AYn (IV)

wherein A is a group having 1 to 4 aromatic groups, Y is a group of the formula: 35 R10

-C-X (V) 40 I R11

in which X is the same as defined above, R10 and R11 are the same and different and each a hydrogen atom or a C-,- C20 monovalent hydrocarbon group and is bonded to an aromatic group, and n is an integer of 1 to 6; a compound of the formula:

BZm (VI)

wherein B is a C4 to C40 hydrocarbon group, Z is a halogen atom or a group of the formula: RCOO- or RO- in which R is the same as defined above and is bonded to a tertiary carbon atom, and m is an integer of 1 to 4; and an oligomer comprising a-halostyrene units. These compounds may be used independently or as a mixture of two or more of them. [0030] In the formula (IV), the group A having 1 to 4 aromatic groups may be a group formed through a condensation reaction or a non-condensation type group. Specific examples of the group having the aromatic group(s) are a monoto hexa-valent phenyl group, a biphenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a pyrene group and a group of the formula: Ph-(CH2)€-Ph in which Ph is a phenyl group and € is an integer of 1 to 10.

4 EP 0 452 875 B2

The group having the aromatic group(s) may be substituted with a C-|-C20 straight or branched aliphatic hydrocarbon group, or a group having a functional group such as a hydroxyl group, an ether group or a vinyl group. [0031] In the compound (VI), Z may be a halogen atom (e.g. F, CI, Br and I), or the RCOO- or RO- group, which is bonded to a tertiary carbon atom, and B may be a C4 to C40 hydrocarbon group, preferably an aliphatic hydrocarbon group. When the number of carbon atoms in the group B is smaller than 4, a carbon atom to which the halogen atom or the RCOO- or RO- group is bonded is not a tertiary carbon atom, so that polymerization difficultly proceeds. [0032] Examples of the oligomer comprising the a-halo-styrene units as a polymerization initiating and chain transfer agent are an oligomer of a-chlorostyrene and an oligomer prepared by copolymerizing a-chlorostyrene and a monomer copolymerizable therewith. [0033] As the polymerization initiating and chain transfer agent, the compound (II) having at least groups selected, from the group consisting of halogen atoms, RCOO- groups or RO- groups or the compound (II) having at least one group, selected from the group consisting of halogen atoms, RCOO-groups or RO- groups and at least one other reactive functional group is effective since the number of functional groups in the produced polymer is increased. [0034] Specific examples of the polymerization initiating and chain transfer agent are:

CHo CH- CH3 C(CH3)3

x-c-< O )-c-x

CH, CH-,, CH3 CX(CH3)2,

CH3 CX(CH3)2 CH- CH-

x-c-< O K O )-c-x

CH3 CX(CH3)2, CH- CH3,

CH- CH-

X-C-< O VcK9CK9CH,-< O )-C-X

CH- CHn,

CH- CH- CH-

X-C-CH2CH2-C-X CH3-C-X

CH- CHn, CH- EP 0 452 875 B2

(n-C8H1?) (n-C8H17)

X-C-CH2CH2CH2CH2-C-X

(n-C8H17) (n-C8H17),

CH- CH- CK-

X-C-CH2CH2-C-CH2CH2-C-X

CH- CH- wherein X is the same as defined above; halogen atom-containing organic compounds such as oligomers of a-chlorostyrene and organic compounds having the RCOO-group. Among them, are preferred halogen atom-containing organic compounds having a group: -C(CH3)2CI or -C(CH3)2Br which easily liberates a stable carbon cation such as

CH- CH- CH- CH-

ci-c-< O )-c-ci Br-C-( O )-C-3r

CH- CH- CH- CH-,

CH3 CC1(CH3)2

CI -C-/Oy (Compound A),

CH3 CC1(CH3)2

CH3 C(CH3)3

ci-c^oJ>

CH3 CC1(CH3)2,

CH3 CH3

Cl-C-^0^)-CH2CH2-^0^)-C-CI

CH3 CH3 EP 0 452 875 B2

CH3 CH3

Cl-C-^Q^-CH2CH2CH2-^0^-C-Cl

CH3 CH3 ,

10 CH, CH, I I Cl-C C-Cl I I CH3 CH3 / 15

and

CH3 CH3 CK3

C1-C-CH2CH2-C-CH2CH2-C-C1

CH3 CI CH- 25

organic compounds having a CH3COO- group such as 30

CH, CH, CH, I I I CH-,COO-C-CH9-C-CH,-C-0-COCH-, 35 III CH3 CH3 CH3

40 CH, CH, CH, I I I CH3COO-C-CH2-C-CH2-C-0-COCH3

CH, 0 CH, 45 I c=o

CH3 50

CH, CH, 1 r\ 1 CH3COO-C-(0)-C-0-COCH3

CH3 CH3

7 EP 0 452 875 B2 and

C(CH3)2-0-COCH3

CH3COO-C

C(CH: 2-0-COCH3 and organic compounds having a CH30- group such as

CH,3 CH,3 CH,3 I I I CH,0-C-CH7-C-CH,-C-0CH I. I. I CH3 CH3

and

C(CH3)2-OCH3

CH,0-C-( O

CH3 C(CH3)2-OCH3

[0035] The above compounds may be used independently or as a mixture of two or more of them. [0036] A molecular weight of the produced polymer can be adjusted by controlling an amount of the above polymerization initiating and chain transfer agent or residual water in the polymerization system. In general, the polymerization initiating and chain transfer agent is used in an amount of from 0.01 to 20 % by weight, preferably from 0.1 to 1 0 % by weight based on the weight of the cationically polymerizable monomer containing isobutylene. [0037] In the present invention, as a polymerization medium in the process 1 or as a polymerization and reaction medium in the process 2, a hydrocarbon solvent such as an aliphatic hydrocarbon or a halogenated hydrocarbon may be used. Among them, the halogenated hydrocarbon, in particular, chlorinated hydrocarbon is preferred. Specific examples of the aliphatic hydrocarbon are pentane and hexane, and specific examples of the halogenated hydrocarbon are chloromethane, chloroethane, methylene chloride, 1,1-dichloroethane, chloroform and 1 ,2-dichloroethane. They may be used independently or as a mixture of two or more of them. In addition, a small amount of other solvent such as an acetate (e.g. ethyl acetate) or an organic compound having a nitro group (e.g. nitroethane) may be used. [0038] There is no specific limitation on procedures for carrying out the process of the present invention, and any of conventional polymerization methods can be used. For example, the process 1 can be carried out by a batchwise method in which the polymerization solvent, the monomer(s), the non-conjugated diene, the catalyst and optionally the polymerization initiating and chain transfer agent are successively charged into a reactor, or a continuous method in which the polymerization solvent, the monomer, the non-conjugated diene, the catalyst and optionally the polymerization initiating and chain transfer agent are continubusly supplied to proceed the polymerization and removing the resulting polymer continuously. [0039] Also, the process 2 can be carried out batchwise or continuously as in the case of the process 1 except that

8 EP 0 452 875 B2

the non-conjugated diene is reacted after polymerization. [0040] In the processes 1 and 2 of the present invention, a polymerization temperature is usually from +10 to -80°C, preferably from 0 to -40°C. A polymerization time is usually from 0.5 to 120 minutes, preferably from 1 to 60 minutes. A monomer concentration is usually from 0.1 to 8 mole/liter, preferably from 0.5 to 5 mole/liter. 5 [0041] In the process 2, a reaction time after the supply of the non-conjugated diene is preferably from 10 to 300 minutes. [0042] In the process 1 , an amount of the non-conjugated diene which is supplied before the polymerization reaction of the cationically polymerizable monomer containing isobutylene is from 0.01 to 1 mole per one mole of the isobutylene monomer, and the supplied non-conjugated diene is uniformly distributed in the polymerization system by stirring. In 10 the process 2, an amount of the non-conjugated diene which is supplied after the polymerization is from 0.01 to 1 mole per one mole of the isobutylene monomer, and the added diene is uniformly distributed in the reaction system by stirring. [0043] In the process 1, the polymerization reaction is terminated preferably by the addition of an alcohol such as methanol in view of easiness of post-treatment. In the process 2, the reaction after the addition of the non-conjugated diene is stopped preferably by the addition of the alcohol. The polymerization reaction in the process 1 or the reaction is in the process 2 may be stopped by any of other conventional methods, or may not be stopped in some cases. [0044] By the above processes 1 and 2, the isobutylene polymer comprising more than one unit (I) per molecule on the average and having a number average molecular weight of 500 to 500,000 is produced. By the process 2, more than one units (I) on the average may be introduced at the molecular ends. [0045] In the isobutylene polymers prepared by the processes 1 and 2, substantially the same number of the func- 20 tional groups are introduced when the amounts of the raw materials are substantially the same as seen from the results of Examples described below. Then, by the process 1 , the units (I) may be introduced at the molecular ends. [0046] The novel isobutylene polymer of the present invention can be easily prepared as described above at a low cost. [0047] Since the polymer of the present invention is prepared using no conjugated diene, it has no olefinically un- 25 saturated bond which may be formed through 1 ,4-addition, so that the polymer has good weather resistance or other properties. [0048] The isobutylene polymer of the present invention can be used as a cross-linkable material as such. In addition, the functional groups in the polymer can be converted to other groups such as a hydroxyl group, an amino group, an alkoxysillyl group, a hydrogensilyl group. 30 [0049] By the process for preparing the isobutylene polymer of the present invention, more than one unsaturated groups on the average are easily introduced in the polymer. [0050] The present invention will be illustrated by the following Examples.

Example 1 35 [0051] A 100 ml pressure-proof glass autoclave, which was equipped with an agitating blade and a three-way stop cock and connected to a vacuum line, was dried by heating it at 100°C for 1 hour while evacuating it through the vacuum line. After cooling down to room temperature, nitrogen gas was introduced in the autoclave up to an atmospheric pressure through the three-way stop cock. 40 [0052] Methylene chloride (40 ml) which had been dried over calcium hydride as a main solvent was introduced with an injector while flowing the nitrogen gas from the three-way stop cook. Thereafter, distilled and purified 1,9-decadiene (20 mmol) was added and then a solution (10 ml) of tricumyl chloride (TCC: above Compound A) (3 mmol) dissolved in methylene chloride was added. [0053] To the three-way stop cock, a glass made liquefied gas collector having a needle valve, isobutylene (7 g), 45 which had been dried by passing it through a column filled with barium oxide, was charged, and the collector was connected to the three-way stop cock. The main part of the autoclave was dipped in a dry ice/acetone bath at -70°C for 1 hour while stirring the content in the autoclave. Thereafter, the autoclave interior was evacuated to reduced pressure through the vacuum line, and the needle valve was opened to introduce isobutylene from the collector to the autoclave. Then, the interior pressure of the autoclave was increased to the atmospheric pressure by introducing the so nitrogen gas through the three-way stop cock, and the autoclave content was cooled for 1 hour while stirring, during which the autoclave temperature rose to -30°C. [0054] Then, TiCI4 (3.2 g, 10 mmol) was added through the three-way stop cock to initiate polymerization. After 60 minutes, methanol, which had been cooled to lower than 0°C, was added to terminate the reaction. [0055] The reaction mixture gas poured in a flask, and unreacted isobutylene, methylene chloride, 1 ,9-decadiene 55 and methanol were evaporated off. The residual polymer was dissolved in n-hexane (100 ml), and the solution was washed with water till washing water became neutral. Thereafter, the n-hexane solution was concentrated to 20 ml and poured in acetone (300 ml) to precipitate the polymer. [0056] The polymer was redissolved in n-hexane (1 00 ml) and dried over anhydrous magnesium»sulfate. After filtra-

9 EP 0 452 875 B2

tion, n-hexane was evaporated off under reduced pressure to obtain an isobutylene polymer. [0057] The yield of the polymer was calculated from a polymer weight, Mn and Mw/Mn were measured by GPC, and a terminal structure of the polymer was defined by measuring 1H-NMR (300 MHz) of the polymer (see Fig. 2) and comparing strengths of resonance signals of protons assigned to respective structures. The results are shown in Table 5 2. [0058] The IR spectrum of the obtained polymer is shown in Fig. 1 .

Examples 2 to 6

10 [0059] In the same manner as in Example 1 but changing the polymerization conditions such as the use of the polymerization initiating and chain transfer agent and/or the kind and amount of the polymerization catalyst as shown in Table 1 , a polymer was prepared and analyzed. The results are shown in Table 2.

Comparative Example 1 15 [0060] In the same manner as in Example 1 but using no non-conjugated diene, a polymer was prepared and analyzed. The results are shown in Table 2.

Table 1 polymerization initiating and chain Polymerization Non-conjugated diene transfer agent catalyst Example No. Kind Amount (mmol) Kind Amount (mmol) 1 TCC 3 TiCI4 1,9-Decadiene 20 2 TCC 3 TiCI4 1,9-Decadiene 10 3 TCC 3 TiCI4 1,9-Decadiene 5 4 TCC 3 SnCI4 1,9-Decadiene 20 5 — - TiCI4 1,9-Decadiene 20 6 — - TiCI4 1,5-Hexadiene 20 Com.1 TCC 3 TiCI4

35 Table 2 Number of functional groups*) Example No. Yield (%) No. Av. Molecular Molecular weight -CH=CH2 -CH=C(CH3)2 -C(CH3)2CI weight distribution 1 90 5800 2.40 4.7 0.1 2 95 7800 2.75 3.6 0.1 3 95 6700 2.80 2.4 0.1 4 92 6500 2.60 6.1 0.2 5 94 9600 3.10 4.2 0.3 6 90 7600 2.95 3.5 0.2 Com.1 95 5100 3.05 0 0.4 2.0 Note: The number of the functional groups per one molecule.

Example 7

55 [0061] A 100 ml pressure-proof glass autoclave, which was equipped with an agitation blade and a three-way stop cock and connected to a vacuum line, was dried by heating it at 100°C for 1 hour while evacuating it through the vacuum line. After cooling down to room temperature, nitrogen gas was introduced in the autoclave up to an atmospheric pressure through the three-way stop cock.

10 EP 0 452 875 B2

[0062] Methylene chloride (40 ml) which had been dried over calcium hydride as a main solvent was introduced with an injector while flowing the nitrogen gas from the three-way stop cock. Thereafter, a solution (10 ml) of tricumyl chloride (TCC: above Compound A) (3 mmol) dissolved in methylene chloride was added. [0063] To the three-way stop cock, a glass made liquefied gas collector having a needle valve, isobutylene (7 g), 5 which had been dried by passing it through a column filled with barium oxide, was charged, and the collector was connected to the three-way stop cock. The main part of the autoclave was dipped in a dry ice/acetone bath at -70°C for 1 hour while stirring the content in the autoclave. Thereafter, the autoclave interior was evacuated to reduced pressure through the vacuum line, and the needle valve was opened to introduce isobutylene from the collector to the autoclave. Then, the interior pressure of the autoclave was increased to the atmospheric pressure by introducing the 10 nitrogen gas through the three-way stop cock, and the autoclave content was cooled for 1 hour while stirring, during which the autoclave temperature rose to -30°C. [0064] Then, TiCI4 (3.2 g, 10 mmol) was added through the three-way stop cock to initiate polymerization. After 60 minutes, distilled and purified 1 ,9-decadiene (20 mmol) was added and the reaction was continued at -30°C for 60 minutes. Thereafter, methanol, which had been cooled to lower than 0°C, was added to terminate the reaction. 15 [0065] The reaction mixture was poured in a flask, and unreacted isobutylene, methylene chloride, 1 ,9-decadiene and methanol were evaporated off. The residual polymer was dissolved in n-hexane (100 ml), and the solution was washed with water till washing water became neutral. Thereafter, the n-hexane solution was concentrated to 20 ml and poured in acetone (300 ml) to precipitate the polymer. [0066] The polymer was redissolved in n-hexane (1 00 ml) and dried over anhydrous magnesium sulfate. After filtra- 20 tion, n-hexane was evaporated off under reduced pressure to obtain an isobutylene polymer. [0067] An yield of the polymer was calculated from a polymer weight, Mn and Mw/Mn were measured by GPC, and a terminal structure of the polymer was defined by measuring 1H-NMR (300 MHz) of the polymer (see Fig. 4) and comparing strengths of resonance signals of protons assigned to respective structures. The results are shown in Table 4. 25 [0068] The I R spectrum of the obtained polymer is shown in Fig. 3.

Examples 8 to 12

[0069] In the same manner as in Example 1 but changing the polymerization conditions such as the use of the 30 polymerization initiating and chain transfer agent and/or the kind and amount of the polymerization catalyst as shown in Table 3, a polymer was prepared and analyzed. The results are shown in Table 4.

Comparative Example 2

35 [0070] In the same manner as in Example 7 but using no non-conjugated diene, a polymer was prepared and analyzed. The results are shown in Table 2.

Example 13

40 [0071] The isolated and purified polyisobutylene having tertiary chlorinated terminals obtained in Comparative Ex- ample 2 (5 g) was dissolved in methylene chloride (40 ml) which had been dried over calcium hydride. To the solution, 1 ,9-decadiene (20 mmol) was added. After cooling down to -30°C, TiCI4 (5 mmol) was added to the solution and stirring was continued for 60 minutes. After terminating the reaction, the polymer was purified and analyzed as in Example 7. The results are also shown in Table 4. 45 Table 3 polymerization initiating and chain Polymerization Non-conjugated diene transfer agent catalyst Example No. Kind Amount (mmol) Kind Amount (mmol) 7 TCC 3 TiCI4 1,9-Decadiene 20 8 TCC 3 TiCI4 1,9-Decadiene 10 9 TCC 3 TiCI4 1,9-Decadiene 5 10 TCC 3 SnCI4 1,9-Decadiene 20 11 — - TiCI4 1,9-Decadiene 20

11 EP 0 452 875 B2

Table 3 (continued) polymerization initiating and chain Polymerization Non-conjugated diene transfer agent catalyst Example No. Kind Amount (mmol) Kind Amount (mmol) 12 — - TiCI4 1,5-Hexadiene 20 Com.2 TCC 3 TiCI4 13 TCC 3 TiCI4 1,9-Decadiene 20

Table 4 Example No. Yield (%) No. Av. Molecular Molecular weight Number of functional groups*) weight distribution -CH=CH2 -CH=C(CH3)2 -C(CH3)2CI 7 92 6500 2.65 4.1 0.1 8 90 5700 2.45 3.4 0.2 9 92 6600 2.90 2.5 0.1 10 95 5600 2.55 4.6 0.1 11 92 5900 3.20 4.0 0.2 12 95 6700 2.80 3.2 0.1 Com.1 95 5100 3.05 0 0.4 2.0 13 99 5200 3.08 2.8 0.1 Note: The number of the functional groups per one molecule.

Claims

1 . An isobutylene polymer comprising 1,1 to 5 units per molecule on the average of the formula

CH2-CH^-

Q (I)

HC=CH2

wherein Q is a C-|-C30 divalent organic group and which has the unit of formula (I) at the polymer chain end(s).

2. The isobutylene polymer according to claim 1, which has a number average molecular weight of from 500 to 500000.

3. The isobutylene polymer according to claim 1 , which has substantially no unsaturated group in the polymer chain.

4. A process for preparing the isobutylene polymer according to claim 1 , which comprises polymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated diene in the presence of a Lewis acid and a polymerization initiating and chain transfer agent having the formula (III)

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R6-C-X (III) i R5

wherein X is a halogen atom or a group of the formula: RCOO- or RO- in which R is a monovalent organic group, R4 and R5 are the same or different and each a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R6 is polyvalent aromatic group or a substituted or unsubstituted polyvalent hydrocarbon group, provided that when R6 is a polyvalent hydrocarbon group, at least one of R4 and R5 is not a hydrogen atom.

5. The process according to claim 4, wherein said non-conjugated diene is a diene of the formula

CH2=CH-Q-CH=CH2 (II)

wherein Q is a C1-C30 divalent organic group.

6. A process for preparing the isobutylene polymer according to claim 1 which comprises polymerizing a cationically polymerizable monomer containing isobutylene in the presence of a Lewis acid and a polymerization initiating and chain transfer agent and reacting the resulting polymer with a non-conjugated diene of the formula

R6-C-X (III) i R5

wherein X is halogen atom or a group of the formula: RCOO- or RO- in which R is a monovalent organic group, R4 and R5 are the same or different and each a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R6 is a polyvalent aromatic group or a substituted or unsubstituted polyvalent hydrocarbon group, provided that when R6 is a polyvalent hydrocarbon group, at least one of R4 and R5 is not a hydrogen atom.

Patentanspriiche

1. Isobutylenpolymer umfassend im Durchschnitt 1,1 bis 5 Einheiten pro Molekul der Formel :

-(CH2-CH

Q (I)

HC=CH2

worin Q eine zweiwertige organische C-|-C30-Gruppe ist, das die Einheit der Formel (I) am (an den) Ende(n) der Polymerkette aufweist.

2. Isobutylenpolymer gemaB Anspruch 1 mit einem Zahlendurchschnitts-Molekulargewicht von 500 bis 500.000.

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3. Isobutylenpolymer gemaB Anspruch 1, das in der Polymerkette im wesentlichen keine ungesattigte Gruppe hat.

4. Verfahren zur Herstellung des Isobutylenpolymers gemaB Anspruch 1 , umfassend das Polymerisieren eines kat- ionisch polymerisierbaren Monomers, enthaltend Isobutylen und eines nicht konjugierten Diens, in Gegenwart einer Lewissaure und eines die Polymerisation initiierenden und kettenubertragenden Mittels der Formel (III):

I R6 - C - X (III)

worin X ein Halogenatom oder eine Gruppe der Formel RCOO- oder RO- ist, worin R eine einwertige organische Gruppe ist, R4 und R5 gleich oder verschieden sind und jeweils ein Wasserstoffatom oder eine substituierte oder unsubstituierte einwertige Kohlenwasserstoffgruppe sind, und R6 eine mehrwertige aromatische Gruppe oder eine substituierte oder unsubstituierte mehrwertige Kohlenwasserstoffgruppe ist mit dem Proviso, dal3 dann, wenn R6 eine mehrwertige Kohlenwasserstoffgruppe ist, wenigstens einer von R4 und R5 kein Wasserstoffatom ist.

5. Verfahren gemaB Anspruch 4, worin das genannte nicht konjugierte Dien ein Dien der Formel

CH2=CH-Q-CH=CH2 (II)

ist, worin Q eine zweiwertige organische C1-C30-Gruppe ist.

6. Verfahren zur Herstellung des Isobutylenpolymers gemaB Anspruch 1 , umfassend das Polymerisieren eines kat- ionisch-polymerisierbaren Monomers, enthaltend Isobutylen in Gegenwart einer Lewissaure und eines die Poly- merisation initiierenden und kettenubertragenden Mittels der Formel

R6 - C - X (III) is

wobei X ein Halogenatom oder eine Gruppe der Formel: RCOO- oder RO- bedeutet, worin R eine einwertige organische Gruppe ist, R4 und R5, die gleich oder verschieden sind, jeweils ein Wasserstoffatom oder eine substituierte oder unsubstituierte einwertige Kohlenwasserstoffgruppe bedeuten, und R6 eine mehrwertige aromatische Gruppe oder eine substituierte oder unsubstituierte mehrwertige Kohlenwasserstoffgruppe bedeutet, mit dem Proviso, dal3 dann, wenn R6 eine mehrwertige Kohlenwasserstoffgruppe ist, wenigstens einer von R4 und R5 kein Wasserstoffatom ist, und Umsetzen des erhaltenen Polymers mit einem nicht konjugierten Dien.

Revendications

1 . Polymere d'isobutylene comprenant en moyenne par molecule de 1 , 1 a 5 motifs de Formule :

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-(CH2-CH-7-

(I)

HC=CH2

dans laquelle Q represente un groupe organique divalent en C-|-C30 et qui presente le motif de Formule (I) a ou aux extremite(s) de la chaTne du polymere.

Polymere d'isobutylene selon la revendication 1 , qui presente une masse moleculaire moyenne en nombre de 500 a 500 000.

Polymere d'isobutylene selon la revendication 1, qui ne contient pratiquement aucun groupe insature dans la chame du polymere.

Procede de preparation du polymere d'isobutylene selon la revendication 1, qui comprend I'etape consistant a polymeriser un monomere cationiquement polymerisable contenant de I'isobutylene et un diene non-conjugue en presence d'un acide de Lewis, et d'un initiateur de polymerisation et agent de transfer! de chaTne ayant la formule :

R4 (in) RG-C-X i R5

dans laquelle X represente un atome d'halogene ou un groupe de formule : RCOO- ou RO- dans laquelle R represente un groupe organique monovalent, R4 et R5 sont identiques ou differents et represented chacun un atome d'hydrogene ou un groupe hydrocarbone monovalent substitue ou non, et R6 represente un groupe aromatique plurivalent ou un groupe hydrocarbone plurivalent substitue ou non, a condition que lorsque R6 represente un groupe hydrocarbone plurivalent, au moins un des groupes R4 et R5 ne represente pas un atome d'hydrogene.

Procede selon la revendication 4, dans lequel ledit diene non conjugue est un diene de Formule :

CH2=CH-Q-CH=CH2 (II) dans laquelle Q est un groupe organique divalent en C1 - C30.

Procede de preparation du polymere d'isobutylene selon la revendication 1, qui comprend les etapes consistant a polymeriser un monomere cationiquement polymerisable contenant de I'isobutylene en presence d'un acide de Lewis, et d'un initiateur de polymerisation et agent de transfert de chaTne de formule :

R6-C-X (HI) i R5

15 EP 0 452 875 B2 dans laquelle X represente un atome d'halogene ou un groupe de formule : RCOO- ou RO- dans laquelle R represente un groupe organique monovalent, R4 et R5 sont identiques ou differents et represented chacun un atome d'hydrogene ou un groupe hydrocarbone monovalent substitue ou non, et R6 represente un groupe aromatique plurivalent ou un groupe hydrocarbone plurivalent substitue ou non, a condition que lorsque R6 represente un groupe hydrocarbone plurivalent, au moins un des groupes R4 et R5 ne represente pas un atome d'hydrogene et a faire reagir le polymere resultant avec un diene non-conjugue.

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