JP2012232954A - Styrene derivative and polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound and a polymer applicable to various functional materials, and to provide the polymer excellent especially in heat resistance and chemical resistance.SOLUTION: This invention relates to a compound represented by formula (a). Symbols in the formula (a) indicate following meanings: Qindicates a single-bond or a divalent linking group, and Zand Zmutually independently indicate an oxygen atom or a sulfur atom.

Description

  The present invention relates to a styrene polymer having a five-membered carbonate structure useful as a functional material and a novel polymerization raw material compound thereof.

A polymer containing a 5-membered carbonate structure in the side chain exhibits high dielectric constant and refractive index, and is known to be useful as various functional materials such as polymer electrolytes and resist materials (non- Patent Literatures 1 to 3). Moreover, the curable resin composition which added the crosslinking agent to this polymer is useful as a mold release agent or a coating material (refer patent documents 1-3).
However, since the polymers proposed in these documents are mainly acrylic acid or methacrylic acid polymers, the heat resistance is not so high, and there is a problem that application to various uses is limited.

  Further, as a method for obtaining a polymer having a 5-membered cyclic carbonate structure, it has been proposed to form a carbonate structure by reacting carbon dioxide with a polymer having an epoxy ring (Non-patent Document 4). However, in this production method, there is no problem in reactivity for acrylic acid or methacrylic acid polymer, but in the case of styrene polymer, the reactivity of epoxy ring and carbon dioxide is low, and epoxy ring and carbonate ring are mixed. Only polymers are obtained.

JP 2005-36081 A JP 2003-327853 A JP 2003-327854 A

Macromolecures, 1995, 28, 3468-3470 Macromolecures, 2007, 40, 7558-7565 Optical Materials 21 (2002) 331-335 Macromolecures, 1995, 28, 4701-4706

  In order to solve such problems, an object of the present invention is to provide a polymer that can be applied to various functional materials and a novel polymer raw material compound. In particular, it is an object of the present invention to provide a polymer having a 5-membered ring carbonate structure having good heat resistance. It is another object of the present invention to provide the polymer having good chemical resistance.

The present invention provides a compound represented by the following formula (a).
Symbols in the formula (1) have the following meanings.
Q ¹ : A single bond or a divalent linking group.
Z ¹ and Z ² : independently of each other, an oxygen atom or a sulfur atom.

In the formula (a), Q ¹ is a compound having a linear or branched alkylene group having 1 to 5 carbon atoms in which one or more —CH ₂ — may be substituted with an etheric oxygen atom. A compound in which Q ¹ is —CH ₂ —O—CH ₂ — is more preferable.

A compound in which Z ¹ and Z ² are both oxygen atoms is preferred.
A compound in which Z ¹ and Z ² are both sulfur atoms is also preferred.

  The present invention also provides a polymer containing a structural unit derived from the compound represented by the formula (a).

Since the polymer according to the present invention has a styrene skeleton, it is excellent in heat resistance, chemical resistance, and the like as compared with an existing acrylic polymer having a 5-membered ring carbonate structure. In addition, the polymer according to the present invention can be suitably used as a reactive polymer, particularly for various functional materials such as a polymer electrolyte, a resist material, an optical material, a paint, a release agent, and an adhesive.
The compound according to the present invention is useful as a raw material compound capable of introducing such a 5-membered carbonate structure of a polymer.

  In the present specification, the compound represented by the formula (a) is also referred to as a compound (a). The compounds represented by other formulas may be expressed similarly. The compound (a) is also referred to as “the compound of the present invention”.

In the formula (a), Q ¹ is a single bond or a divalent linking group.
Examples of the divalent linking group include a linear or branched alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, a 6-membered aromatic group, a saturated 4- to 6-membered ring, Examples thereof include an unsaturated aliphatic group and a 5- to 6-membered heterocyclic group. These divalent linking groups may be combined, and a plurality of ring groups may be condensed. Further, the hydrogen atom in these divalent linking groups may have a halogen atom substituent. One or more —CH ₂ — in the alkylene group may be substituted with an etheric oxygen atom.

Q ¹ can be appropriately selected as long as it is a single bond or a divalent linking group, and is not limited to the above examples. Among these, one or more —CH ₂ — in the group is ethereal. A linear alkylene group having 1 to 5 carbon atoms which may be substituted with an oxygen atom is preferred, and —CH ₂ —O—CH ₂ — is particularly preferred. This is because when Q ¹ is such a group, the heat resistance and chemical resistance of the polymer of the present invention are particularly good and the stability is improved.

In the formula (a), Z ¹ and Z ² are each independently an oxygen atom or a sulfur atom. When both are oxygen atoms, a 5-membered cyclic carbonate structure is formed, and when both are sulfur atoms, a 5-membered cyclic dithiocarbonate structure is formed. Z ¹ and Z ² can be appropriately selected depending on the application. In addition, from the viewpoint that no bad odor due to sulfide is generated even when heated, it is preferable that both Z ¹ and Z ² are oxygen atoms. Further, from the viewpoint of increasing the refractive index and being suitable for a plastic lens or the like, it is preferable that both Z ¹ and Z ² are sulfur atoms. In addition, when used in a crosslinking site, the reaction rate between Z ¹ and Z ² both being a sulfur atom and an amine compound is significantly higher than that when both Z ¹ and Z ² are oxygen atoms. Since it is fast, it is possible to control the crosslinking reaction rate.

  Although the manufacturing method of the compound of this invention is not specifically limited, If it is the method of making the compound which has an epoxy ring, and carbon dioxide or carbon disulfide react, it is possible to manufacture by various methods.

For example, the compound of the present invention can be obtained by reacting a compound having both a styrene skeleton and an epoxy ring with carbon dioxide or carbon disulfide. The reaction scheme is shown below.

More specifically, the compound of formula (a) in which Q ¹ is —CH ₂ —O—CH ₂ — will be described as an example. Vinyl benzyl glycidyl ether is converted to an alkali metal halide salt such as LiBr. By reacting with carbon dioxide or the like in the presence, the compound of the present invention can be obtained. Vinylbenzyl glycidyl ether can be synthesized by referring to known literature such as JP-A-9-227540.

It is also possible to introduce a styrene skeleton after forming a 5-membered ring. For example, a compound having an epoxy ring such as epichlorohydrin (such as Tokyo Kasei) or glycidol (such as Aldrich) is reacted with carbon dioxide to form a 5-membered ring, and then vinylbenzyl, a compound having a styrene skeleton. Examples thereof include a method of reacting with alcohol or vinyl benzyl chloride (such as chloromethylstyrene manufactured by AGC Seimi Chemical). The reaction scheme is shown below.
Vinylbenzyl alcohol is obtained by hydrolyzing vinylbenzyl chloride. The same applies when carbon disulfide is used.

  The polymer of the present invention is a polymer containing a structural unit derived from the compound (a) (hereinafter referred to as the structural unit (A)). The polymer of the present invention may be a homopolymer of the compound (a) or a copolymer containing a structural unit derived from another polymerizable compound (b) (hereinafter referred to as a structural unit (B)). .

  Other polymerizable compounds (b) include compounds having an unsaturated group such as styrene compounds (b1) and (meth) acrylic acid compounds (b2) other than the compound of the present invention and compound (c) (b And a compound (b3) which is another polymerizable compound. Although the specific example of such a compound (b) is shown below, it is not limited to these.

As said (b1), the styrene-type compound represented by a following formula is mentioned.
^{_{Wherein, R 2: -H, CH 3}} , -Cl, -CHO, -CH 2 Cl, -CH 2 NH 2, -CH 2 N (CH 3) 2, -CH 2 N + (CH 3) 3 Cl ^{_{-, -CH 2 N + H 3}} Cl -, -CH 2 CN, -CH 2 N (CH 2 COOH) 2, a _-CH 2 SH or _-CH 2 OCOCH _3.

Examples of the compound (b2) include α-chloroacrylic acid and (meth) acrylate represented by the following formula.
^{_{CH 2 = C (R 1)}} -COO-Q 2 -R 3
In the formula, R ¹ : H or CH ₃ , Q ² : a single bond or a divalent linking group, R ³ : —OH, —Si (OAk) ₃ (“Ak” is a straight chain having 1 to 3 carbon atoms or Branched alkyl group), —CH ₃ , —CH ₂ CH ₂ N (CH ₃ ) ₂ , — (CH ₂ ) _m H (m = 2 to 20), —CH ₂ CH (CH ₃ ) ₂ , _{-CH 2 -C (CH 3) 2} -OCO-Ph, ( "Ph" and so on means a phenyl _{group..) - CH 2 Ph,} -CH 2 CH 2 OPh, -CH 2 N + ( CH ₃ ) ₃ Cl ⁻ , — (CH ₂ CH ₂ O) _m CH ₃ (m is an integer of 2 to 20), — (CH ₂ ) ₂ —NCO, or the following group.
As the divalent linking group for Q ^2, includes the same structure as that to Q ¹ said compound (1). Q ² is preferably a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms.

Examples of the compound (b2) also include (meth) acrylamide represented by the following formula.
^{_{CH 2 = C (R 1)}} -CONH-R 4
In the formula, R ^{1 is} H or CH ₃ , R ^{4 is} —C _m H _{2m + 1} (m is an integer of 2 to 20) or —H.

Examples of the compound (b2) include (meth) acrylic acid diesters, and (meth) acrylic acid polyesters such as compounds represented by the following formulas.
And RCH ₂ CH ₂ R.
R in the above formula is a (meth) acryloyloxy group.

In addition, examples of the compound (b3) include vinyl compounds other than the above (b1) and (b2), for example, vinyl chloride (CH ₂ ═CHCl) or acrylonitrile (CH ₂ ═CHCN).

  The structural unit (B) contained in the polymer of the present invention may be derived from one type of the compound (b) or may be derived from two or more types.

The molecular weight of the polymer of the present invention is not particularly limited, but is preferably 1 × 10 ³ to 1 × 10 ⁷ in terms of weight average molecular weight (Mw), and more preferably 1 × 10 ⁴ to 1 × 10 ^6. . Further, the number average molecular weight (Mn) is preferably 1 × 10 ³ to 1 × 10 ⁷ , and more preferably 5 × 10 ³ to 1 × 10 ⁵ .

  The polymer of the present invention is not particularly limited in the form of polymerization. The form of polymerization in the case of a copolymer is not particularly limited and may be any of random, block, graft and the like, but is preferably a random polymer.

  The method for producing the polymer is not particularly limited as long as the 5-membered carbonate structure of the compound (a) is maintained, and various known methods can be adopted. For example, addition polymerization can be performed based on an unsaturated group in each compound. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source.

  The polymer of the present invention has high selectivity that it does not react with alcohol or carboxylic acid but reacts with amine. Further, due to the high reactivity with amines, the addition of diamine to the polymer makes it possible to easily form a crosslinking reaction and synthesize a network polymer. This shows that it is useful also as a paint.

As described above, the polymer of the present invention can be applied to various functional materials. For example, when LiPF ₆ or the like is used as an electrolyte in a non-aqueous electrolyte secondary battery, a coordination structure is formed with Li and a 5-membered ring portion by using the polymer of the present invention as a polymer support, It is considered to be a stable gel. As a result, it is conceivable that safety is improved without causing problems such as leakage and evaporation as compared with a liquid electrolyte. In addition, the polymer of the present invention has good heat resistance and good chemical resistance such as alkali resistance, and is therefore suitable for applications requiring high safety. The polymer of the present invention has a high polarity because it has a carbonate structure or a dithiocarbonate structure. Therefore, the wettability of the base material can be improved by adding it internally to the resin or by applying it to the surface as a paint.

  The present invention will be specifically described below, but the present invention is not limited to the following examples. The reagents used in the examples and the measurement conditions are shown below.

<Reagents>
Vinylbenzyl glycidyl ether (VBGE) was synthesized by a known method and distilled under reduced pressure using 3,5-dinitrotoluene as a polymerization inhibitor.
As lithium bromide (LiBr), commercially available anhydrous LiBr (Kanto Chemical) was vacuum-dried at 120 ° C. before use.
Carbon dioxide was used by filling the air-collecting balloon with liquefied carbon dioxide gas (Fukutoei acid) at atmospheric pressure.
A commercially available product (Wako Pure Chemical Industries) was used for carbon disulfide.
2,2′-Azobis (isobunitronitrile) (AIBN) was used by recrystallizing a commercial product (Wako Pure Chemical Industries) with methanol.
Styrene (St) was used after washing a commercially available product (Wako Pure Chemical Industries) with 1 mol / L sodium hydroxide aqueous solution and pure water, drying over sodium sulfate, and distillation under reduced pressure.
For methyl methacrylate (MMA), a commercially available product (Wako Pure Chemical Industries) was washed with 1 mol / L sodium hydroxide aqueous solution and pure water, dried over sodium sulfate and distilled.
As 1,2-bis (2-aminoethoxy) ethane, a commercially available product (Tokyo Chemical Industry) was used.
N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), methyl ethyl ketone (MEK) and tetrahydrofuran (THF) are commercially available products (Wako Pure Chemical Industries) distilled by conventional methods. Used after purification.

<Measurement conditions>
¹ H-NMR (300 MHz) and ¹³ C-NMR (100 MHz) spectra were measured using a JEOL-AL300 nuclear magnetic resonance spectrophotometer. The chemical shift was determined based on tetramethylsilane.
The IR spectrum was measured by the ATR method with a Smart iTR sample accessory attached to Nicolet iS10 (Thermo Scientific).
In thermogravimetric analysis (TGA), TG-DTA 6200 (Seiko Instruments Inc.) was used, and about 4 mg of a sample was placed in an aluminum container in a nitrogen (50 mL / min) stream and the temperature was raised to 500 ° C. at 10 ° C./min. Measured.
Differential scanning calorimetry (DSC), until 160 ° C. at ⁵ o C / min by sealing the sample about 4mg an aluminum container with nitrogen (20 mL / min) in a stream with a DSC-6200 (Seiko Instruments Inc.) The temperature increase was repeated and the second temperature increase data was recorded.

Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are 0.01 mol / L-LiBr for HLC-8220 GPC (Tosoh) equipped with TSKgel super AW2500, AW3000, and AW4000 columns. The DMF solution of was measured as an eluent and was determined on a polystyrene basis.
The density of each monomer and polymer was measured using a micromeritic dry automatic density meter AccuPyc 1340 (Shimadzu Corporation).
In each of the above measurements, the solid sample was finely ground in a ceramic mortar before measurement.

Example 1 Synthesis of Compound (a-1)

LiBr (220 mg, 2.5 mmol), VBGE (9.45 g, 50 mmol), and DMF (30 mL) are added to a 100 mL eggplant flask, and a 5 L air collection balloon filled with carbon dioxide is connected to reduce the pressure and the inside of the reaction vessel is oxidized. Carbon substitution.
The mixture was heated at 100 ° C. for 24 hours under a carbon dioxide atmosphere. After cooling to room temperature, the reaction solution is poured into pure water, the organic matter is extracted with ethyl acetate, the obtained organic phase is washed five times with pure water, dried over sodium sulfate, and concentrated under reduced pressure to give compound (a- The crude product of 1) (10.6 g) was obtained with a crude yield of 91%.
The crude product was purified by silica gel column chromatography (developing solvent hexane / ethyl acetate = 5: 1 (v / v)), and the compound (a-1) was isolated in a yield of 81%.

IR (ATR): 712, 765, 824, 904, 984, 1038, 1100, 1160, 1510, 1625, 1781, 2836 cm ⁻¹ .
¹ H-NMR (CDCl ₃ ): 3.68 (dd, J = 3.7, 11.0 Hz, 1H), 3.75 (dd, J = 3.7, 11.0 Hz, 1H), 4.34 (Dd, J = 6.3, 8.5 Hz, 1H), 4.44 (dd, J = 8.4, 8.5 Hz, 1H), 4.52 (d, J = 11.8 Hz, 1H), 4.75 (d, J = 11.8 Hz, 1H), 4.78 (dddd, J = 3.7, 3.7, 6.3, 8.4 Hz, 1H), 5.25 (d, J = 10.8 Hz, 1 H), 5.75 (d, J = 17.2 Hz, 1 H), 6.70 (dd, J = 10.8, 17.2 Hz, 1 H), 7.26 (d, J = 8 .2 Hz, 2H), 7.39 (d, J = 8.2 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): 67.33, 68.86, 73.35, 75.15, 114.3, 126.4, 127.2, 128.0, 136.4, 137.4, 155 .1.

Example 2 Synthesis of Compound (a-2)

To a 100 mL eggplant flask, LiBr (220 mg, 2.5 mmol) and VBGE (9.45 g, 50 mmol) were added, and after nitrogen substitution, THF (30 mL) was added and cooled to 0 ° C., and carbon disulfide (4.67 g, 62.5 mmol) was added. ) Was added and stirred for 2 hours, followed by stirring at room temperature for 3 hours. The reaction solution was poured into pure water, the organic matter was extracted with diethyl ether, and the resulting organic phase was washed five times with pure water, dried over sodium sulfate, and concentrated under reduced pressure to give crude compound (a-2). The product (11.6 g) was obtained with a crude yield of 86%.
The crude product was purified by silica gel column chromatography (developing solvent hexane / ethyl acetate = 3: 1 (v / v)) to isolate compound (a-2) in a yield of 78%.

IR (ATR): 822, 905, 984, 1031, 1181, 1225, 1510, 1624, 2859 cm ⁻¹ .
¹ H-NMR (CDCl ₃ ): 3.61 (dd, J = 7.3, 11.1 Hz, 1H), 3.70 (dd, J = 8.2, 11.1 Hz, 1H), 3.78 (Dd, J = 4.4, 10.6 Hz, 1H), 3.85 (dd, 5.1, 10.6 Hz, 1H), 4.59 (d, J = 11.9 Hz, 1H), 4. 64 (d, J = 11.9 Hz, 1H), 5.25 (dddd, J = 4.4, 5.1, 7.3, 8.2 Hz, 1H), 5.26 (d, J = 1.11. 0 Hz, 1H), 5.77 (d, J = 17.7 Hz, 1H), 6.73 (dd, J = 11.0 Hz, 1H), 7.31 (d, J = 8.1 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): 36.13, 68.57, 73.46, 89.20, 114.2, 126.4, 128.1, 136.4, 136.7, 137.4, 212 0.0.

Next, production examples of the polymer of the present invention are shown. In the polymerization of these examples, the structural units (A-1) to (B-2) shown below are derived from the respective polymerization raw material compounds (a-1) to (b-2).

(Example 3) Production of homopolymer (1-1) of compound (a-1) Compound (a-1) obtained in Example 1 under a nitrogen atmosphere using a 20 mL Schlenk tube with a three-way cock A solution of the crude product (699 mg, 3 mmol) and AIBN (14.7 mg, 0.09 mmol) in DMF (3 mL) was heated at 60 ° C. for 24 hours and then cooled to room temperature.
A portion was sampled and subjected to ¹ H-NMR measurement, and the monomer conversion rate was determined from the integrated intensity ratio of the 5.8 ppm vinyl group CH peak and the 4.9 ppm 5-membered carbonate CH peak. The reaction mixture is poured into methanol, and the solid is recovered by centrifugation. The obtained solid is dissolved in a small amount of acetone, reprecipitated with methanol, recovered by centrifugation, and vacuum-dried to give a polymer (1- A white solid (433 mg) of 1) was obtained in a yield of 62%.

The spectral data measured for the polymer (1-1) are shown below.
IR (ATR): 710, 767, 809, 832, 1035, 1100, 1160, 1511, 1781, 2901, 2845 cm ⁻¹ .
¹ H-NMR (DMSO-d ₆ ) 0.70-2.15 (m, 3H), 3.40-4.00 (m, 4H), 4.25-4.65 (m, 2H), 5 .35-5.55 (m, 1H), 6.10-6.80 (m, 2H), 6.80-7.35 (m, 2H).

In the above, the compound (a-1) was polymerized under the same conditions except that DMAC, DMSO, and MEK were used instead of DMF. Table 1 shows the conversion, yield, M _n , M _w , and M _w / M _n for each solvent.

(Example 4) Production of homopolymer (1-2) of compound (a-2) <In the case of 1 mol% of initiator>
Using a 20 mL Schlenk tube with a three-way cock, in a nitrogen atmosphere, the crude product of compound (a-2) obtained in Example 2 (810 mg, 3 mmol) and AIBN (4.9 mg, 0.03 mmol) When the DMSO (3 mL) solution was heated to 60 ° C. and cooled to room temperature after 6 hours, a gel-like reaction mixture was obtained.
The gel-like reaction mixture was placed in methanol, and the solid was collected by centrifugation and vacuum dried to obtain a white solid with a yield of 47% (380 mg).
In the above, the gel-like reaction mixture obtained in the same manner except that DMSO was replaced with DMF or MEK was similarly centrifuged and dried to obtain white solids in a yield of 26% (211 mg) and a yield of 31%, respectively. (251 mg).
None of the solids obtained above was dissolved in DMSO or DMF. The results are shown in Table 2.

<In the case of initiator 3 mol%>
In the above, it carried out similarly except having used the solution of AIBN (14.7 mg, 0.09 mmol) in DMSO (6 mL) as the initiator solution. A part of the reaction mixture after heating at 60 ° C. for 6 hours was extracted and subjected to ¹ H-NMR measurement. From the integrated intensity ratio of CH peak of 5.8 ppm vinyl group and CH peak of 5.6 ppm 5-membered ring dithiocarbonate. The monomer conversion was determined to be 38%.
The reaction mixture is poured into methanol, and the solid is recovered by centrifugation. The obtained solid is dissolved in a small amount of THF, re-precipitated in methanol, and the solid is recovered by centrifugation. -2) white solid (259 mg) was obtained in a yield of 32%.
In the above, it carried out similarly except having made the heating time in 60 degreeC into 12 hours and 24 hours. The results are shown in Table 2.

The spectral data measured for the polymer (1-2) are shown below.
IR (ATR): 808, 831, 1034, 1088, 1184, 1223, 1337, 1507, 2845, 2909 cm ⁻¹ .
¹ H-NMR (DMSO-d ₆ ): 0.62 to 2.30 (m, 3H), 3.42 to 3.78 (m, 2H), 4.10 to 4.35 (m, 1H), 4.35-4.65 (m, 3H), 4.82-5.05 (m, 1H), 6.18-6.80 (m, 2H), 6.80-7.25 (m, 2H) ).

Example 5 Copolymerization of Compound (a-1) Using a 20 mL Schlenk tube with a three-way cock, under a nitrogen atmosphere, a crude product (545 mg, 2) of compound (a-1) obtained in Example 1 .25 mmol), St (78 mg, 0.75 mmol) and AIBN (14.4 mg, 0.09 mmol) in DMF (3 mL) were heated at 60 ° C. for 72 hours and then cooled to room temperature.
The reaction mixture is poured into methanol, and the solid is recovered by centrifugation. The obtained solid is dissolved in a small amount of acetone, re-precipitated in methanol, and the solid is recovered by centrifugation. A white solid (480 mg) of 3) was obtained in a yield of 81%.

  Polymer (1-4) and polymer (1-5) were obtained in the same manner except that the ratio of compound (a-1) to St was changed to the charge ratio shown in Table 3. These results are shown in Table 3.

The copolymer composition in the polymer obtained was that the peak of the 5-membered carbonate CH of the 4.9 ppm constituent unit (A-1) of the ¹ H-NMR spectrum and the 6.2-7.4 ppm constituent unit (B It was calculated | required from the integral intensity ratio with the peak of aromatic ring CH of -1).

Example 6 Copolymerization of Compound (a-2) In the production of the polymer (1-3) of Example 5, the compound obtained in Example 2 instead of the crude product of compound (a-1) Compound (a-2) and St were copolymerized in the same manner except that the crude product of (a-2) (599 mg, 2.25 mmol) was used, and the polymer (1-6) white solid ( 568 mg) was obtained in a yield of 84%.
A polymer (1-7) and a polymer (1-8) were obtained in the same manner except that the ratio of the compound (a-2) and St was changed to the charging ratio shown in Table 4. These results are shown in Table 4.

The copolymer composition in the polymer obtained was as follows: the CH peak of the 5-membered cyclic dithiocarbonate of the 5.4 ppm constituent unit (A-2) of the ¹ H-NMR spectrum, and the 6.2-7.3 ppm constituent unit. It calculated | required from the integral intensity ratio of the peak of aromatic ring CH of (B-1).

(Example 7)
Using a 20 mL Schlenk tube equipped with a three-way cock, under a nitrogen atmosphere, the crude product (350 mg, 1.50 mmol), MMA (151 mg, 1.50 mmol) and AIBN (14. A solution of 4 mg, 0.09 mmol) in DMF (3 mL) was heated at 60 ° C. for 24 hours, and then cooled to room temperature. The reaction mixture is poured into methanol, and the solid is recovered by centrifugation. The obtained solid is dissolved in a small amount of acetone, re-precipitated in methanol, and the solid is recovered by centrifugation, followed by vacuum drying. : A white solid (243 mg) of the polymer (1-9) of 50 (molar ratio) was obtained in a yield of 48%.
The copolymer composition in this polymer (1-9) is such that the CH peak of the aromatic ring of 6.5 to 7.4 ppm of the structural unit (A-1) of the ¹ H-NMR spectrum (solvent acetone-d ₆ ) and 0 It calculated | required from the integral intensity ratio of the peak of the corresponding proton of a structural unit (A-1) of .3-3.9 ppm, and the corresponding proton of a MMA unit.

Example 8 Crosslinking Reaction Into a DMSO (2 mL) solution of the polymer (1-1) (466 mg, 2.0 mmol / in terms of structural unit) in a 5 mL sample tube, 1,2-bis (2-aminoethoxy) When ethane (30 mg, 0.2 mmol) was added and heated at 70 ° C. for 14 hours, the fluidity of the mixture disappeared and colorless and transparent gelation was obtained.
Similarly, in a 5 mL sample tube, a DMSO (2 mL) solution of the polymer (1-2) (541 mg, 2.0 mmol / constitutional unit) was added to 1,2-bis (2-aminoethoxy) ethane (30 mg, 0.00 mg). 2 mmol) was added at room temperature and after 1 minute, the fluidity of the mixture disappeared and a yellow transparent gel was obtained.
From this result, it was found that the crosslinking reaction rate can be controlled by appropriately selecting the structures of Z ¹ and Z ² .

(Example 9) Measurement of density and shrinkage rate Table 5 shows the results of measuring the density of the compound, the shrinkage rate during polymerization, and the density of the polymer.
As shown in Table 5, the compound of the present invention has a high density compared to styrene, and the shrinkage rate during polymerization is low, and the polymer of the present invention has the characteristics that it has a higher density than polystyrene. .

(Example 10) Thermophysical property measurement The thermal decomposition temperature Td and the glass transition temperature Tg of the polymer (1-1) and the polymer (1-2) were measured. The results are shown in Table 6.

In Table 6, PDOA is a polymer of an acrylic acid derivative having a 5-membered cyclic carbonate structure described in Non-Patent Document 2.
As shown in Table 6, it was found that the polymer of the present invention has high heat resistance.

  From these results, since the polymer of the present invention has high heat resistance and low shrinkage, it can be considered that it can be suitably used as a heat resistant adhesive and an optical material.

Claims (6)

A compound represented by the following formula (a).
Symbols in the formula (a) have the following meanings.
Q ¹ : A single bond or a divalent linking group.
Z ¹ and Z ² : independently of each other, an oxygen atom or a sulfur atom. The compound according to claim ¹ , wherein Q ¹ is a linear alkylene group having 1 to 5 carbon atoms in which one or more —CH ₂ — may be substituted with an etheric oxygen atom. Wherein ^{Q 1} is _-CH 2 -O-CH ₂ - A compound according to claim 1 or 2. The compound according to any one of claims 1 to 3, wherein Z ¹ and Z ² are both oxygen atoms. The compound according to any one of claims 1 to 3, wherein Z ¹ and Z ² are both sulfur atoms.   A polymer comprising a structural unit derived from the compound according to claim 1.