JPH06322029A - Ethylenically unsaturated cyclic carbonate monomer and polymer producued therefrom - Google Patents

Abstract

PURPOSE:To obtain a cross-linked polymer which does not virtually undergo vol. change by cross-linking a homopolymer of an ehtylenically unsatd. cyclic carbonate monomer or a copolymer thereof with another ethylenically unsatd. monomer using an ionic cattalyst etc. CONSTITUTION:A mixture comprising 5-100mol% ethylenically unsatd cyclic monomer of formula I 'wherein R<1> is a polymerizable vinly group such as a (meth)acryloyloxy, a styryl, or a vinylbenzyloxy group; and R<2> is H or a 1-10C hydrocarbon group' and 95-0mol% ethylenically unsatd. monomer of formula II (wherein X is H or metyl; Y is CN, COOR<3>, OCOR<3>, halogen, or an optionally substd. arom. group; and R<3> is an alkyl group having 1-8C an arom. group) is cross-linked with an inoic catalyst (e. g. boron triflouride or t-butoxypotassium) in an amt. of 0.001-20mol% based on cyclic carbonate groups of the cyclic monomer or with an aliph. ployamine, giving a cured polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel ethylenically unsaturated monomers having cyclic carbonate groups and polymers derived therefrom, and further to a non-shrinkable crosslinkable modification by a suitable ionic catalyst. Regarding polymers. It also relates to modified polymers which can additionally be crosslinked with aliphatic polyamines having active hydrogen.

[0002]

2. Description of the Related Art Generally, a crosslinkable resin causes shrinkage due to polymerization during molding, which greatly affects the physical properties of a cured product. In extreme cases, the occurrence of sink marks, warps, voids, cracks, etc., or adhesive strength. Cause a decrease in. Further, unlike thermoplastic resins, it is very difficult to recycle defective products with crosslinkable resins, and the occurrence of such defects has a great influence on the product yield of cured products. For this reason, for example, unsaturated polyester resins are reduced in shrinkage by adding a series of thermoplastic resins called inorganic fillers and / or shrinkage reducing agents.

However, the addition of such an inorganic filler is effective in improving rigidity and strength or improving electrical characteristics depending on the kind of filler, but on the other hand, there is a problem that the specific gravity is increased and the impact resistance or mechanical strength is lowered. is there. Polystyrene, polymethylmethacrylate, polyvinyl acetate, or saturated polyester resins are known as shrinkage reducing agents for thermoplastic resins, but addition of these shrinkage reducing agents often results in chemical resistance and impact resistance. There are problems such as deterioration of the heat resistance, heat resistance and mechanical strength, and devitrification due to poor compatibility with the thermoplastic resin.

In view of the above situation, an unsaturated polyester type low shrinkage BMC using a core / shell type reactive microgel having a polymerizable vinyl group in the shell layer has also been proposed (Kataoka et al., No. 36). FRP General Lecture Summary, A
-23, p. 97, 1991). On the other hand, apart from these techniques, a monomer exhibiting non-shrinkage during polymerization and a polymer using these are being developed. For example, W
W. J. Bailey US Patent No. 4,
No. 387,215, a cation-catalyzed ring-opening polymerization of spiro-orthocarbonate compounds, spiro-orthoester compounds showed a swelling of 0.14 to 14%, and also of M.R. Piggott. In U.S. Pat. No. 4,427,735, as a fiber reinforced composite material, the addition of spiropolymer to the toughness reinforcement of epoxy resin and the like is further described in DC Sayle.
s) U.S. Pat. Nos. 4,515,912 and 4,53
No. 0,728 proposes the use of a fiber reinforced composite of DGEBPA and diglycidyl ester of dimer acid with norbornene spiro orthocarbonate for the production of motor cases for missiles.

Further, various compounds having a spiro-orthoester group, a compound having a spiro-orthocarbonate group or a compound having a bicycloorthoester group, and various methods of using these compounds have been proposed (for example, JP-A-56-72007). JP-A-56-108792, JP-A-56-108793 and JP-A-58-3332.
No. 0, No. 58-49724, No. 58-105.
No. 934, No. 58-189211, No. 59-
49228, 62-263225, and 6
No. 3-218719, No. 63-275638, No. 63-277220, and No. 63-29558.
No. 4, JP-A 1-259025, 2-18.
7454, etc.).

[0006] However, some of these compounds have drawbacks in that they require a multi-step reaction for synthesis, are unstable in humidity, or require a high curing temperature, and are not practical. On the other hand, it has recently been found that a 6-membered or 7-membered aliphatic cyclic carbonate undergoes ring-opening polymerization with a suitable anion or cation catalyst and exhibits a volume expansion of 8.4% (T. .. Endo)
Polymer Preprints Japan (Polym.Pre
pr. Jpn), Vol. 39, No. 2, 284 (1990)
And Vol. 40, No. 2, 340 (1991)). These monocyclic compounds have the advantages of simpler synthesis and ring-opening polymerization under mild conditions, as compared with conventional bicyclic compounds.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel ethylenically unsaturated monomer having a cyclic carbonate group, a polymer made from the same, and a non-shrinkable modified polymer using the same. .

[0008]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention has the following general formula (I)

[0009]

[Chemical 3]

(Wherein R ¹ represents at least one polymerizable vinyl group selected from the group consisting of a (meth) acryloyloxy group, a styryl group and a vinylbenzyloxy group, and R ² represents hydrogen or a carbon number of 1). The present invention provides an ethylenically unsaturated cyclic carbonate monomer represented by 10 to 10 hydrocarbon groups).

The present invention also provides the above-mentioned ethylenically unsaturated cyclic carbonate monomer in which R ¹ is a methacryloyloxy group and R ² is an ethyl group.

The present invention further provides the above-mentioned ethylenically unsaturated cyclic carbonate monomer in which R ¹ is a vinylbenzyloxy group and R ² is an ethyl group.

Further, the present invention provides the above-mentioned ethylenically unsaturated cyclic carbonate monomer in which R ¹ is a styryl group and R ² is hydrogen.

In the present invention, the polymer is a homopolymer obtained by polymerization using the radical polymerization initiator of the ethylenically unsaturated cyclic carbonate monomer described above or the ethylenically unsaturated cyclic carbonate monomer. The present invention provides a polymer having a cyclic carbonate group, which is a copolymer obtained by polymerizing a radical polymerization initiator with an ethylenically unsaturated monomer (A) copolymerizable with. .

Further, in the present invention, the ethylenically unsaturated monomer (A) is represented by the general formula (II)

[0016]

[Chemical 4]

(Wherein X represents hydrogen or a methyl group,
Y represents —CN, —COOR ³ , —OCOR ³ , halogen or an aromatic group which may contain a substituent, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aromatic group).
The present invention provides a copolymer having the above-mentioned cyclic carbonate group selected from the group consisting of two or more ethylenically unsaturated monomers.

Furthermore, in the present invention, the ethylenically unsaturated monomer (A) is maleic anhydride or a derivative thereof,
The ring according to the above or above, which is at least one α, β-disubstituted ethylenically unsaturated monomer selected from the group consisting of fumaric acid derivative, itaconic anhydride and its derivative, and citraconic anhydride and its derivative. It is intended to provide a copolymer having a carbonate group.

In the present invention, the ethylenically unsaturated monomer (A) is at least one ethylenically unsaturated monomer represented by the general formula (II) and an α, β-disubstituted ethylenically unsaturated monomer. A copolymer having a cyclic carbonate group as described in any one of 1 to 3 above which is a monomer is provided.

Furthermore, in the present invention, the polymer has a polystyrene-equivalent number average molecular weight of 0.1 to 150,000, and the ethylenically unsaturated cyclic carbonate monovalent monomer represented by the general formula (I) in the polymer is used. To provide a polymer having a cyclic carbonate group as described in any one of 1 to 3 above, wherein the molar fraction of the polymer and the ethylenically unsaturated monomer (A) is 5/95 to 100/0. .

The present invention also provides a copolymer having a cyclic carbonate group according to any one of the above 1 to 3,
Provided is a crosslinkable polymer composition containing an aliphatic polyamine.

The present invention will be described in more detail below.
That is, the present invention has the general formula (I)

[0023]

[Chemical 5]

(In the formula, R ¹ represents a polymerizable vinyl group consisting of a (meth) acryloyloxy group, a styryl group and a vinylbenzyloxy group, and R ² represents hydrogen or a carbon number of 1 to 10).
, Which represents a hydrocarbon group of the above).

The ethylenically unsaturated cyclic carbonate monomer represented by the general formula (I) of the present invention includes 2-oxo-5-acryloyloxymethyl-5-ethyl-1,3.
-Dioxane, 2-oxo-5-acryloyloxymethyl-5-methyl-1,3-dioxane, 2-oxo-
5-ethyl-5-methacryloyloxymethyl-1,3
-Dioxane, 2-oxo-5-methyl-5-methacryloyloxymethyl-1,3-dioxane, 2-oxo-5-ethyl-5- (p-vinylbenzyloxy) methyl-1,3-dioxane, 2- Oxo-5-ethyl-5
-(M-Vinylbenzyloxy) methyl-1,3-dioxane and mixtures of these p-vinylbenzyl form and m-vinylbenzyl form, 2-oxo-5-methyl-5
-(P-Vinylbenzyloxy) methyl-1,3-dioxane, 2-oxo-5-methyl-5- (m-vinylbenzyloxy) methyl-1,3-dioxane and these p-vinylbenzyl compounds and m -Mixture with vinylbenzyl derivative, 2-oxo-5- (p-vinylbenzyl)-
Examples thereof include 1,3-dioxane, 2-oxo-5- (m-vinylbenzyl) -1,3-dioxane, and a mixture of these p-vinylbenzyl and m-vinylbenzyl compounds.

These ethylenically unsaturated cyclic carbonate monomers are described, for example, in Polymer Pre-Prints Japan (T. Endo) et al.
r. Jpn Vol. 39, No. 2, 284 (1990) or Journal of Polymer Science Polymer Chemistry Edition (Polym. Sci. Pol).
ym. Chem. Ed. ) According to the method described in Vol. 29, page 781 (1991), etc., a 1,3-propanediol derivative substituted with a corresponding ethylenically unsaturated group and ethyl chlorocarbonate are dehydrochlorinating agents such as triethylamine. Obtained by condensing in the presence of

As the ethylenically unsaturated monomer (A) copolymerizable with the ethylenically unsaturated cyclic carbonate monomer used in the present invention, acrylic acid or methacrylic acid ester is acrylic acid. Alternatively, methacrylic acid methyl, ethyl, butyl, 2-ethylhexyl, benzyl, phenyl, 2-tetrahydrofurfuryl, glycidyl ester and the like; styrene and its derivatives include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α- Methyl styrene, divinyl benzene, p-methoxy styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 2-vinyl anthracene and the like; and further as a hetero atom-containing aromatic vinyl monomer, 2-vinyl pyridine, 4-vinyl pyridine , N-
Vinylcarbazole, 2-vinylfuran, etc .; Vinyl ester derivatives include vinyl acetate, isopropenyl acetate, vinyl chloroacetate, vinyl propionate, vinyl benzoate, vinyl versatate, etc .; Vinylketone derivatives include methyl vinyl ketone , Methyl isopropenyl ketone, phenyl vinyl ketone, etc .; and the vinyl halide includes vinyl chloride, etc. In addition, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like can be mentioned. Also α, β
-Disubstituted ethylenically unsaturated monomers include maleic acid, itaconic acid, anhydrides of citraconic acid and their esters such as dimethyl maleate, dibutyl maleate,
Examples thereof include dimethyl itaconate, dibutyl itaconate, dibutyl citracone. Other examples include fumaric acid esters such as dibutyl fumarate.

The ethylenically unsaturated cyclic carbonate monomer alone or the copolymerization thereof with the ethylenically unsaturated monomer can be carried out by usual radical polymerization such as heat, ultraviolet ray, electron beam or microwave. .

As the thermal polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azo-di- (2,4
-Dimethylvaleronitrile), azo compounds, benzoylperoxide, di-t-butylperoxide, acetylperoxide, t-butylperbenzoate,
Examples thereof include peroxides such as methyl ethyl ketone peroxide, and persulfates such as ammonium persulfate and potassium persulfate. Redox initiator systems of these peroxides with cobalt naphthenate or aromatic amines are also useful.

Examples of the photoinitiator used in the UV polymerization include benzoin and its derivatives such as benzoin, benzoin methyl ether and benzoin isobutyl ether, benzyl derivatives such as benzyl and benzyl dimethyl ketal, and 4,4-bis ( Dimethylamino)
Examples thereof include benzophenone, 2-chloroanthraquinone, 2-methylanthraquinone, thioxanthone, diphenyldisulfide, dimethyldithiocarbamate and the like.

In the case of polymerization by ionizing radiation such as electron beam, it is usually carried out without a catalyst.

The amount of these initiators used is generally 0.01 based on the total amount of the ethylenically unsaturated cyclic carbonate monomer or the ethylenically unsaturated monomer (A) copolymerizable therewith. It is -10 mol%, preferably 0.1-5 mol%. If it is less than 0.01 mol%, the polymerization proceeds, but it requires a long time, which is not preferable. On the other hand, 1
If the initiator concentration exceeds 0 mol%, a low molecular weight product is likely to be formed, which is not preferable.

The molar fraction of the ethylenically unsaturated cyclic carbonate in the copolymer composed of the ethylenically unsaturated cyclic carbonate monomer and the ethylenically unsaturated monomer is the ethylenically unsaturated monomer to be copolymerized. Since the composition ratio varies depending on the type, the polymerization method, the polymerization conditions, etc., it cannot be specified unconditionally, but if it is 5 mol% or more, substantially non-contractibility is exhibited.

Polymerization may be carried out in any of bulk, solution, suspension and emulsion polymerizations. In the case of solution polymerization, examples of the solvent to be used include ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloroethylene and methylene chloride, and acetone. Examples thereof include ketones such as methyl ethyl ketone, methyl cellosolve, cellosolves such as ethyl cellosolve, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide.

In the case of solution polymerization, the monomer concentration is
It is 0.5 to 10 mol / l, preferably 1 to 5 mol / l. Although the polymer can be obtained even when the monomer concentration is less than 0.5 mol / l, the recovery yield is lowered due to the dilute solution, which is not preferable. On the other hand, if the concentration exceeds 10 mol / l, the solvent tends to remain in the copolymer, and a large amount of non-solvent is used, which is not preferable.

The polymerization temperature varies depending on the polymerization method, the ethylenically unsaturated cyclic carbonate monomer used, the type of ethylenically unsaturated monomer copolymerizable therewith, the type of initiator, the type of polymerization solvent and the like. Therefore, the temperature is usually 0 to 200 ° C., preferably 25 to 150 ° C., although it cannot be specified unconditionally. Even if the temperature is lower than 0 ° C, the polymerization proceeds, but it takes a long time and is not preferable. On the other hand, if the polymerization temperature is higher than 200 ° C., the polymer can be obtained in a short time, but the polymerization reaction rapidly occurs, which is not preferable.

The polymerization time varies depending on the polymerization method, the type of ethylenically unsaturated monomer used, the monomer concentration, the type and concentration of the initiator, etc., and therefore cannot be specified unconditionally, but it is usually 0.1 to 50. The time is preferably 1 to 25 hours.
Although the polymer is obtained depending on the polymerization temperature for less than 0.1 hour, the yield is low. Also, it is not economical to select a polymerization time that exceeds 50 hours.

The produced polymer is obtained by precipitating it in a non-solvent such as diethyl ether, methanol, hexane, etc., and washing and purifying it.

The polymer containing the ethylenically unsaturated cyclic carbonate of the present invention has a number average molecular weight of 0.1 to 150,000 in terms of polystyrene.

Since the ethylenically unsaturated cyclic carbonate monomer of the present invention and the polymer containing the same have a non-contractile cyclic carbonate group in the molecule, they are polymerized or crosslinked by a suitable ionic catalyst, In this case, it has a characteristic that it does not substantially change in volume. Therefore, since various problems associated with the polymerization shrinkage are solved, it is extremely useful for producing adhesives, casting materials, composite materials and the like. In addition, since it is crosslinked by an aliphatic polyamine having active hydrogen, it is also useful as a new crosslinkable polymer.

The ethylenically unsaturated cyclic carbonate monomer of the present invention and the polymer containing the same can be polymerized in the case where the cyclic carbonate group is ring-opened by any of anionic and cationic ionic catalysts. However, in the case of a polymer, crosslinking is carried out, and examples of the cationic catalyst used at this time include Lewis acids such as boron trifluoride, antimony trifluoride, iron trichloride, titanium tetrachloride, trifluoride, etc. Lewis acid complexes such as boron diethyl ether complex and boron trifluoride-aniline complex, benzenediazonium tetrafluoroborate, diphenyliodosonium tetrafluoroborate, dimethylphenacylsulfonium tetrafluoroborate, benzyltetramethylenesulfonium hexafluoroantimolybdate Various onium salts such as nate or methyl trif Oro methanesulfonate and the like.

Examples of the anionic catalyst include potassium t-butoxy, n-butyllithium, t-butyllithium and sodium methoxide.

In this case, the amount of the catalyst used is 0.001 to 20 mol%, preferably 0.1 to 10 mol% based on the cyclic carbonate group in the ethylenically unsaturated cyclic carbonate monomer or the polymer containing the same. Mol%. When it is less than 0.001 mol%, polymerization of the ethylenically unsaturated cyclic carbonate monomer or crosslinking of the polymer is substantially unlikely to occur. On the other hand, if the catalyst concentration exceeds 20 mol%, the utility of using a large amount of catalyst cannot be found and it is not economical.

As the aliphatic polyamine used in the present invention, any primary or secondary alkyl-substituted linear aliphatic or alicyclic amine can be used. Specific examples thereof include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, pentamethylenediamine, hexamethylenediamine, 2,4-diaminopentane, octamethylenediamine, decamethylenediamine, 1,2,3-triaminopropane, diethylenetriamine, triethylenetetramine, α, ω-diaminidiethyl ether, menthanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, bis (4-amine-3-methyldicyclohexyl) ) Methane, 1,4-bis (aminomethyl) cyclohexane, m
-Xylylenediamine, p-xylylenediamine, 1,
3,5-tris (aminomethyl) benzene, polyamines obtained from m-xylylenediamine and epichlorohydrin, unsubstituted polyamines such as amine-terminated polybutadiene-acrylonitrile copolymers, piperazine, N-ethylethylenediamine, N, N N-alkyl substituted aliphatic polyamines such as'-diethylethylenediamine are indicated.

These polyamines can be used either individually or in combination of two or more. The amount used is 0.01 to 50 with respect to the cyclic carbonate unit of the copolymer.
It is mol%, preferably 25 to 50 mol%. If the amount of these polyamines used is less than 0.01 mol% with respect to the cyclic carbonate unit, a cross-linked product is not substantially obtained, and even if it is used in excess of 50 mol%, the significance of using a large amount is recognized. Absent.

The temperature of the cross-linking reaction between the copolymer and the polyamine varies depending on the kind of the diamine used, but is 0 to
200 degreeC, Preferably it is 20-80 degreeC. Even if the temperature is lower than 0 ° C, the crosslinking reaction proceeds, but the reaction rate is slow. While 2
Although the cross-linking reaction exceeding 00 ° C is completed in a short time,
Coloring or side reaction is likely to occur, which is not preferable.

The time for the cross-linking reaction between the copolymer and the polyamine varies depending on the type of diamine used, but is 10
It is completed in seconds to 50 hours, usually less than 25 hours.

The crosslinking reaction is carried out in the presence or absence of a solvent. When a solvent is used, dioxane, ethers such as tetrahydrofuran, benzene,
Aromatic hydrocarbons such as toluene, xylene and chlorobenzene, ketones such as acetone and methyl ethyl ketone, dimethylformamide, dimethylacetamide and dimethylsulfoxide are shown.

[0049]

EXAMPLES The present invention will now be described in more detail with reference to Examples and Reference Examples. In the following examples and reference examples,
The analysis method used is as follows. 1. Specific gravity: Measured at 25 ° C. using a density gradient tube. 2. Number average molecular weight: CCP & 8 manufactured by Toyo Soda Kogyo Co., Ltd.
000 high performance liquid chromatograph (GPC) analyzer (column: 3 TSK gel-GHXL) was used and dimethylformamide was used as an eluent to measure at a flow rate of 1 ml / min. 3. Infrared absorption spectrum: FT / I manufactured by JASCO Corporation
It measured using R-5300. 4. Compositional analysis of copolymer: JNM-EX9 manufactured by JEOL Ltd.
It was analyzed by ¹ H-NMR spectrum using a 0 nuclear magnetic resonance apparatus (NMR).

Example 1 Synthesis of 2-oxo-5-ethyl-5- (p-vinylbenzyloxy) methyl-1,3-dioxane (hereinafter abbreviated as VBECC) 21 g of oily sodium hydride having a content of 55% or more ( About 12.6 g as sodium hydride, about 525 mmol)
Was gradually added to 400 ml of purified N, N-dimethylformamide stirred under a nitrogen stream. After cooling the flask to 10 ° C. or lower in an ice bath, 83.3 g (478 mmol) of trimethylolpropane dimethyl ketal was gradually added dropwise from the dropping funnel. After the dropping was completed, the reaction solution was returned to room temperature and further stirred for 30 minutes. Again 10 flasks
Cooled to below ℃, p-chloromethylstyrene 73.0g
(478 mmol) was slowly added dropwise. After that, the temperature was returned to room temperature and the mixture was stirred overnight. After confirming that the raw materials were consumed by silica gel thin layer chromatography using n-hexane as an eluent, the contents were poured into 1 l of water and extracted with diethyl ether three times. The organic layer was washed 3 times with water, N, N
After complete removal of dimethylformamide, it was dried over anhydrous magnesium sulfate overnight. The organic layer is then concentrated and 2,2-dimethyl-5-ethyl-5- (p-vinylbenzyloxy) methyl-1,3-dioxane 120
g (yield 87%) was obtained. A flask charged with 70 g (241 mmol) of this compound and 280 ml of methanol was cooled to 10 ° C. in an ice bath, and 20 ml (240 mmol) of concentrated hydrochloric acid was added thereto while stirring the contents, followed by solvolysis at room temperature. And the mixture was stirred for another 15 minutes. Then, the flask was cooled again on an ice bath, and 25 g (250 mmol) of triethylamine was gradually added to stop the reaction. Thereafter, the content was extracted with benzene, the organic layer was washed with water three times, and then dried over anhydrous magnesium sulfate overnight. Then, the organic layer was concentrated and recrystallized with diethyl ether, and 42.5 g of 2-ethyl-2- (p-vinylbenzyloxy) methyl-1,3-propanediol was added.
(Yield 70%) was obtained. The resulting diol 6.36 g (2
5.4 mmol) was dissolved in 130 ml of tetrahydrofuran, and the flask was cooled to 0 to 10 ° C. in an ice bath, and then 5.52 g (50.9 mmol) of ethyl chloroformate,
Triethylamine (5.15 g, 50.9 mmol) was added dropwise at the same time. After completion of the dropping, the reaction product was returned to room temperature and stirring was continued for further 5 hours. The triethylamine hydrochloride formed was filtered off, the tetrahydrofuran was distilled off under reduced pressure, and the contents were recrystallized from diethyl ether to give a melting point of 47-49.
4.2 g of white needle crystals at ℃ were obtained (yield 60%). As a result of infrared absorption (IR) spectrum and elemental analysis of the compound, 2-oxo-5-ethyl-5- (p-vinylbenzyloxy) methyl-1,3-dioxane (VBECC)
Was found to be The IR spectrum of the obtained VBECC is shown in FIG. At 1755 cm ^-1 , characteristic absorption of cyclic carbonate was observed. The results of elemental analysis were as follows. Elemental analysis value (as C ₁₆ H ₂₀ O ₄ ) C: measured value 69.68% (calculated value 69.54%) H: measured value 7.30% (calculated value 7.32%)

Example 2 Synthesis of 2-oxo-5- (p-vinylbenzyl) -1,3-dioxane (hereinafter abbreviated as VBCC) Journal of Polymer Science, T. Endo et al. Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. E
d. ) 2- (p-vinylbenzyl) -obtained by reducing the reaction product of diethyl malonate potassium salt and p-chloromethylstyrene according to the method described in Vol. 25, page 2595 (1987). After dissolving 4.36 g (21.0 mmol) of 1,3-propanediol in 100 ml of tetrahydrofuran and cooling the flask to 10 ° C. or lower on an ice bath, 4.56 g of ethyl chloroformate (4
2.0 mmol) and triethylamine 4.42 g (44.
(2 mmol) was added dropwise at the same time. After completion of the dropwise addition, the reaction product was returned to room temperature and further stirred for 5 hours, the generated triethylamine hydrochloride was filtered, and the tetrahydrofuran was concentrated, and then the content was subjected to silica gel thin layer chromatography to obtain hexane / ethyl acetate (volume ratio 1 / Development and purification with the mixed solvent of 1) gave 2.7 g of a colorless liquid (yield 59%).
From the IR spectrum of the compound and the result of elemental analysis, VB
It was confirmed to be CC. IR of the obtained VBCC
The spectrum is shown in FIG. At 1757 cm ^-1 , characteristic absorption of cyclic carbonate was observed. The results of elemental analysis were as follows. Elemental analysis value (as C ₁₃ H ₁₄ O ₃ ) C: measured value 71.24% (calculated value 71.53%) H: measured value 6.40% (calculated value 6.48%)

Example 3 Synthesis of 2-oxo-5-ethyl-5-methacryloyloxymethyl-1,3-dioxane (hereinafter abbreviated as CMA) 8.77 g (50 of trimethylolpropane dimethyl ketal was added to a flask equipped with a stir bar. Mmol), diethyl ether 50 ml, triethylamine 10.1 g (10
(0 mmol) was charged and the flask was cooled to 10 ° C or lower. 5.22 g (50 mmol) of methacrylic acid chloride was gradually added dropwise thereto. Then, the reaction solution was returned to room temperature and stirred for 5 hours. The generated triethylamine hydrochloride was filtered, the organic layer was concentrated, and then developed and purified by silica gel chromatography with hexane / diethyl ether (volume ratio 1/10) to obtain 2,2-dimethyl-5-methacryloyloxymethyl-1, 3-dioxane 8.01
g (yield 66%) was obtained. Methanol 20 in this flask
ml, cooled on an ice bath and concentrated hydrochloric acid 1.7 ml (20.
(4 mmol) was gradually added, and the mixture was stirred at room temperature for 15 minutes for solvolysis, and the flask was cooled again. Then, 2.02 g (20 mmol) of triethylamine was added to stop the reaction. Thereafter, methanol was distilled off under reduced pressure, and triethylamine hydrochloride produced by adding diethyl ether was filtered to obtain 2-methacryloyloxymethyl-1,3-propanediol. The obtained diol 3.6 g (1
(7.8 mmol) was dissolved in 70 mL of tetrahydrofuran, and the flask was cooled, and then 3.9 g (36 mmol) of ethyl chloroformate and 3.7 g of triethylamine were added.
(36.6 mmol) was added dropwise at the same time. After completion of dropping, the reaction solution was returned to room temperature and stirred for 5 hours. Triethylamine hydrochloride was removed from the reaction solution, tetrahydrofuran was distilled off under reduced pressure, and the residue was recrystallized from diethyl ether to obtain 2.4 g of white crystals having a melting point of 51 to 52 ° C. (yield 59%).
From the IR spectrum of the compound and the result of elemental analysis, C
It was confirmed to be MA. The IR spectrum of the obtained CMA is shown in FIG. At 1757 cm ^-1 , characteristic absorption of cyclic carbonate was observed. The results of elemental analysis were as follows. Elemental analysis value (as C ₁₁ H ₁₆ O ₄ ) C: measured value 57.76% (calculated value 57.89%) H: measured value 7.08% (calculated value 7.02%)

Example 4 Synthesis of VBECC / Styrene Copolymer N, N-dimethylformamide 4 ml, VBECC 2.75 g (10 mmol), styrene 1.05 g (10 mmol) were placed in a polymerization sealed tube equipped with a stir bar. , 14.5 mg of benzoyl peroxide (3 mol% of the total amount of the monomers) were charged, and the polymerization sealed tube was freeze-deaerated and sealed at 80 ° C for 3 hours.
Stir for hours. After opening the sealed tube, 6 ml of N, N-dimethylformamide was added to dilute the copolymer, and then the content was dropped into 400 ml of methanol with stirring to obtain a white precipitate. The obtained copolymer was filtered, further washed with 200 ml of methanol, and vacuum dried at 60 ° C. overnight to obtain 1.91 g (yield 50%) of a white solid. The IR spectrum of the copolymer is shown in FIG. 17
A characteristic absorption of cyclic carbonate was observed at 57 cm ^-1 . The content of VBECC in this copolymer was δ = 6.5 to 7. in the nuclear magnetic resonance spectrum ( ¹ H-NMR).
6 ppm (proton of benzene nucleus) and δ = 4.4 ppm
5 calculated from the integral ratio with (benzylic proton)
It was 3 mol%. The number average molecular weight of the copolymer (M
n) is 68,000 in terms of polystyrene based on GPC analysis.
It was 0 and the specific gravity was 1.17.

Examples 5 to 15 Copolymerization with various ethylenically unsaturated monomers (A) was carried out in the same manner as in Example 4, and the results are shown in Table 1.

[0055]

[Table 1]

Example 16 Synthesis of homopolymer of VBCC In the same manner as in Example 1, N, N-dimethylformamide was added to a polymerization solvent (concentration of VBCC of 1 mol / mol) in a polymerization sealed tube.
l), V as benzoyl peroxide as a polymerization initiator
It was used at 3 mol% with respect to BCC and reacted at 80 ° C. for 5 hours to obtain a white polymer with a conversion rate of 94%. VB in Figure 5
1 shows an IR spectrum of a CC homopolymer. 1755c
Characteristic absorption of cyclic carbonate is observed at m ^-1 .
The number average molecular weight by GPC was 30,000.

Reference Example 1 276 mg of VBECC obtained in Example 1 was added to toluene 1
It was dissolved in ml, and as an anionic ring-opening catalyst, t-
After adding 30 μl of butoxypotassium (1 mol / l tetrahydrofuran solution) and reacting at 0 ° C. for 24 hours,
Precipitation in 40 ml of methanol gave a syrupy polymer. This polymer is tetrahydrofuran,
It was soluble in common organic solvents such as methylene chloride and acetone. The IR spectrum of the polymer is shown in FIG. 6, as can be seen from the IR spectrum, disappeared absorption of cyclic carbonates of 1757cm ^-1, a new absorption chain carbonate to 1750 cm ^-1 appeared, 1630 cm ^-1 It was confirmed that the polymerization was due to the ring-opening polymerization of the cyclic carbonate because the absorption of the olefin of (1) remained unchanged. Also, since the specific gravity is 1.193 and the specific gravity of VBECC is 1.231, the volume expansion due to polymerization is 3.31.
It was 0%.

Reference Example 2 VBECC / styrene copolymer 20 obtained in Example 4
0 mg was dissolved in 1 ml of N, N-dimethylformamide, to which 5.6 mg of sodium methoxide (corresponding to 10 mol% based on the cyclic carbonate group in the copolymer) was added as an anionic ring-opening catalyst. The mixture was reacted at 0 ° C for 40 hours to obtain a white precipitate. This reaction product was crosslinked and was insoluble in ordinary solvents such as methylene chloride, N, N-dimethylformamide and toluene. In the IR spectrum of this crosslinked polymer, the characteristic absorption of the cyclic carbonate group at 1760 cm ^-1 decreased, and a new absorption derived from the ester of chain carbonate at 1240 cm ^-1 appeared. Further, since the specific gravity of the crosslinked polymer was 1.15 and the specific gravity of the polymer before crosslinking was 1.17, a volume expansion of 1% was observed due to the crosslinking.

Reference Example 3 CMA / styrene copolymer 150 obtained in Example 12
mg was dissolved in 1 ml of N, N-dimethylformamide, 4.8 mg of sodium methoxide (corresponding to 8.7 mol% based on the cyclic carbonate group in the copolymer) was added, and reacted at 80 ° C. for 20 hours. And a white precipitate was obtained.
The reaction product is crosslinked and contains methylene chloride, N,
It was insoluble in ordinary solvents such as N-dimethylformamide and toluene. Shows the IR spectrum of the crosslinked polymer in Figure 7, reduces the characteristic absorption of the cyclic carbonate groups 1766Cm ^-1, new absorption appeared to be derived from esters of a chain carbonate of the 1240 cm ^-1. Further, since the specific gravity of the crosslinked polymer was 1.209 and the specific gravity of the polymer before crosslinking was 1.216, volume expansion of 0.6% was recognized.

Reference Example 4 VBECC / styrene copolymer 18 obtained in Example 4
8 mg was dissolved in 1 ml of N, N-dimethylformamide, and 15 mg of hexamethylenediamine (corresponding to 50 mol% with respect to the cyclic carbonate unit in the copolymer) was added thereto and stirred at room temperature for 1 hour. Stirring became difficult within. This reaction product was crosslinked and was insoluble in methylene chloride, N, N-dimethylformamide, toluene and the like. The IR spectrum of this crosslinked product is 1
Characteristic absorptions annular carbonate in 760 cm ^-1 is reduced, absorption derived from ester and 1690 cm ^-1 of the chain carbonate in the 1240 cm ^-1 was emerging.

[0061]

INDUSTRIAL APPLICABILITY The novel ethylenically unsaturated cyclic carbonate monomer of the present invention and its polymer have non-contractile cyclic carbonate group in the molecule, and therefore, they can be cured by crosslinking with a suitable ionic catalyst. It has the characteristic that it shows substantially no volume change. Therefore, since various problems associated with polymerization shrinkage are solved, it is extremely useful for manufacturing adhesives, casting materials, composite materials and the like. In addition, it is also extremely useful as a new crosslinkable polymer that can be crosslinked with an aliphatic polyamine having active hydrogen.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of VBECC, which is an ethylenically unsaturated cyclic carbonate of the present invention.

FIG. 2 is a diagram showing an infrared absorption spectrum of VBCC, which is an ethylenically unsaturated cyclic carbonate of the present invention.

FIG. 3 is a diagram showing an infrared absorption spectrum of CMA, which is an ethylenically unsaturated cyclic carbonate of the present invention.

FIG. 4 is a diagram showing an infrared absorption spectrum of the copolymer of VBECC and styrene obtained in Example 1.

FIG. 5 is a diagram showing an infrared absorption spectrum of a homopolymer of VBCC.

FIG. 6 shows t- as an anionic ring-opening catalyst of VBECC.
It is a figure which shows the infrared absorption spectrum of the ring-opening polymer obtained by butoxy potassium.

FIG. 7 is a diagram showing an infrared absorption spectrum of a crosslinked polymer of the CMA / styrene copolymer obtained in Example 12 using an anionic ring-opening catalyst.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08F 214/00 MKT 218/04 MLH 220/18 MLY 220/44 MMY 7242-4J 222/00 MLU

Claims (10)

[Claims] 1. The following general formula (I): (In the formula, R ¹ represents at least one polymerizable vinyl group selected from the group consisting of a (meth) acryloyloxy group, a styryl group and a vinylbenzyloxy group, and R ² represents hydrogen or a C 1-10 group. An ethylenically unsaturated cyclic carbonate monomer represented by (which represents a hydrocarbon group). 2. The ethylenically unsaturated cyclic carbonate monomer according to claim 1, wherein R ¹ is a methacryloyloxy group and R ² is an ethyl group. 3. The ethylenically unsaturated cyclic carbonate monomer according to claim 1, wherein R ¹ is a vinylbenzyloxy group and R ² is an ethyl group. 4. The ethylenically unsaturated cyclic carbonate monomer according to claim 1, wherein R ¹ is a styryl group and R ² is hydrogen. 5. A homopolymer obtained by polymerizing the polymer using the radical polymerization initiator of the ethylenically unsaturated cyclic carbonate monomer according to claim 1, or the ethylenically unsaturated cyclic carbonate monomer. A polymer having a cyclic carbonate group, which is a copolymer obtained by polymerizing a copolymerizable ethylenically unsaturated monomer (A) with a radical polymerization initiator. 6. The ethylenically unsaturated monomer (A) has the general formula (II): (In the formula, X represents hydrogen or a methyl group, Y represents —CN,
-COOR ^3, -OCOR ^3, represents an aromatic group which may contain a halogen or a substituent, R ³ is 1 to 8 carbon atoms
The copolymer having a cyclic carbonate group according to claim 5, which is selected from one or more ethylenically unsaturated monomers (which represent an alkyl group or an aromatic group). 7. The ethylenically unsaturated monomer (A) is selected from the group consisting of maleic anhydride and its derivatives, fumaric acid derivatives, itaconic anhydride and its derivatives, and citraconic anhydride and its derivatives. The copolymer having a cyclic carbonate group according to claim 5 or 6, which is at least one α, β-disubstituted ethylenically unsaturated monomer. 8. The ethylenically unsaturated monomer (A) is at least one ethylenically unsaturated monomer represented by the general formula (II) and an α, β-disubstituted ethylenically unsaturated monomer. A copolymer having a cyclic carbonate group according to any one of claims 5 to 7. 9. The polymer has a number average molecular weight in terms of polystyrene of 0.1 to 150,000 and has the general formula (I) in the polymer.
The molar fraction of the ethylenically unsaturated cyclic carbonate monomer represented by and the ethylenically unsaturated monomer (A) is 5/95.
The polymer having a cyclic carbonate group according to any one of claims 5 to 8, which is -100/0. 10. A crosslinkable polymer composition comprising the copolymer having a cyclic carbonate group according to any one of claims 5 to 8 and an aliphatic polyamine.