JPH036207A - Acrylic or methacrylic ester, its production and production of polymer and copolymer therefrom - Google Patents

Abstract

NEW MATERIAL:A compound of formula I wherein R1 is H or CH3. USE:Raw material of polymers useful as optical material, adhesive, coating material and resin modifier. PREPARATION:A compound of formula II (wherein R2 is H or acetyl) is reacted with a compound of formula III (wherein R3 is R1 or C2H5).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Minute Hand) The present invention relates to an acrylic ester or a methacrylic ester, a method for producing the same, and a method for producing polymers and copolymers using the same.

(Prior Art) In recent years, polymethyl methacrylate has been widely used as a thermoplastic transparent molding resin due to its excellent transparency and optical properties. In addition to transparency, polymethyl methacrylate has excellent weather resistance and mechanical properties, but on the other hand, it has high water absorption.

It has the disadvantage that it is difficult to use in precision optical parts because it tends to undergo dimensional changes during use. Also.

Another problem is that it has insufficient heat resistance, which limits the environment in which it can be used.

Therefore, various attempts have been made to improve the water absorption resistance and heat resistance of polymethyl methacrylate by copolymerizing methyl methacrylate with other monomers.

For example, JP-A-56-81322, JP-A-58-
No. 87104, etc., describes styrene.

A method has been proposed in which α-methylstyrene, maleic anhydride, etc. are copolymerized with methyl methacrylate. Although heat resistance can be improved by these methods, the flowability of the resin during molding is significantly reduced, and moldability is significantly impaired. Also, these vinyl monomers and methyl methacrylate.

Because of the large difference in polymerization reactivity, it is difficult to prepare a copolymer, and optically non-uniform molded products are likely to be produced.

Therefore, 9% publication No. 58-162651, Japanese Patent Application Publication No. 61
Publication No. 152708 proposes a method of copolymerizing a methacrylic acid ester having an alicyclic structure such as inbornyl methacrylate or norbornyl methacrylate with methyl methacrylate.

(Problem to be solved by the invention) However, in the method of copolymerizing these methacrylic acid esters with an alicyclic structure and methyl methacrylate, water absorption resistance can be improved without impairing the transparency or optical properties of the resulting resin. Although it is possible to improve heat resistance such as glass transition temperature, heat distortion temperature, etc. to some extent, when inbornyl methacrylate is used, the thermal decomposition initiation temperature is significantly lowered and the thermal decomposition resistance is poor. When resin is heated and melted for purposes such as injection molding, thermal decomposition occurs, making it difficult to mold items that require precision or minute shapes.

This is extremely difficult and impractical.

Also, when norbornyl methacrylate is used, it is different from the case where inbornyl methacrylate is used.

Since the temperature at which thermal decomposition starts does not drop that much, it is possible to mold the product without causing thermal decomposition that would cause problems in moldability. The improvement effect is not sufficient.

The present invention has good transparency and moldability, and also has low water absorption and
An acrylic ester or a methacrylic ester that can be used as a raw material for producing a polymer with excellent heat resistance, a method for producing the same, a method for producing a polymer using the acrylic ester, and the acrylic ester and the acrylic ester. The object of the present invention is to provide a method for producing a copolymer using other polymerizable unsaturated monomers.

(Means for Solving the Problems) The present invention relates to an acrylic ester or a methacrylic ester represented by the general formula +11.

Hereinafter, acrylic ester or methacrylic ester will be abbreviated as (meth)acrylic ester.

(In the formula, R1 represents hydrogen or a methyl group) The (meth)acrylic acid ester of the present invention is usually a compound represented by R1° or a compound represented by U (However, in these formulas, sR1 is a compound represented by the general formula (I). is a mixture of isomers (same meaning as ). In this case, although it is possible to obtain pure single compounds, it is complicated. In actual use, it is not necessary to use a single product, so it is sufficient to use a mixture of these isomers.Also, it is possible to understand it as a compound of the formula (I+).

Furthermore, one aspect of the present invention is a compound represented by the general formula (II+) and (
In the formula, R1 is hydrogen or a methyl group, and 3 is hydrogen, a methyl group, or an ethyl group. The present invention relates to a method for producing a (meth)acrylic acid ester (representing a group).

The present invention also relates to a method for producing a polymer, which comprises polymerizing a (meth)acrylic acid ester represented by the general formula (I).

(In the formula, R2 represents hydrogen or an acetyl group)
A compound represented by I) (I1 (in the formula, ! represents hydrogen or a methyl group) and a (meth)acrylic ester represented by the general formula (I) and a compound capable of polymerizing with the acrylic ester The present invention relates to a method for producing a copolymer, characterized by polymerizing the copolymer with other unsaturated monomers.

(In the formula, R1 represents hydrogen or a methyl group.) Here, the compound of the general formula +ff+ can be synthesized, for example, as follows. That is, cyclopentadiene and styrene are subjected to a Diels-Alder reaction to obtain phenylnorbornene (for example.

Journal of American Chemistry, Vol. 84, P2327 (method described in I9621). For example, take this phenylnorbornene.

A compound of general formula (n) in which 9 atoms are hydrogen can be obtained by carrying out a water conservation reaction by the method described in French Patent No. 1,414,969. Further, by reacting phenylnorbornene and acetic acid in the presence of an acid catalyst by a conventional method, a chemical synthesis of the general formula +It> in which 几2 is an acetyl group can be obtained.

When reacting the thus obtained compound of the general formula tn> with the compound of the general formula (nl), the general formula (
When R2 of the compound of n) is hydrogen, the compound of general formula (II
Rs in the compound of [) may be hydrogen, a methyl group, or an ethyl group, but if R2 of the compound of general formula (II) is an acetyl group, R3 of the compound of the general formula (rabbit) may be a methyl group or Preferably it is an ethyl group.

Furthermore, since the form of the reaction is slightly different between the case where R3 of the compound of general formula (III) is hydrogen and the case where +R3 is a methyl group or an ethyl group, each case will be explained separately below.

<When R3 of the compound of general formula (II[l] is hydrogen)
As a compound of the general formula (IIll) where 几3 is hydrogen,
Acrylic acid or methacrylic acid. in this case.

In the compound of general formula (If), R2 is preferably hydrogen, ie, phenylnorborneol.

In this case, it is preferable to use acrylic acid or methacrylic acid in a ratio of 1 to 5 moles per mole of phenylnorborneol. If the amount is less than this, unreacted phenylnorborneol will remain and this will be removed! ftm is extremely difficult. Further, even if acrylic acid or methacrylic acid is used in a larger amount than this, there is no particular advantage and the operation of neutralizing and purifying the reaction solution 9 becomes complicated.

In this case, the catalyst for the reaction is 9, for example, sulfuric acid.

Paratoluenesulfonic acid, benzenesulfonic acid.

Acidic ion exchange resin etc. can be used, and Cholera usually contains about 1 to 30% by weight of phenylnorborneol.
used at a rate of If the amount used is less than this, the reaction will not progress sufficiently, and if it is too much, the neutralization and purification steps of the reaction solution will become complicated.

Solvent: haubenzen, toluene, xylene.

Hydrocarbon solvents such as hexane are preferred, and these are preferably 10 to 8 % of the total weight including the compounds to be subjected to the reaction.
It is used at a weight of 0 weight, more preferably from 20 to 600 to 60 weight.

It is also preferable to use a polymerization inhibitor to prevent polymerization of raw materials and products during the 9 reactions.

Examples of polymerization inhibitors include hydroquinone.

Hydroquinone monomethyl ether, tertiary-butylhydroquinone, butylated hydroxytoluene, phenothiazine, methylene blue, copper compounds, etc. can be used, and combinations of these and molecular oxygen are also preferred.

The amount of polymerization inhibitor used is 20 to 1. oooppm is preferred.

Too much polymerization inhibitor may have an adverse effect when the final ester compound is cured.
If the amount is too small, the effect of preventing polymerization will not be sufficient. Moreover, it is preferable to use molecular oxygen as air.

The reaction temperature is preferably 60 to 130°C and the reaction is preferably carried out under normal pressure or reduced pressure. If the reaction temperature is too high, a polymer may be produced, and if the reaction temperature is too low, the reaction progresses slowly, which is disadvantageous.

During the reaction, it is advantageous to carry out the reaction after the by-produced water is removed by distillation from the system as an azeotrope with the above-mentioned reaction solvent.

The reaction can be completed under such conditions usually in about 2 to 20 hours. After the reaction is completed, cool the reaction solution,
After neutralizing with an alkaline aqueous solution such as sodium hydroxide aqueous solution, sodium carbonate aqueous solution, aqueous ammonia, etc. and washing with water, the excess water is separated.

The acrylic ester of the present invention is obtained by distilling off the remaining solvent under reduced pressure. When neutralizing and washing with water, the reaction solution may be further diluted with a solvent as appropriate.

A neutral salt such as sodium chloride or ammonium sulfate may be dissolved in an alkaline aqueous solution or water.

Further, the obtained acrylic ester may be further purified by vacuum distillation using a thin film distillation apparatus, a centrifugal molecular distillation apparatus, or the like.

<When R3 in the compound of general formula (III) is a methyl group or an ethyl group> Examples of the compound of the general formula (Ill) in which R3 is a methyl group or an ethyl group include methyl acrylate and ethyl acrylate.

Methyl methacrylate or ethyl methacrylate. In this case, in the compound of general formula CI, R may be hydrogen or an acetyl group. Namely.

Both phenylnorborneol and phenylnorbornyl acetate can be suitably used. In this case, the general formula (
It is preferable to use the compound l[I) in a proportion of 1 to 10 moles, more preferably 1.5 to 5 moles. When the amount is less than this, unreacted compounds of general formula (n) remain, and it is extremely difficult to remove and purify them. Moreover, there is no particular advantage in using a larger amount of the compound of the general formula [II[) than this, and after the completion of the 9 reactions, the excess of the compound of the general formula (I
Only a complicated operation is required when removing and recovering the compound II).

As a catalyst for the reaction in this case, two catalysts commonly used in transesterification reactions can be used. Examples of such catalysts include basic catalysts such as hydroxides and alkoxides of sodium, potassium, and lithium, acidic catalysts such as sulfuric acid and paratoluenesulfonic acid, titanium alkoxides, aluminum alkoxides, tin compounds, lead compounds, etc. metal catalysts can be used. The amount of catalyst used is approximately 0.1 to 10% by weight of the compound of general formula (II).
The entire amount may be added before the start of the reaction, or a portion may be added in portions during the reaction. If the amount used is too small, the reaction will not progress sufficiently, and if it is too large, the removal of the catalyst after the reaction and the purification process will become complicated.

In addition, there is no need to use a particular solvent during the 9 reaction, but
In some cases, benzene and toluene.

Hydrocarbon solvents such as xylene and hexane can also be used.

It is also preferred to use a polymerization inhibitor to prevent polymerization of raw materials and products during one reaction.

Examples of polymerization inhibitors include hydroquinone.

Hydroquinone monomethyl ether, tertiary-butylhydroquinone, butylated hydroxytoluene, catechol, phenothiazine, methylene blue, copper compounds, diphenylamine, etc. can be used, and combinations of these and molecular oxygen are also preferred. Use of polymerization inhibitor□ agent-11
20-1,000 for the compound of H-Momona (III)
ppm is preferred. If the amount of polymerization inhibitor is too large, it may have an adverse effect when the ester compound of the final product is mixed with a cured product.

If the amount is too small, the effect of preventing polymerization will not be sufficient. Also.

Preferably, molecular oxygen is used as air.

The reaction temperature is preferably 60 to 130°C and the reaction is preferably carried out under normal pressure or reduced pressure. If the reaction temperature is too high, a polymer may be produced, and if the reaction temperature is too low, the progress of the reaction will be slow and disadvantageous.

Methanol, ethanol, methyl acetate produced as by-products during the reaction,
Alternatively, it is advantageous to carry out the reaction while distilling and removing ethyl acetate from the system. In this case, the compound indicated by - Monna (■) is distilled out azeotropically or at the same time.

When carrying out distillation removal from the reaction vessel, it is advantageous to carry out the distillation through a rectification column.

After the reaction is completed, the catalyst is removed by filtration, washing, hydrolysis followed by separation, etc., and the remaining excess compound of general formula (III) is distilled off under reduced pressure to obtain the acrylic ester of the present invention. is obtained. Also, from one reaction solution the general formula (I
The acrylic ester may be obtained by distilling off the compound II) and then removing the catalyst.

Further, the obtained acrylic ester may be further purified by vacuum distillation using a thin film distillation apparatus, a centrifugal molecular distillation apparatus, or the like. In some cases, it is also possible to distill off the compound (III) without removing the catalyst, and then to obtain an acrylic ester by distillation.

The (meth)acrylic acid ester of the present invention produced by the above method is a homopolymer or the general formula +
Copolymers of acrylic ester represented by 11 and other polymerizable unsaturated monomers, such as optical materials, adhesives, paints, and fiber treatment agents.

It can be used for purposes such as mold release agents, resin modifiers, optical fiber protectants, and selectively permeable membranes. As a method for producing the polymer, known methods such as radical polymerization and ionic polymerization can be applied. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and suspension polymerization in the presence of a polymerization initiator.

Examples of polymerization initiators include 2, such as benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate, t-butylperoxy-2-ethylhexanony), 1,1-di-t-butylperoxy-3 ,3,
5-41J Organic peroxides such as methylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-
2,4-dimethylvaleronitrile.

Azobiscyclohexanone-1-carbonitrile.

Azo compounds such as azodibenzoyl, water-soluble catalysts such as potassium persulfate and ammonium persulfate, and redox catalysts based on combinations of peroxides, persulfates, and reducing agents, etc. 2. Which of the following can be used for normal radical polymerization? can also be used. The polymerization catalyst is preferably used in an amount of 0.01 to 10% by weight based on the total amount of monomers. A mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer, etc. as a polymerization regulator may be added as necessary to adjust the molecule f. The polymerization temperature is preferably selected appropriately within the range of 0 to 200°C, particularly preferably 50 to 120°C. As a solvent in solution polymerization.

Benzene, toluene, xylene, methyl ethyl ketone,
Methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc. can be used. Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. As a suspending agent.

Examples include water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium birophosphate. The water-soluble polymer has a ratio of 0.03 to 1 weight relative to the total amount of monomers,
The slightly soluble inorganic substance has a value of 0.05 to 0 relative to the total iK of the monomer.
．． It is preferable to use a weight factor of 5. @ As a clouding aid,
When an anionic surfactant such as sodium dodecylbenzenesulfonate is used and a poorly soluble inorganic substance is used as a 1M suspension agent, it is preferable to use a suspension aid in combination. The suspension aid is preferably used in an amount of 0.001 to 0.02 weight relative to the total amount of monomers.

In the present invention, other polymerizable monomers having unsaturated bonds include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, N-substituted maleimides, and the like.

Examples of unsaturated fatty acid esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, cyclohexyl acrylate, and tricyclo acrylate [: 5.
2.1.0”) Dec-8-yl.

Acrylic acid cycloalkyl esters such as isobornyl acrylate and norbornyl acrylate, acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, acrylic acid esters such as glycidyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate , butyl methacrylate, hexyl methacrylate,
Methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, cyclohexyl methacrylate, tricyclo I methacrylate: 5.2. ．． 1.02.6] Deka-8
-yl, isobornyl methacrylate, norbornyl methacrylate, methacrylic acid cycloalkyl esters, methacrylic acid aromatic esters such as phenyl methacrylate, benzyl methacrylate, etc., methacrylic acid esters such as glycidyl methacrylate, and the like.

Examples of aromatic vinyl compounds include styrene or α-substituted styrenes such as α-methylstyrene and α-ethylstyrene;
Chlorostyrene, vinyltoluene.

Examples include nuclear-substituted styrenes such as t-butylstyrene.

Examples of vinyl cyanide compounds include acrylonitrile and metacyclonitrile.

As the N-substituted maleimide, N-methylmaleimide,
N-ethylmaleimide, N-inpropylmaleimide,
Aliphatic N-substituted maleimides such as N-butylmaleimide and N-laurylmaleimide.

Examples include alicyclic N-substituted maleimides such as N-cyclohexylmaleimide, aromatic N-substituted maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, and N-methoxyphenylmaleimide.

In order to obtain a polymer resin with excellent heat resistance, transparency, moldability, and moisture absorption resistance, -(meta) represented by Monka (I)
It is preferable to contain acrylic ester in an amount of 5 weight range or more. If the weight is less than 5.

It is difficult to fully achieve the above effects.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Synthesis Example 1 <Synthesis of phenylnorbornene> 66 g of styrene and 1049 g of dicyclopentadiene were placed in a 500 d autoclave. 70.2 g of tertiary-butylhydroquino was charged and reacted at 180° C. for 6 hours with stirring. Under these conditions, dicyclopentadiene was thermally decomposed to become cyclopentadiene and then reacted with styrene. After cooling the reaction solution, unreacted styrene and dicyclopentadiene were distilled off under reduced pressure to give a boiling point of 98~98.
A fraction 60.59 containing phenylnorbornene as a main component and having a temperature of 102'C/3.6 mmHg was obtained. Purity by gas chromatography analysis was 98.2% by weight.

Synthesis Example 2 Synthesis of phenylnorbornylacet f'po > 11! equipped with a stirrer, thermometer, and reflux condenser! 9 Phenylnorbornene obtained by the method of Synthesis Example 1 1709. 42°9 of acetic acid and 1.79° of sulfuric acid were charged and heated while stirring.

The reaction was carried out under reflux (I23-124°C) for 8 hours.

After cooling the reaction solution, it was diluted by adding toluene 6009, washed several times with water, and then washed with a 5% NaOH aqueous solution.

Excess acetic acid and catalytic sulfuric acid were removed. After drying the oil layer over anhydrous sodium sulfate and distilling off toluene under reduced pressure, 108 g of a fraction containing phenylnorbornyl acetate as a main component with a boiling point of 122 to 126°C and 10.6 mmHH was obtained.
I got it. Purity by gas chromatography: 9 g;
7. He was in charge of quantity.

Example 1 Synthesis of phenylnorbornyl methacrylate>II equipped with a stirrer, a thermometer, an air introduction tube, and a rectification column with a reflux condenser (sneader - 5 stages)! Phenylnorbornyl acetate (23) obtained in Synthesis Example 2 was placed in a glass four-bottle flask.
09. Methyl methacrylate 4009. Hydroquino/monomethyl ether 0.05129 and titanium tetraisopropoxide 2g were charged, and dry air was introduced at 100 m
The temperature was raised while blowing at a rate of 5/min, and under heating and reflux, methyl acetate and a small amount of methyl methacrylate, which were produced as by-products, were removed by distillation from the system through a rectification column to cause a reaction. At the beginning of the reaction, the distillate extraction cock was adjusted so that the temperature at the top of the rectification column was about 60°C. Near the end of the reaction, the top temperature gradually rises to about 100
℃ and summer thoughts. The temperature of the reaction solution during this time was 102 to 110°C, and the reaction was carried out by heating for 3 hours. After the reaction was completed, excess methyl methacrylate was first distilled off from the reaction solution under reduced pressure.

Then, 183 g of a fraction containing phenylnorbornyl methacrylate as a main component with a boiling point of 127 to 130°C/0.4 mmHg was obtained.

When this fraction was analyzed by gas chromatography,
Four peaks were observed, and they were 7.5 weight percent, 4.5 weight percent, 16 weight percent, and 72 weight i%, respectively, from the low boiling point side. Moreover, as a result of gas chromatography mass spectrometry, it was found that all of the above four peaks had a molecular weight of 256.

From these, it was confirmed that the fraction was an isomer mixture of phenylnorbornyl methacrylate.

In addition, the results of elemental analysis are Theoretical value Measured value C79, 65 yen 79.59 person H7, 86% 7.90 person Well, the theoretical value and the measured value matched.

The IH-NMR spectrum and infrared absorption spectrum of the fraction are shown in Figures 1 and 2, respectively.

Example 2 Phenylnorbornyl methacrylate 1 obtained in Example 1 above was placed in a 500-cm Erlenmeyer flask equipped with a three-way stopcock.
oog, 0.4 g of lauroyl peroxide, and 0.29 g of lauroyl mercaptan were charged, mixed, and dissolved. After replacing the inside of the flask with nitrogen gas, the flask was immersed in a constant temperature water bath at 60°C while stirring and shaking.

Polymerization was carried out for 30 minutes under a nitrogen stream to obtain a two-part polymer.

Subsequently, this partially polymerized product was injected into a glass cell, and 65
It was polymerized at 100° C. for 5 hours, and then for 2 hours at 100° C. to obtain a transparent sheet-like polymer (A).

Example 3 In the same Erlenmeyer flask as in Example 2, 30 g of phenylnorbornyl methacrylate, 70 g of methyl methacrylate,
0.49 g of lauroyl peroxide and 2 g of lauroyl mercaptan O were charged, and the same operation as in Example 2 was carried out to obtain 1 polymer fB).

Example 4 In the same Erlenmeyer flask as in Example 2, methyl methacrylate 1009. 0.4 g of lauroyl peroxide and 0.2 g of lauroyl mercaptan were charged, and the same operation as in Example 2 was conducted to obtain Polymer 9 (C).

Example 5 Into the same Erlenmeyer flask as in Example 2, 100 g of inbornyl methacrylate, 0.49 g of lauroyl peroxide, and 0.29 g of lauroyl mercaptan were charged, and the same operation as in Example 2 was carried out to obtain 9 polymer (D). I got it.

Between the polymers obtained as above, CB), (C
) and fD) were measured for water absorption, glass transition temperature, and thermal decomposition by the following methods. The results are shown in Table 1.

Measurement method Water absorption $: Approximately 7
It was immersed in water at 0°C, and the water absorption rate (%) when it reached a saturated state was measured.

Glass transition temperature °C: After dissolving 100g of polymer in 200gK of tetrahydrofuran, the resulting solution was stirred into 51ml of methanol to precipitate 9 polymers, and dried on the 9th side to form a white powdery polymer. Obtained. The glass transition temperature ('a (mid point)) of this polymer was measured using a differential scanning calorimeter (D, SC).

Thermal decomposability: Using a thermogravimetric analyzer (TGA), the polymer prepared in the glass transition temperature measurement above was used as a sample for measurement. The weight loss rate (correspondence) was measured when the temperature was raised to 260'C in air at a rate of 40C/min and kept at 260C for 20 minutes.

In addition, the glass transition temperature and thermal decomposition measuring device used was DuPont Model 9900.

(Effects of the Invention) The (meth)acrylic acid ester of the present invention is a new compound and is easily polymerized by a normal radical polymerization method, and the polymer obtained using it has excellent heat resistance and heat decomposition resistance. ,
It exhibits water absorption resistance and is useful as optical materials, adhesives, paints, and other resin modifiers.

[Brief explanation of drawings]

Figure 1 shows lH-N of the compound (fraction) obtained in Example 1.
The MR spectrum and FIG. 2 are the infrared absorption spectrum of the compound.

Claims (1)

[Claims] 1. An acrylic ester or methacrylic ester represented by the general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents hydrogen or a methyl group) 2. - Compounds represented by general formula (II) and % formula 5 (II) (In the formula, R_2 represents hydrogen or acetyl group) general formula (I
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R_1 represents hydrogen or a methyl group, and R_3 represents hydrogen, a methyl group, or an ethyl group.) A method for producing an acrylic ester or methacrylic ester represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents hydrogen or a methyl group) 3. Characterized by polymerizing acrylic ester or methacrylic ester represented by general formula (I) Polymer manufacturing method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 in the formula represents hydrogen or methyl group) 4. Can be polymerized with acrylic ester or methacrylic ester represented by general formula (I) and the acrylic ester A method for producing a copolymer, characterized by polymerizing it with other unsaturated monomers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 in the formula represents hydrogen or methyl group)