JP3103388B2 - Spiro orthocarbonate copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The spiro orthocarbonate copolymer of the present invention is useful as a raw material for molding materials, composite materials, casting materials, sealing materials, medical materials, dental materials, paints and adhesives.

[0002]

2. Description of the Related Art Volume shrinkage when a thermosetting resin such as an epoxy resin or a phenol resin is cured has become a major problem in the fields of casting materials, sealing materials, adhesive materials and the like.

[0003] If a material exhibiting non-shrinkage property upon curing can be obtained, improvement in dimensional accuracy, reduction in warpage, distortion, generation of gaps, reduction in internal stress, and improvement in material strength and adhesive strength can be expected.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a spiro-orthocarbonate-based copolymer in which the volume shrinkage during curing is extremely small or shows volume expansion as compared with conventional epoxy resins and phenolic resins. is there.

[0005]

Means for Solving the Problems The present inventors have obtained a copolymer by copolymerizing a specific spiro orthocarbonate compound, a vinyl monomer having a benzylsulfonium salt structure, and, if necessary, an ethylenically unsaturated compound. It has been found that the resulting resin is cured by heating, and exhibits a very small volume contraction or a large volume expansion upon curing, thereby completing the present invention.

That is, according to the present invention, the polymer structural units A, B and C represented by the following formula 1

[0007]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ and R ¹³ each represent a hydrogen atom or carbon number 8
The following alkyl ^{radicals, R 9, R 10, R} 11 and R ¹² are each a hydrogen atom, the number 8 an alkyl group having a carbon alkyl group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group Or an ester group, X ^- is Sb
An anion selected from F ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ and BF ₄ ⁻ , and M represents a vinyl polymer constituent unit of an ethylenically unsaturated compound. ) Each in the molar% ratio of a, b and c (1 ≦
a ≦ 99.9, 0.1 ≦ b ≦ 30, 0 ≦ c ≦ 99) The present invention relates to a spiro orthocarbonate copolymer formed by bonding.

In the above formula 1, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹³ each have 8 carbon atoms
Examples of the following alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl, n-hexyl, and n -Heptyl group, n-octyl group and the like. Examples of the alkyl group having 8 or less carbon atoms represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include , for example, methyl group, ethyl group, n-propyl group, i -Propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the alkyloxy group include methyl. Oxy group, ethyloxy group,
n-propyloxy group, i-propyloxy group, n-
A butyloxy group, an n-pentyloxy group and the like are mentioned, and a halogen group is, for example, a chloro group and a bromo group, and an amino group is, for example, an N-methylamino group, an N, N-dimethylamino group. Examples of the amide group include an aminocarbonyl group and a formylamino group, and examples of the ester group include a methoxycarbonyl group and an acetyloxy group.

In the above chemical formula 1, the proportion of the structural unit having a spiro orthocarbonate structure is at least 1 mol% and 99.9.
Mol% or less, preferably 10 mol% or more and 90 mol% or less. When the proportion of the constituent units is 1 mol% or less, curing is insufficient, and when it is 99.9 mol% or more, curing is insufficient.

In the above chemical formula 1, the proportion of the structural unit having a benzylsulfonium salt structure is from 0.1 mol% to 30 mol%, preferably from 3 mol% to 20 mol%. If the proportion of the constituent unit is less than 0.1 mol%, curing becomes insufficient, and if it is 30 mol% or more, problems such as coloring of the cured product occur, which is not preferable.

In the above chemical formula 1, the vinyl polymer constituting unit of the ethylenically unsaturated compound represented by M is methyl (meth)
(Meth) acrylates such as acrylate and ethyl (meth) acrylate; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide; and polymerized units such as maleic anhydride and dimethyl maleate. No.

The spiro orthocarbonate copolymer of the present invention is represented by the following chemical formula 2.

[0014]

Embedded image Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸
Is a hydrogen atom or an alkyl group having 8 or less carbon atoms, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each a hydrogen atom,
It represents an alkyl group having 8 or less carbon atoms , an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group or an ester group. ) And a spiro orthocarbonate compound represented by the following formula

[0015]

Embedded image (Wherein, R ¹³ represents a hydrogen atom or a lower alkyl group, X ⁻
Represents an anion selected from SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ and BF ₄ ⁻ . )) And, if necessary, radical copolymerization of a vinyl monomer having a benzylsulfonium salt structure and an ethylenically unsaturated compound.

Preferred examples of the spiro orthocarbonate compound used in the present invention include a compound represented by the following chemical formula 4.

[0017]

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The method for producing the spiro orthocarbonate compound represented by Chemical Formula 2 is not particularly limited. An example of an industrially advantageous production method is as follows.

That is, the following chemical formula 5

[0020]

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(Wherein Ar represents an aromatic group and Y represents a halogen group) and a dihalodiaryloxymethane compound represented by the following formula:

[0022]

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(Wherein R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms;
Z represents a halogen group. ) Is dehydrohalogenated with a diol compound represented by the following formula:

[0024]

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(Wherein, Ar is an aromatic group, R ¹ , R ² , R ³
And R ⁴ each represent A <br/> alkyl group having 8 or less hydrogen or C, Z is a halogen group. ) Is produced, and a dioxolane compound represented by the following formula (7) and a dioxolane compound represented by the following formula (7) are produced.

[0026]

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(Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms;
R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, a carbon atom
It represents an alkyl group, alkyloxy group, halogen group, nitro group, cyano group, amino group, amide group, hydroxyl group or ester group of the number 8 or less . ) Is removed from the diol compound to give

[0028]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or a carbon atom 8;
The following alkyl groups are represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Represents a hydrogen atom, an alkyl group having 8 or less carbon atoms, an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group or an ester group, and Z represents a halogen group. ) Is produced by dehydrohalogenating the spiro orthocarbonate compound shown in Chemical formula 9.
A method for producing a spiro orthocarbonate compound represented by the following formula, or by subjecting a dihalodiaryloxymethane compound represented by the formula 5 and a diol compound represented by the formula 8 to dehydrohalogenation,

[0030]

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(Wherein, Ar is an aromatic group, R ⁵ , R ⁶ , R
R ⁷ and R ⁸ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group having 8 or less carbon atoms, an alkyloxy group; Represents a group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group or an ester group. ) Is produced, and the spiroorthocarbonate compound represented by the formula (9) is produced by removing the dioxolane compound represented by the formula (10) and the diol compound represented by the formula (6). A method for producing a spiro orthocarbonate compound represented by the following formula 2 by dehydrohalogenating the spiro orthocarbonate compound is preferred.

In the dihalodiaryloxymethane compound represented by the above formula 5, the aromatic group represented by Ar is, for example, a phenyl group, a p-methylphenyl group, a p-ethylphenyl group, a p-propylphenyl group, a p-propylphenyl group. -Phenylphenyl group, 1-naphthyl group, 2-naphthyl group and the like;
Examples of the halogen group represented by include a chloro group, a bromo group, and an iodo group.

In the diol compound represented by the above formula 6,
Examples of the halogen group represented by Z include a chloro group, a bromo group, and an iodo group.

The dehalogenation reaction between the dihalodiaryloxymethane compound represented by the chemical formula (5) and the diol compound represented by the chemical formula (6) or (8) is carried out by reacting the dihalodiaryloxymethane compound represented by the chemical formula (5) with It is carried out by mixing the diol compound represented by Chemical formula 8 in the presence of an amine such as trimethylamine, triethylamine, and tri-n-propylamine. It is preferable that the dihalodiaryloxymethane compound represented by the chemical formula 5 and the diol compound represented by the chemical formula 6 or 8 are mixed in equimolar amounts. The amine is added to the dihalodiaryloxymethane compound shown in Chemical Formula 5 by 100
To 300 mol%, preferably 100 to 150 mol%.

The reaction temperature is in the range of -78 to 100 ° C, preferably -20 to 50 ° C. The reaction is usually performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

The above reaction may be carried out in the absence of a solvent, but is preferably carried out in the presence of a solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform, tetrachloroethylene, etc. This is preferable in terms of ease of operation.

The reaction time is usually selected from the range of 1 to 100 hours. After the desired conversion has been reached, the reaction solution is washed with water, and then obtained by a known method.
The dioxolane compound represented by 0 is isolated and purified.

The dioxolane compound represented by the formula (7) and the formula (8)
The dearylol reaction with the diol compound represented by the following formula or the deallylol reaction between the dioxolane compound represented by the formula (10) and the diol compound represented by the formula (6) is carried out by the dioxolane compound represented by the formula (7) and the diol compound represented by the formula (8) or A dioxolane compound represented by the chemical formula 10 and a diol compound represented by the chemical formula 6,
It is carried out by mixing in the presence of an acid catalyst such as benzenesulfonic acid. A dioxolane compound represented by the following formula:
It is preferable that the diol compound represented by the chemical formula 8 or the dioxolane compound represented by the chemical formula 10 and the diol compound represented by the chemical formula 6 are mixed in equimolar amounts. The acid catalyst is Chemical formula 7 or Chemical formula 1.
0.01 to the dioxolane compound represented by 0
10 mol%, preferably 0.1 to 5 mol% is used.

The reaction temperature is in the range of -78 to 100 ° C, preferably -20 to 50 ° C. The reaction is usually performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

The above reaction may be carried out in the absence of a solvent, but is preferably carried out in the presence of a solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform, tetrachloroethylene or the like, in order to remove the reaction heat and perform the operation. This is preferable in terms of ease of operation.

The reaction time is usually selected from the range of 1 to 100 hours. After reaching the desired conversion, the reaction solution is washed with water, and the spiro orthocarbonate compound represented by Chemical formula 9 obtained by a known method is isolated and purified.

The dehydrohalogenation reaction of the spiro orthocarbonate compound represented by the chemical formula (9) is carried out by reacting the spiro orthocarbonate compound represented by the chemical formula (9) with sodium alkoxide such as sodium methoxide, potassium methoxide, potassium tert-butoxide, It is performed by mixing potassium alkoxide. Sodium alkoxide and potassium alkoxide are 100 to 200 mol% based on the spiro orthocarbonate compound represented by the formula (9),
Preferably, it is used in an amount of 100 to 130 mol%.

The reaction temperature is in the range of -78 to 100 ° C, preferably -20 to 50 ° C. The reaction is usually performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

The above reaction may be carried out in the absence of a solvent. However, the reaction is carried out in the presence of a solvent such as N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, etc. to remove the heat of the reaction and to carry out the operation. It is preferable in terms of easiness and the like.

The reaction time is usually selected from the range of 1 to 100 hours. After the desired conversion is reached, the reaction solution is washed with water, and the spiro orthocarbonate compound represented by Chemical Formula 2 obtained by a known method is isolated and purified.

The monomer having a benzylsulfonium salt structure represented by Chemical formula 3 used in the present invention is a sulfonium halide salt obtained by reacting the corresponding halomethylstyrene or halomethyl α-alkylstyrene with tetrahydrothiophene, By exchange, Sb
It can be easily obtained by using F ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , or BF ₄ ⁻ salt.

Examples of the radical polymerization initiator used in producing the resin of the present invention include azobisisobutyronitrile, azobisisobutyrate, azobis-2,4-dimethylvaleronitrile, and azobiscyclohexanecarbonitrile. System polymerization initiator: diisopropylperoxydicarbonate, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, p-menthanehydro Peroxide,
Peroxide polymerization initiators such as pinane hydroperoxide and cumene hydroperoxide are exemplified.

The radical polymerization initiator is used in an amount of 0.01 to 10 mol%, preferably 0.05 to 3 mol%, based on the total number of moles of the monomer.

The temperature of the radical polymerization reaction varies depending on the kind of the radical polymerization initiator used, but it ranges from room temperature to 80.
C, preferably a temperature in the range of room temperature to 60C. If the temperature is lower than room temperature, the polymerization reaction rate is low, and if the temperature is higher than 80 ° C., the crosslinking curing reaction proceeds, which is not preferable.

The radical polymerization reaction can be carried out under any pressure from reduced pressure to increased pressure, but is preferably carried out at normal pressure.

The radical polymerization reaction may be carried out in the absence of a solvent, but aromatic hydrocarbons such as benzene, toluene, xylene, hemimelitene, pseudocumene and mesitylene; aliphatic hydrocarbons such as hexane, heptane and octane; The reaction may be performed in the presence of a solvent such as an alicyclic hydrocarbon such as cyclohexane and cyclooctane; and a halogenated hydrocarbon such as methylene chloride, chloroform, tetrachloroethylene, chlorobenzene, dichlorobenzene, and trichlorobenzene.

The radical polymerization reaction time is usually selected from the range of 1 to 100 hours. After reaching the desired degree of polymerization,
The resin obtained by a known method is isolated and purified.

The spiro orthocarbonate copolymer obtained by the above method can be cured by, for example, charging the polymer in a solution of acetonitrile or the like into a container made of glass, plastic, ceramic, or rubber, and heating the mixture. The orthocarbonate ring undergoes ring-opening isomerization to obtain a crosslinked product.

The heating temperature at the time of curing is in the range of 80 to 300 ° C., preferably 100 to 150 ° C.

The heating time during curing is selected from the range of 1 to 100 hours.

[0056]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, the physical property value was measured by the following method. ¹ H-NMR: JMX PMX60 _SI (measurement frequency; 60 MHz) IR: JASCO Fourier transform infrared spectrophotometer FT
/ IR-3 melting point: Yanagimoto Seisakusho trace melting point analyzer MP type Elemental analysis: Yanagimoto Seisakusho CHN-coder MT2 type Viscosity; Ubbelohde type viscometer (solvent; 1 mol / L of sodium salt of anion of measurement resin) Acetonitrile solution, measurement temperature; 30 ° C.) Density: Density gradient tube method specific gravity measurement device A type (manufactured by Shibayama Scientific Instruments) (density gradient solution; calcium bromide aqueous solution, measurement temperature;
25 ℃)

Reference Example 1 The inside of a 100-mL glass container equipped with a stirrer was sufficiently replaced with dry nitrogen gas. Into this vessel were charged 6.1 g (55 mmol) of chlorohydrin, 10.1 g (100 mmol) of triethylamine and 25 mL of methylene chloride, and 13.5 g (50 mmol) of diphenoxydichloromethane in 35 ml of methylene chloride was added to this solution.
The L solution was added over 45 minutes with stirring at 25 ° C.
After stirring at room temperature for 4 hours, the reaction mixture was washed twice with 25 mL of water, and the organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous sodium sulfate, concentrated and distilled under reduced pressure to a boiling point of 17
8. Colorless and transparent liquid of 1 to 173 ° C / 0.35 mmHg
76 g were obtained. This liquid was identified as 2,2-diphenoxy-4-chloromethyl-1,3-dioxolane from the ¹ H-NMR spectrum and the IR spectrum. The isolation yield was 64%.

¹ H-NMR spectrum (the result is shown in FIG. 1
Measurement solvent; heavy chloroform Internal standard substance; tetramethylsilane

[0059]

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[0060]

[Table 1]

IR spectrum (the results are attached as FIG. 2)

The inside of a glass container having a stirrer and having a capacity of 100 mL was sufficiently replaced with dry nitrogen gas. The 2,2-diphenoxy- obtained by the above reaction is placed in the container.
9.00 g of 4-chloromethyl-1,3-dioxolane
(29 mmol), p-toluenesulfonic acid monohydrate 1
35 mg (0.72 mmol) and methylene chloride 15
mL was added, and a solution of 4.05 g (29 mmol) of ortho-xylylene glycol in 20 mL of methylene chloride was added to the solution with stirring at 25 ° C. Stirring was continued at 25 ° C., and after 50 hours, 1N aqueous sodium hydroxide solution 20
mL was added and the organic layer was separated from the aqueous layer, and the organic layer was washed twice with 1N aqueous sodium hydroxide solution (30 mL) and water (30 mL). After the organic layer was dried over anhydrous sodium sulfate and concentrated, a white solid precipitated. The white solid was purified by recrystallization with a mixed solution of n-hexane / ethyl acetate = 3/1 (volume ratio) to obtain 2.85 g of colorless crystals. From the ¹ H-NMR spectrum and IR spectrum, this solid was spiro [1,5-dihydro-4′-chloromethyl-2,4-benzodioxepin-3,2 ′-[1,
3] dioxolane]. The isolation yield was 38%.

¹ H-NMR spectrum (the result is shown in FIG.
Measurement solvent; heavy chloroform Internal standard substance; tetramethylsilane

[0064]

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[0065]

[Table 2]

IR spectrum (the results are attached as FIG. 4)

The inside of a 100-mL glass container equipped with a stirrer was sufficiently replaced with dry nitrogen gas. 702 mg of sodium methoxide (13 mmol
l) and 10 mL of dimethylformamide, and spiro [1,5-dihydro-4′-chloromethyl-2,4-benzodioxepin-3,2 ′-[1, 3] dioxolane] 2.57 g (1
(0 mmol) in 7.5 mL of dimethylformamide was added at 25 ° C. with stirring over 15 minutes. Stirring was continued at 25 ° C., and after 41 hours, 60 mL of water was added, and organic matter in the aqueous layer was extracted with 60 mL of ether. After the organic layer was dried over anhydrous sodium sulfate and concentrated, a white solid precipitated. The white solid was purified by recrystallization from ethyl acetate to obtain 0.88 g of colorless crystals having a melting point of 126 to 127 ° C. This solid was obtained from ¹ H-NMR spectrum and IR spectrum of spiro [1,5-dihydro-4′-methylene-2,4-benzodioxepin-3,2 ′-[1,3].
Dioxolane]. The isolation yield was 40%.

¹ H-NMR spectrum (the result is shown in FIG.
Measurement solvent; heavy chloroform Internal standard substance; tetramethylsilane

[0069]

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[0070]

[Table 3]

IR spectrum (the results are attached as FIG. 6)

Elemental analysis

[0073]

[Table 4]

REFERENCE EXAMPLE 2 Orthoxylylene glycol 4.05 in Reference example 1
The reaction was carried out in the same manner except that 5.00 g (29 mmol) of 4-chloroorthoxylylene glycol was used instead of g (29 mmol), and spiro [1,5-dihydro-
7-chloro-4'-methylene-2,4-benzodioxepin-3,2 '-[1,3] dioxolane] 1.02 g
I got

Elemental analysis

[0076]

[Table 5]

Reference Example 3 In Reference Example 1, 6.1 g of chlorohydrin (55 mmol) was used.
5. 4-chloro-2,3-butanediol in place of l)
The reaction was carried out in the same manner except that 9 g (55 mmol) of 4-chloroorthoxylylene glycol was used instead of orthoxylylene glycol, and spiro [1,5-
Dihydro-7-chloro-4'-methylene-5'-methyl-2,4-benzodioxepin-3,2 '-[1,3]
Dioxolane] 1.24 g was obtained.

Elemental analysis

[0079]

[Table 6]

Example 1 Spiro [1,5-dihydro-4'-methylene-2,4-benzodioxepin-3,2 '-[1,
3] dioxolane] 176 mg (0.8 mmol), p
176 mg (0.4 mmol) of vinylbenzyltetramethylenesulfonium hexafluoroantimonate,
Acrylonitrile 42 mg (0.8 mmol) and azobisisobutyronitrile 9.9 mg (0.06 mmol
l) was charged into a glass container, degassed, sealed, and heated at 60 ° C. for 20 hours to obtain a pale yellow transparent liquid. This liquid was re-precipitated in 100 mL of methanol to obtain 312 m of a single yellow solid.
g was obtained. The intrinsic viscosity of the product was 0.19.

[0081] When the IR spectrum of the product was measured, the absorption disappeared derived from C = CH ₂ of 1,695 cm ^-1, C-O in 1217,1167 and 1076cm ^-1
Absorption due to -C was observed.

The structure of the product determined by ¹ H-NMR spectrum and elemental analysis was as follows:

[0083]

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The density of the product was 1.310.

The product (102 mg) was dissolved in acetonitrile (0.1%).
It was dissolved in 2 mL and heated at 120 ° C. for 10 hours to obtain a pale yellow crosslinked product. The density of the crosslinked product was 1.299, and the volume expansion rate during heat curing was 0.8%.

Example 2 In Example 1, spiro [1,5-dihydro-4′-methylene-2,4-benzodioxepin-3,2′-
[1,3] dioxolane] 176 mg (0.8 mmo
Spiro [1,5-dihydro-4′-methylene-2,4-benzodioxepin-3,2 ′-[1,1)
3] dioxolane] 44 mg (0.2 mmol), p-
Instead of 176 mg (0.4 mmol) of vinylbenzyltetramethylenesulfonium hexafluoroantimonate, 88 mg (0.2 mmol) of p-vinylbenzyltetramethylenesulfonium hexafluoroantimonate
l) Polymerization and crosslinking were carried out in the same manner except that 85 mg (1.6 mmol) of acrylonitrile was used instead of 42 mg (0.8 mmol) of acrylonitrile. The volume expansion rate at the time of crosslinking was -0.2%.

Example 3 In Example 1, spiro [1,5-dihydro-4′-methylene-2,4-benzodioxepin-3,2′-
[1,3] dioxolane] 176 mg (0.8 mmo
Spiro [1,5-dihydro-7-chloro-4'-methylene-2,4-benzodioxepin-3,2 '-[1,3] dioxolane] 20 synthesized in Reference Example 2 instead of l)
Polymerization and crosslinking were carried out in the same manner except that 3 mg (0.8 mmol) was used. 1.0% volume expansion during crosslinking
Met.

Example 4 In Example 1, spiro [1,5-dihydro-4′-methylene-2,4-benzodioxepin-3,2′-
[1,3] dioxolane] 176 mg (0.8 mmo
spiro [1,5-dihydro-7-chloro-4'-methylene-5'-methyl-synthesized in Reference Example 3 instead of l)
Using 2,4-benzodioxepin-3,2 '-[1,3] dioxolane] mg (1.0 mmol) instead of 176 mg (0.4 mmol) of p-vinylbenzyltetramethylenesulfonium hexafluoroantimonate 146 mg of p-2-propenylbenzyltetramethylenesulfonium hexafluorophosphonate (0.4 mm
ol) and acrylonitrile 42 mg (0.8 mm
ol) instead of methyl acrylate 52 mg (0.6 m
mol)), polymerization and cross-linking were carried out in the same manner. The volume expansion rate at the time of crosslinking was 0.9%.

[0089]

According to the present invention, there is provided a spiro-orthocarbonate-based copolymer exhibiting extremely small volume shrinkage upon curing or showing volume expansion.

[Brief description of the drawings]

FIG. 1 is a diagram showing an NMR spectrum of a spiro orthocarbonate compound used in the present invention.

FIG. 2 is a view showing an IR spectrum of a spiro orthocarbonate compound used in the present invention.

FIG. 3 is a diagram showing an NMR spectrum of another spiro orthocarbonate compound used in the present invention.

FIG. 4 is a view showing an IR spectrum of another spiro orthocarbonate compound used in the present invention.

FIG. 5 is a diagram showing an NMR spectrum of another spiro orthocarbonate compound used in the present invention.

FIG. 6 is a view showing an IR spectrum of another spiro orthocarbonate compound used in the present invention.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 224/00 C08F 230/00-230/04 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The polymer structural units A, B and C represented by the following chemical formula 1 (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹³ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms; ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group having 8 or less carbon atoms, an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group,
A hydroxyl group or an ester group, X ⁻ is SbF ₆ ⁻ , As
An anion selected from F ₆ ⁻ , PF ₆ ⁻ , and BF ₄ ⁻ , and M represents a vinyl polymer constituent unit of an ethylenically unsaturated compound. )
The molar percentages of a, b and c are respectively (1 ≦ a ≦ 99.
9, 0.1 ≦ b ≦ 30, 0 ≦ c ≦ 99) Spiro-orthocarbonate copolymers formed by bonding.