JP2001031714A - Polymer and curable composition - Google Patents

Abstract

(57) Abstract: The present invention easily converts (meth) acryloyl-based groups from halogen-terminated hydrocarbon-based polymers obtained by cationic polymerization without using a special reagent such as a hydride-borane reagent. The purpose is to provide a polymer having a terminal. A protected hydroxyl group obtained by reacting a halogen-terminated hydrocarbon polymer (a) obtained by cationic polymerization with a compound having a protected hydroxyl group and a carbon-carbon double bond (b) is obtained. Hydrocarbon polymer having a hydroxyl-terminated polymer main chain and having a saturated main polymer chain obtained by deprotecting a hydrocarbon polymer having a saturated main polymer chain at the terminal (C) and (meth) acryloyl-based polymer By reacting the halide, the desired (meth)
A hydrocarbon polymer having an acryloyl group at the terminal can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrocarbon polymer having a (meth) acryloyl group at the terminal and having a saturated main chain, and a curable composition using the polymer.

[0002]

[0002] Hydrocarbon polymers containing reactive functional groups are known in the art. Unlike polymers containing hydrocarbon-based unsaturated groups such as allyl groups and methallyl groups, compounds in which (meth) acryloyl-based groups have been introduced at the ends of the polymer can be used as active energy ray-curable compositions including UV and electron beams. It is very desirable for use as a thermosetting composition.

[0003] Polyisobutylene is known as a polymer having a (meth) acryloyl group and obtained by cationic polymerization. In particular, a reaction for quantitatively introducing a functional group to the terminal of polyisobutylene by living cationic polymerization is known. J. P. Kennedy et al. First synthesized polyisobutylene having a chlorine group at the terminal by living cationic polymerization, and then conducted dehydrochlorination of the terminal using ^t BuOK to lead to the isopropenyl group terminal, or in the presence of titanium tetrachloride. After synthesizing allyl group-terminated polyisobutylene by reacting with allyltrimethylsilane, quantitative reaction is carried out by reacting an isopropenyl group or an allyl group with a hydride-borane reagent such as BH ₃ or 9-BBN and hydrogen peroxide. To introduce a hydroxyl group at the terminal (for example, B.
Ivan, JP Kennedy, and VSC Chang, J. Polym.
Sci., Polym. Chem, Ed., 1980, 18, 3177 and B. Iv.
an, and JP Kennedy, Polym. Mater. Sci. Eng., 198
8, 58, 866) One of the methods for introducing a (meth) acryloyl group is to react (meth) acrylic acid chloride with the terminal hydroxyl group of polyisobutylene obtained by the above-mentioned method (B. Ivan, JP Kennedy, CARBOCA
TIONIC MACROMOLECULAR ENGINEERING, HANSER Publishe
rs, 1992, 179). In this method, the hydrido-borane reagent used for introducing a hydroxyl group into a terminal is difficult to obtain compared to other general reagents, is flammable, and is dangerous because it reacts violently with water. There is a problem that the oxidation of the oxidation product with hydrogen peroxide adds to the complexity of this synthesis method.

As another introduction method, a hydrosilane having a hydrolyzable group is hydrosilylated into a terminal vinyl group or an allyl group of the polyisobutylene obtained by the above method, and a silyl group having a hydrolyzable group is introduced. By synthesizing silanol-terminated polyisobutylene by hydrolysis and then reacting it with a silane having both a group containing an acryl group and a hydrolyzable group bonded to silicon in the molecule, (meth) A method of introducing an acryloyl group into a terminal is disclosed (JP-A-10-8).
7726). However, this synthesis method has a problem that the route is long and the synthesis is complicated.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a hydride
An object of the present invention is to easily provide a polymer having a (meth) acryloyl-based group at the terminal from a halogen-terminated hydrocarbon-based polymer obtained by cationic polymerization without using a special reagent such as a borane reagent.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a halogen-terminated hydrocarbon polymer obtained by cationic polymerization (a).
And a compound having a protected hydroxyl group and a carbon-carbon double bond (b), which is a polymer having a protected hydroxyl group at its terminal, and deprotects a saturated hydrocarbon-based polymer. And a hydrocarbon polymer having a hydroxyl-terminated polymer main chain and having a saturated main chain, represented by the following general formula 3: XC (O) C (R) = CH ₂ (3) (where R is hydrogen, Or X represents an organic group having 1 to 20 carbon atoms. X represents chlorine or bromine.) The compound represented by the general formula 4: -OC (O) C (R) = CH ₂ (4) wherein, in the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms.
The present invention relates to a hydrocarbon polymer characterized by having a polymer at a molecular end, and a curable composition using the polymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon polymer having a saturated polymer main chain in the present invention is a polymer having a CC double bond in the main chain obtained by cationic polymerization forming a carbon-carbon single bond. It means a hydrocarbon polymer having no (i.e., saturated) hydrocarbon group. However, the graft group hanging on the main chain may have a C-C double bond. Further, the polymerization initiator used in the cationic polymerization may have a CC double bond.

The process for producing a saturated hydrocarbon polymer (c) according to the present invention obtained by cationic polymerization in which a polymer main chain having a hydroxyl group at a terminal forms a carbon-carbon single bond, comprises:
For example, see J. P. It can be obtained by the method of Kennedy et al.

In addition, a saturated hydrocarbon polymer (c) obtained by cationic polymerization in which a polymer main chain having a hydroxyl group at a terminal forms a carbon-carbon single bond is a cation capable of forming a carbon-carbon single bond. A hydrocarbon-terminated hydrocarbon-terminated hydrocarbon compound obtained by reacting a halogen-terminated hydrocarbon polymer (a) obtained by polymerization with a compound having a protected hydroxyl group and a carbon-carbon double bond (b) Obtained by deprotecting the polymer. Here, the structure of the protected saturated hydrocarbon polymer having a hydroxyl group at the terminal is such that the halogen-terminated hydrocarbon polymer (a) obtained by cationic polymerization has the formula (1): R ¹ (AX) _a ( 1) (wherein, R ¹ is a monovalent to tetravalent hydrocarbon group containing a single ring or a plurality of aromatic rings, X is a chlorine group or a bromine group, a is an integer of 1 to 4. A is one or two or more. (A) may be the same or different when a is 2 or more, and a compound having a protected hydroxyl group and a carbon-carbon double bond (b) ) Is the formula (2): CH ₂ ＣC (R ² ) -B-OG (2) (wherein, R ² is hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, and B is 1 to 30 carbon atoms) And G represents a hydroxyl-protecting group.).

In the formula (2), B represents a group having 1 to 30 carbon atoms.
A divalent hydrocarbon group having 0 to 5 carbon-carbon double bonds (excluding those having a CH ₂ ＣC (R ² ) -group (R ² is the same as described above)) and / or Alternatively, it is preferable to have 0 to 3 aromatic rings. B in the equation (2) is 0
It is more preferred to have up to three divalent groups represented by -CH = CH-.

The compound of the formula (2) includes a compound of the formula (4): CH ₂ ＣC (R ² )-(CH ₂ ) _b -｛-CH ＝ CH— (CH ₂ ) _c ｝ _n -OG ( 4) (wherein, R ² represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and b and c are integers of 1 to 30 and are the same or different. And n is an integer of 0 to 5, and G represents a hydroxyl-protecting group.)

The protected hydrocarbon-terminated hydrocarbon-terminated hydrocarbon polymer obtained by this method is easily dehydroxylated by a hydroxyl-terminated hydrocarbon-terminated hydrocarbon polymer. (C) can be converted.

The cationically polymerizable monomer in the above formula (1) is not particularly limited, but preferable monomers include, for example, isobutylene, indene, pinene, styrene, methoxystyrene, chlorostyrene and the like.

When the polymer of the present invention is used as a raw material for a curable composition, it is necessary to produce an isobutylene-based polymer which is in a liquid state before cross-linking and gives a rubber-like cured product after cross-linking. preferable.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having a copolymer with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good.

Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes and the like. Examples of such a copolymer component include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane,
Vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinyl Methylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallylmethoxymethoxy, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ
-Methacryloyloxypropylmethyldimethoxysilane.

Further, in order to obtain sufficient strength, weather resistance, gel fraction and the like when a cross-linkable polymer compound is obtained by a cross-linking reaction, a of the polymer of the formula (1) must be 2 or 3
Preferred is a saturated hydrocarbon polymer which is a chlorine-terminated polyisobutylene.

The protecting group of the compound (b) containing a protected hydroxyl group and a carbon-carbon double bond is not particularly limited as long as it provides a hydroxyl group by deprotection.
Usually, it is an inorganic or organic group having 0 to 54 carbon atoms. Preferred protecting groups that can be deprotected under mild conditions include the following.

[0019]

Embedded image (Wherein, R ³ , R ⁴ , and R ⁵ are hydrogen or C 1 to C 1)
8 represents a saturated or unsaturated hydrocarbon group, and the groups containing a plurality of Rs may be the same or different. X
Is a functional group selected from Cl, Br and I. M ¹ is L
a monovalent metal selected from i, Na and K, M ² is Mg, C
a, a divalent metal selected from Sr and Ba, M ³ is B or A
1, a trivalent metal selected from Ga, M ⁴ is Ti, Zr,
It is a tetravalent metal selected from Hf, Si, Ge, Sn, and Pb. Examples of the protecting group include an alkyl group, an acyl group, and an RC (O) — group (where R is 1 to 10 carbon atoms) in view of availability, ease of separation of the polymer and the protecting group component after deprotection. Preferred are a saturated hydrocarbon group), a silyl group and a metal alkoxide, and a methyl group, an ethyl group, n- and i-propyl groups, and n
-, I- and t-butyl, formyl, acetyl,
Propionyl group, butyryl group, benzoyl group, trimethylsilyl group, triphenylsilyl group is more preferable,
It is particularly preferred that these protecting groups have from 0 to 54 carbon atoms.

The compound (b) represented by the formula (2), which is a substrate to be reacted with the halogen-terminated hydrocarbon polymer (a), is protected at the monosubstituted or 1,1'-2-substituted terminal. Although it is not particularly limited as long as the olefin has a hydroxyl group, allyl alcohol, methallyl alcohol, 3-butene-1 when G is hydrogen in the above formula (2) because of high reactivity. -All, 3
-Methyl-3-buten-1-ol, 4-pentene-1
-Ol, 5-hexen-1-ol, 6-heptene-
1-ol, 7-octen-1-ol, 8-nonene-
1-ol, 9-decene-1-ol and 10-undecene-1-ol, 2,5-hexadienol, 2,6
-Heptadienol, 3,6-heptadienol, 2,7
-Octadienol, 3,7-octadienol, 4,7-
Octadienol, 2,8-nonadienol, 3,8-nonadienol, 4,8-nonadienol, 5,8-nonadienol, 2,9-decadienol, 3,9-decadienol,
Compounds selected from 4,9-decadienol, 5,9-decadienol or 6,9-decadienol are preferred.

Compound (b) containing a protected hydroxyl group and a carbon-carbon double bond represented by the formula (2) in a halogen-terminated hydrocarbon polymer (a) obtained by the cationic polymerization of the formula (1) Is reacted, a Lewis acid can be used as a catalyst. In this case, there is no particular limitation as long as it is a Lewis acid, but TiCl ₄ ,
AlCl ₃ , BCl ₃ , and SnCl ₄ are preferable because they have high reaction activity and good selectivity.

In the present invention, a single or mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons can be used as the reaction solvent. Must be at least one component selected from methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride and n-butyl chloride as halogenated hydrocarbons in terms of solubility and reactivity. Is preferred. For the same reason, the aromatic hydrocarbon is preferably toluene, and the aliphatic hydrocarbon is pentane, n-hexane,
One or more components selected from cyclohexane, methylcyclohexane and ethylcyclohexane are preferred.

By using toluene, ethylcyclohexane, or a mixed solvent thereof as a reaction solvent that does not use halogenated hydrocarbons, which may cause adverse effects on the environment, a saturated hydrocarbon group having a protected hydroxyl group at its terminal can be used. Production of the polymer can be easily achieved.

The deprotection reaction is not particularly limited as long as it is a reaction for introducing a protecting group into a hydroxyl group. Preferred reactions include a hydrolysis reaction and a thermal decomposition reaction.

The hydrolysis reaction can be carried out in either a solvent system or a non-solvent system. The solvent used for the solvent-based reaction is not particularly limited, but it is preferable to use a solvent that produces a saturated hydrocarbon-based polymer having a protected hydroxyl group at the terminal. The conditions for performing the hydrolysis may be either acidic or basic conditions, but it is preferable to perform the hydrolysis reaction using a basic aqueous solution in view of the efficiency of the hydrolysis reaction.

The reagent used in the hydrolysis under basic conditions is not particularly limited as long as it is an organic or inorganic basic compound used in a usual hydrolysis reaction. , Potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium acetate, potassium acetate, lithium acetate, calcium acetate, magnesium acetate, t-butoxy Particularly preferred are potassium, sodium t-butoxide, potassium methoxide, sodium methoxide and the like.

In the hydrolysis reaction, the reaction can be efficiently advanced by adding a catalyst. As such a catalyst, any of an organic catalyst and an inorganic catalyst can be reacted, but an organic salt is preferable in terms of easiness of the reaction, and a quaternary ammonium salt is particularly preferable. Representative ammonium salts include triethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, n-butylammonium, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide. Tetra-n-butylammonium bromide, tetrabutylammonium hydrogen sulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, iodine tetra-n-butylammonium, N-lauryl-4-picolinium chloride, N-lauryl Picolinium chloride and the like.

For example, a saturated hydrocarbon polymer (C) obtained by cationic polymerization in which a polymer main chain having a hydroxyl group at a terminal forms a carbon-carbon single bond is specifically obtained by the following production method. Chloroform is used as a reaction solvent with 1 to 4 equivalents of a protected hydroxyl group-terminated olefin compound (b) represented by the formula (2) in the polymer (a) having a halogen group at the terminal represented by the formula (1). Methylene chloride,
1,1-dichloroethane, 1,2-dichloroethane, n
-Propyl chloride, n-butyl chloride, toluene, pentane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane are dissolved in a solvent comprising at least one component selected from the group consisting of: to this,
Pyridine, 2-methylpyridine, 3-methylpyridine,
-100 ° C to -30 ° C in the presence of an electron donor such as 4-methylpyridine and 2,6-di-t-butylpyridine
TiCl ₄ , AlCl ₃ , BCl ₃ , SnC
adding a Lewis acid catalyst l _4, etc., by reacting 30 minutes to 5 hours, hydrocarbon polymer is obtained having a protected hydroxyl group at the end. By deprotecting this, a hydrocarbon polymer having a hydroxyl group at the terminal (c) is obtained.

The compound to be reacted with the hydrocarbon polymer having a hydroxyl group at the terminal (c) to introduce a (meth) acryloyl group is represented by the general formula 3 XC (O) C (R) = CH ₂ (3) (In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine or bromine.) General formula 3
Although in no particular limitation is imposed on the compounds represented by, specific examples of R, for _{example, -H, -CH 3, -CH 2} C
_{H 3, - (CH 2)} n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and preferably -H, -CH ₃ It is. When a hydrocarbon polymer having a hydroxyl group at the terminal (c) is reacted with a compound represented by the general formula 3 to introduce a (meth) acryloyl-based group, HX generated in order to accelerate the reaction, A base for capturing hydrogen or hydrogen bromide may be added. Examples of the base to be added include amine compounds such as diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-i-propylamine, tri-i-propylamine, di-n-butylamine, tri-n -Butylamine, di-i-butylamine,
Examples include tri-i-butylamine, pyridine, aniline, methylaniline, dimethylaniline and the like. When a hydrocarbon polymer having a hydroxyl group at a terminal (c) is reacted with a compound represented by the general formula 3 to introduce a (meth) acryloyl group, either a solvent system or a non-solvent system may be used. When is used, it is preferably a dehydrating solvent. The reaction temperature is -70 ° C to 100 ° C, preferably 0 ° C.
The reaction is performed at room temperature to room temperature for 30 minutes to 12 hours to obtain a hydrocarbon-based polymer having a (meth) acryloyl-based group-terminated saturated polymer main chain.

The hydrocarbon polymer having a (meth) acryloyl group at the terminal and having a saturated main chain according to the present invention can be made into a curable composition containing the same. The curable composition of the present invention is preferably cured by active energy rays such as UV rays and electron beams and / or heat.

The active energy ray and / or thermosetting composition of the present invention preferably contains a light and / or thermal polymerization initiator.

Although the photopolymerization initiator used in the present invention is not particularly limited, a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable. For example, acetophenone, 2,2-diethoxyacetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, -Methoxyacetophene, 3-bromoacetophenone, 4-allylacetophenone, p-
Diacetylbenzene, 3-methoxybenzophenone, 4
-Methylbenzophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4-chloro-
4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-
Nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like can be mentioned. These initiators may be used alone or in combination with other compounds. Specific examples include a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

As the near-infrared light polymerization initiator, a near-infrared light absorbing cationic dye may be used. As a near-infrared light-absorbing cationic dye, it is excited by light energy in the range of 650 to 1500 nm, for example, as disclosed in JP-A-3-11.
It is preferable to use a near-infrared light-absorbing cationic dye-borate anion complex or the like disclosed in JP-A-1402 and JP-A-5-194609, and it is more preferable to use a boron sensitizer in combination.

The method for curing the active energy ray-curable composition of the present invention is not particularly limited. Depending on the properties of the photopolymerization initiator, a high-pressure mercury lamp, a low-pressure mercury lamp, an electron beam irradiation device, a halogen lamp, Light and electron beam irradiation by a light emitting diode, a semiconductor laser, or the like can be given.

The thermal initiator used in the present invention is not particularly limited, and includes an azo initiator, a peroxide, a persulfate, and a redox initiator.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-
2,4-dimethylvaleronitrile) (VAZO 33),
2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyro) Nitrile) (VAZO 64), 2,2'-
Azobis-2-methylbutyronitrile (VAZO 67),
1,1-Azobis (1-cyclohexanecarbonitrile) (VAZO 88) (All DuPont Chemical)
al), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries). Can be

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t- Butylcyclohexyl) peroxydicarbonate (Perkadox)
16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t
-Butyl peroxypivalate (Luppersol 1
1) (available from Elf Atochem), t-butylperoxy-2-ethylhexanoate (Trig
onox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

[0038] Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Suitable redox (redox) initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; And tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

Other initiators include, but are not limited to, pinacols such as tetraphenyl 1,1,2,2-ethanediol. Preferred thermal radical initiators are selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,
2'-azobis (methylisobutyrate), t-butylperoxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The method of curing the thermosetting composition of the present invention is not particularly limited. The temperature varies depending on the type of the thermal initiator used, the compound to be added, and the like.
Preferably in the range of 0 ° C to 150 ° C, 70 ° C to 130 ° C
Is more preferable. The curing time varies depending on the used polymerization initiator, monomer, solvent, reaction temperature and the like, but is usually in the range of 1 minute to 10 hours.

The initiator used in the present invention is present in a catalytically effective amount, and such an amount is not limited, but is typically based on 100 parts by weight of the polymer of the composition. About 0.001 to 10 parts by weight, more preferably about 0.0
25 to 2 parts by weight. If a mixture of initiators is used, the total amount of the mixture of initiators is as if only one initiator was used.

Specific applications of the active energy ray and / or thermosetting composition of the present invention include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, photopolymer plates,
Paint, powder paint, woodworking coating, hard coating, PVC floor coating, optical fiber coating, disc coating, metal coating,
Film coating, offset ink, gravure ink, metal printing ink, silk screen ink,
Foams, potting materials for electric and electronic devices, films, gaskets, silk screen resists, dry film resists, liquid resists, electrodeposition resists, semiconductor resists, color filter resists, various molding materials, stereolithography, artificial marble, etc. .

[0044]

EXAMPLES Next, the present invention will be further clarified with reference to examples, but the present invention is not limited by the examples. In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)”
It was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, as a GPC system, LC Mo made by Waters is used.
Dule1 was filled with a polystyrene crosslinked gel as a GPC column (Shodex GPC K-80).
4: Showa Denko KK), chloroform was used as a GPC solvent. (Example 1) A 5000 ml separable flask was equipped with a three-way cock, a thermocouple, and a stirrer equipped with a vacuum seal, and the atmosphere in the flask was replaced with nitrogen. This is molecular sieves 3A
592 ml of toluene and 73.6 ml of ethylcyclohexane were added to the mixture, and 1,4-bis (1-
Chlor-1-methylethyl) benzene (5.56 g, 2
4.0 mmol), 2-methylpyridine (264 mg,
(2.83 mmol) and cooled to -70 ° C. After cooling, isobutylene monomer (120 ml, 1.44 mo
l) and at this temperature titanium tetrachloride (2.
(52 ml, 23.0 mmol) was added to initiate polymerization. At this time, the temperature was raised by about 15 ° C. The polymerization was completed in about 60 minutes (with this, no exothermic reaction system was observed). After completion of the polymerization, octadienyl acetate (32.4 g,
193 mmol) and titanium tetrachloride (39.8 ml,
386 mmol) was added. After 5 hours reaction, 80
The reaction mixture was introduced into 1.5 L of ion-exchanged water heated to ° C. and stirred for 20 minutes. After standing, remove the aqueous layer,
1 L of 2N aqueous sodium hydroxide solution and 10.0 g of tetrabutylammonium bromide are added,
Stirring was performed for hours. After completion of the reaction, the aqueous alkali solution was removed, and the resultant was washed three times with 1 L of ion-exchanged water, and then the organic layer was isolated. 10 L of acetone was added thereto to reprecipitate the polymer, and low molecular compounds were removed. The precipitate is further washed twice with 1 L of acetone, and 500 ml of hexane is further added.
Was dissolved. The solution was transferred to a 1-L shaped flask and heated under an oil bath (180 ° C.) under reduced pressure (final 1).
The solvent was distilled off at a pressure of not more than Torr to obtain polyisobutylene having a desired hydroxyl group at the terminal (number average molecular weight 5600, molecular weight distribution 1.2). The functionalization rate of the obtained polyisobutylene was analyzed using NMR. (NMR) Gemini-300 manufactured by Varian
Measurement solvent: carbon tetrachloride / acetone heavy = 4/1 mixed solvent,
Quantitative method; based on the signal of the initiator residue (7.2 ppm), the signal of methylene adjacent to the terminal hydroxyl group (4.
(00 ppm). Fn (CH ₂ O
H) is the amount of functional group introduced into the polymer terminal, and when quantitatively introduced, it is 2.0 for the initiator used this time. The amount of hydroxyl groups introduced into the polymer obtained in Example 1 is as follows:
Fn (CH ₂ OH) = 1.90. Example 2 In a 200 ml separable flask, the hydroxyl-terminated polyisobutylene obtained in Example 1 (number-average molecular weight 5600, molecular weight distribution 1.2, Fn (C
(H ₂ OH) = 1.90) 15.01 g (hydroxyl equivalent 5.
1 mmol), 30 ml of n-butyl chloride dehydrated by molecular sieve 3A, 0.6 m of pyridine
1 (7.6 mmol) was added, and the atmosphere was replaced with nitrogen by attaching a three-way cock, a thermocouple, and a stirrer equipped with a vacuum seal. After cooling to 0 ° C, methacrylic acid chloride 0.75m
1 (7.6 mmol) was added, and after the addition was completed, the temperature was raised to 23 ° C. and the mixture was stirred for 2 hours. Since the reaction was not completed in NMR, the mixture was cooled to 0 ° C., and then 0.5 ml (5.1 mmol) of methacrylic acid chloride and 0.4 ml of pyridine were added.
(5.1 mmol), and after the addition was completed, the temperature was raised to 23 ° C. and 1
After stirring for an hour, NMR confirmed that the reaction was completed. Thereafter, the resultant was washed four times with 200 ml of water to obtain an intended 18% by weight solution of polyisobutylene having a terminal (meth) acryloyl group in n-butyl chloride. (Example 3) 100 parts of a (meth) acryloyl-terminated polyisobutylene 18% by weight n-butyl chloride solution obtained in Example 2 (parts by weight: the same applies hereinafter) were added to 2,2-
0.18 parts of diethoxyacetophenone (manufactured by Tokyo Kasei) was added and mixed well. The composition thus obtained was treated with a corona-treated polyethylene terephthalate film (manufactured by Toray Industries, Inc.) having a thickness of 50 μm and a thickness of about 1.2 mm.
After the volatile components are distilled off under reduced pressure, the film is sandwiched with a polyethylene terephthalate film and a high-pressure mercury lamp (SHL-
100UVQ-2; manufactured by Toshiba Lighting & Technology Corp.)
By irradiating light at an irradiation distance of 50 cm for 5 minutes, a good cured product was obtained.

[0045]

The polymer obtained according to the present invention is a polymer having a (meth) acrylolyl group at a terminal, and it is conventionally necessary to use a special reagent such as a hydride-borane reagent, There was a problem that it was long and complicated. In this method, a polymer having a (meth) acryloyl-based group at the terminal can be easily synthesized from a halogen-terminated hydrocarbon-based polymer obtained by cationic polymerization.

The curable composition using this polymer can be preferably cured by an active energy ray or heat, and can exhibit properties such as rubber elasticity since a functional group is introduced at a terminal.

Further, since the introduction ratio of the (meth) acryloyl group is high, a cured product having a high gel content can be obtained, and it is also a rapid curing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09D 123/26 C09D 123/26 4J100 125/04 125/04 125/18 125/18 145/00 145 / 00 C09J 123/26 C09J 123/26 125/04 125/04 125/08 125/08 145/00 145/00 C09K 3/10 C09K 3/10 Z F term (reference) 4H017 AA03 AA04 AA31 AB01 AB07 AC03 AC08 AC16 4J011 QB01 SA02 SA12 SA14 SA16 SA17 SA18 SA19 SA22 SA24 SA25 SA26 SA27 SA28 SA29 SA32 SA34 SA38 SA54 SA58 SA61 SA62 SA63 SA64 SA78 SA82 SA87 SA88 UA02 UA03 UA06 UA08 WA01 WA02 WA03 WA05 WA06 WA07 4J0CB CB02 CB02 CB02 CB02 CB02 CC04 CC06 CC07 CD01 CD03 CD08 CD09 CD10 4J038 FA231 HA366 JA07 JA20 JA22 JA29 JA31 JA33 JA34 JA51 JA66 JA69 JB02 JB06 JB16 JB23 JB27 JC18 KA03 LA02 NA12 PA17 PA19 4J040 FA231 GA03 GA07 HA246 HA256 HB10 HB1 2 HB13 HB17 HB19 HB20 HB21 HB27 HB41 HB43 HC01 HC07 HC14 HC18 HC21 HD19 JA01 JB02 JB07 KA12 KA13 4J100 AA06P AB02P AB07P AB08P AR03P AR10P BA02H BA03H BA04H BA05P BA13H BA15HBA31B17 HA17 HA03B12 HC11 HC12 HC27 HC43 HC44 HC45 HC63 HD16 HE14 JA01 JA03 JA07 JA38 JA67

Claims (10)

[Claims] (1) Formula (1): R ¹ (AX) _a (1) (wherein, R ¹ is a monovalent to tetravalent hydrocarbon group containing a single ring or a plurality of aromatic rings, and X is Chlorine or bromine, a is an integer of 1 to 4. A is a polymer of one or more cationically polymerizable monomers, and when a is 2 or more, A may be the same or different; And a halogen-terminated hydrocarbon polymer (a) obtained by cationic polymerization represented by the following formula (2): CH ₂ ＣC (R ² ) -B-OG (2) (where R ² is A protected hydroxyl group represented by hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, B represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and G represents a hydroxyl-protecting group. The polymer main chain having a protected hydroxyl group at the terminal obtained by reaction with the compound having a carbon-carbon double bond (II) is saturated. Japanese hydrocarbon polymer (C)
Is further deprotected to obtain a hydrocarbon polymer having a hydroxyl-terminated terminal and having a saturated main chain (d), and a general formula 3: XC (O) C (R) = CH ₂ (3) (Wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms; X represents chlorine or bromine.) A general formula 4: obtained by a reaction with a compound (e) represented by the following formula: OC (O) C (R) = CH ₂ (4) (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms). Coalescing (f). 2. A compound (b) having a protected hydroxyl group and a carbon-carbon double bond is represented by the formula (5): CH ₂ ＣC (R ² )-(CH ₂ ) _b -｛-CH ＝ CH- (CH ₂ ) _c ｝ _n -OG (5) (wherein, R ² represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and b and c are integers of 1 to 30) Wherein n is an integer from 0 to 5, and G represents a hydroxyl-protecting group.) . 3. The hydrocarbon polymer according to claim 1, wherein the halogen-terminated hydrocarbon polymer (a) obtained by cationic polymerization is a halogen-terminated isobutylene polymer. 4. The compound (b) having a protected hydroxyl group and a carbon-carbon double bond is allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-
3-buten-1-ol, 4-penten-1-ol,
5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecene-1-
All, 2,5-hexadienol, 2,6-heptadienol, 3,6-heptadienol, 2,7-octadienol, 3,7-octadienol, 4,7-octadienol, 2,8-nonadienol, 3,8-nonadienol,
4,8-nonadienol, 5,8-nonadienol, 2,9-
The hydroxyl group (OH) of a compound selected from the group consisting of decadienol, 3,9-decadienol, 4,9-decadienol, 5,9-decadienol and 6,9-decadienol
The hydrocarbon-based polymer (f) according to any one of claims 1 to 3, wherein the hydrocarbon-based polymer (f) is selected from a group of compounds in which the OG group (G represents a protecting group for a hydroxyl group). 5. A general formula 4: -OC (O) C (R) = CH ₂ (4) (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms). 5. The hydrocarbon polymer according to claim 1, wherein R in the group is hydrogen or a methyl group. 6. 6. A curable composition containing the hydrocarbon polymer according to any one of claims 1 to 5. 7. The curable composition according to claim 5, which is cured by active energy rays and / or heat. 8. The curable composition according to claim 6, further comprising a polymerization initiator. 9. The curable composition according to claim 8, wherein the polymerization initiator is a light and / or thermal radical initiator. 10. The curable composition according to claim 8, wherein the polymerization initiator is a photoanion initiator.