JPH036208A - Fluorinated acrylic 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 H or C2H5).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a fluorine-containing acrylic 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 is an excellent resin with good weather resistance and mechanical properties, but on the other hand, it has high water absorption and is prone to dimensional changes during use.

The disadvantage is that it is difficult to use in precision optical parts. 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-58-81322, JP-A-58-8
No. 7104 and other publications propose a method of copolymerizing styrene, α-methylstyrene, maleic anhydride, etc. with methyl methacrylate.

Although these methods can improve heat resistance, the flowability of the resin during molding is significantly reduced.

Formability is significantly impaired. Further, since these vinyl monomers and methyl methacrylate have significantly different dipolymerization reactivity, it is difficult to prepare a homogeneous copolymer, and optically non-uniform molded products are likely to be produced.

Therefore, Japanese Patent Application Laid-open No. 58-162651, Japanese Patent Application Laid-open 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 alicyclic methacrylic esters and methyl methacrylate, the durability can be improved without impairing the transparency or optical properties of the resulting resin. Although it is possible to improve heat resistance such as water absorption, glass transition temperature, and heat distortion temperature to some extent, when inbornyl methacrylate is used, the thermal decomposition initiation temperature decreases significantly, resulting in poor thermal decomposition resistance. When W resin is thermally melted for purposes such as injection molding, it undergoes thermal decomposition, making it extremely difficult to mold items that require precision or have minute shapes, and is therefore impractical.

In addition, 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, thermal decomposition that poses a problem in terms of formability does not occur, but in this case, the effect of improving heat resistance such as glass transition temperature and heat distortion temperature is sufficient. isn't it.

The present invention provides a fluorine-containing acrylic acid ester that can be used as a raw material for producing a polymer having good transparency and moldability, as well as excellent heat resistance and low water absorption, and a method for producing the same. The purpose of the present invention is to provide a method for producing a polymer using an acid ester and a method for producing a copolymer using the fluorine-containing acrylic ester and another unsaturated monomer polymerizable with the acrylic ester. do.

(Means for Solving the Problems) The present invention relates to a fluorine-containing acrylic ester represented by -Momon [I].

The fluorine-containing acrylic ester of the present invention is usually a compound represented by R+ (wherein R1 represents hydrogen or a methyl group) and a compound represented by (However, in these formulas, R1 has the same meaning as in the general formula ).In this case, it is possible to obtain a pure single compound, but it is complicated.In actual use, it is not necessary to obtain a single compound, so a mixture of these isomers is obtained. It may be used for practical purposes, and the structural formula may be grasped as a compound represented by -Momona (1).

In addition, one aspect of the present invention is a compound represented by the general formula fI[+ and (
The present invention relates to a method for producing a fluorine-containing acrylic ester (in which R1 represents hydrogen or a methyl group).

The present invention also relates to a method for producing a polymer, which comprises polymerizing a fluorine-containing acrylic ester represented by -Momona (1).

1 (in the formula, R8 represents hydrogen or an acetyl group) - Monna [11
A compound represented by 11 and R.

CHz=CCORs　　　　　　(If)1 (In the formula, & represents hydrogen or a methyl group, and R3 is hydrogen.

R represented by general formula (1), which is characterized by reacting with (representing a methyl group or an ethyl group).

(In the formula, R represents hydrogen or a methyl group.) The present invention relates to a fluorine-containing acrylic ester represented by the general formula (I) and other polymerizable unsaturated monomers that can be polymerized with the acrylic ester. This invention relates to a method for producing a copolymer characterized by polymerizing the following.

R+ (In the formula, R1 represents hydrogen or a methyl group) Here, the compound represented by -Momonena (I []) can be synthesized in the following manner. That is, by combining cyclopentadiene and vinyl acetate. Norbornenyl acetate was obtained by Diels-Alder reaction.

By subjecting this norbornenyl acetate to an addition reaction with hydrogen fluoride, the general formula [1] in which R2 is an acetyl group is obtained.
The compound 1), ie, fluorinated norbornyl acetate, is obtained. By hydrolyzing this fluorinated norbornyl acetate, the general formula (Ill
A compound of fluorinated norborneol can be obtained. Here, the reaction between vinyl acetate and cyclopentadiene can be carried out under normal Diels-Alder reaction conditions. For example, the addition reaction of hydrogen fluoride is 1.

5synthesis (Synthesis>1973 P77
It can be carried out according to the method described in 9.

When reacting the compound of the general formula (II) obtained in this way with the compound of the general formula (III3), when the charge of the compound of the general formula (III) is hydrogen, the general formula (
R3 in the compound of Jull may be hydrogen, methyl group, or ethyl group, but R2 of the compound of -Momonana tU+
When is an acetyl group, Rs in the compound of general formula (III) is preferably a methyl group or an ethyl group.

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

Ku-monna (when R3 of the compound of I[[] is hydrogen)
Examples of the compound of general formula (1) in which R8 is hydrogen include acrylic acid and methacrylic acid. in this case.

- In the compound of Ill, R2 is preferably hydrogen, ie, norborneol fluoride.

In this case, it is preferable to use acrylic acid or methacrylic acid in a ratio of 1 to 5 moles per mole of fluorinated norborneol. When the amount is less than this, unreacted fluorinated norborneol remains, and it is extremely difficult to remove and purify it. Further, there is no particular advantage in using a larger amount of acrylic acid or methacrylic acid, and the operation of neutralizing and purifying one reaction solution becomes complicated.

In this case, the catalyst for the reaction is 1, for example, sulfuric acid.

Paratoluenesulfonic acid, benzenesulfonic acid.

Acidic ion exchange resins and the like can be used, usually in proportions of about 1 to 30% by weight of norborneol fluoride. If the amount used is less than this, the reaction will not progress sufficiently, and if it is too large, the neutralization and purification steps of the reaction solution will become complicated.

Solvents include benzene, toluene, and 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 in proportions ranging from 0% to 1% by weight, preferably from 20 to 60% by weight.

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

Polymerization inhibitors include, for example, hydroquinone.

Hydroquino/monomethyl ether, tertiary-butyl hydroquino/, butylated hydroxytoluene, fetch-azimuth 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 2 times the amount of acrylic acid or methacrylic acid.
0 to 1,000 ppm is preferred. If the amount of polymerization inhibitor is too large.

Turn the final product ester compound into a cured product! P:, case.

It may have an adverse effect, and if it 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, there is a risk that a polymer will be produced; if the reaction temperature is too low, the reaction may proceed slowly. Reacting.

The water produced as a by-product is an azeotrope with the aforementioned reaction solvent.

It is advantageous to carry out the reaction while distilling off the reaction mixture out of the system.

Under such conditions, the reaction can usually be completed in about 2 to 20 hours.

After the reaction is completed, the reaction solution is cooled and converted into an alkaline aqueous solution.

For example, the fluorine-containing acrylic of the present invention can be prepared by neutralizing with an aqueous sodium diluted solution, an aqueous sodium carbonate solution, aqueous ammonia, etc., washing with water, separating the aqueous layer, and distilling off the remaining solvent under reduced pressure. An acid ester is obtained. Neutralization,
When washing with water, the reaction solution may be further diluted with a solvent, or
A neutral salt such as sodium chloride or ammonium sulfate may be dissolved in an alkaline aqueous solution or water.

First, the obtained dead gold fluorine acrylic ester is subjected to vacuum distillation using a thin film distillation device, a centrifugal molecular distillation device, etc., and then fl! You can also use sea bream.

Ku-monna (I [When R3 of the compound of I is a methyl group or ethyl group)> R3 is a methyl group or an ethyl group (compounds of the general formula IIll include methyl acrylate, ethyl acrylate,
Methyl methacrylate or ethyl methacrylate. In this case, in the compound of the general formula [nl, R8 may be hydrogen or an acetyl group. Namely.

Either fluorinated norborneol or fluorinated norbornyl acetate can be suitably used. In this case, for 1 mol of the compound of the general formula (II)
The compound I) is preferably used 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 cleave them. Furthermore, there is no particular advantage in using a larger amount of the compound (III) than this, and only requires a complicated operation when removing and collecting the excess compound (Ichimonana plate) after the completion of the 9 reactions. .

As a catalyst for the reaction in this case, any of the catalysts used in ordinary transesterification reactions can be used. Examples of such catalysts include hydroxides such as sodium, potassium, and lithium, basic catalysts such as alphoxide, 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 usually 2.

- About 0.1 to 10% by weight of the compound of Monka (II).

The entire amount may be charged 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.

Also, there is no need to use a particular solvent during the two reactions, 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. The amount of polymerization inhibitor used is 20 to 1,000 ppm based on the compound of general formula (I[[)
is preferred. If the amount of the polymerization inhibitor is too large, it may have an adverse effect when the final ester compound is cured, and if it is too small, the effect of preventing polymerization will not be sufficient.

Moreover, it is preferable to use bimolecular 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 it is too low, the reaction progresses slowly, which may be disadvantageous.

It is advantageous to carry out the reaction while removing methanol, ethanol, methyl acetate or ethyl acetate, which are by-produced during the reaction, by distillation out of the system. In this case, since the compound of the general formula [I[[1] is distilled out azeotropically or simultaneously, it is advantageous to carry out the distillation removal from one reaction tank through a rectification column.

After the reaction is completed, the catalyst is removed by filtration, washing, hydrolysis, etc., and the remaining excess compound of the general formula (I'll) is distilled off under reduced pressure to obtain the fluorinated acrylic acid of the present invention. An ester is obtained.

Alternatively, the fluorine-containing acrylic ester may be obtained by distilling off the compound of general formula (III) from the reaction solution and then removing the catalyst.

In addition, the obtained fluorine-containing acrylic ester is subjected to vacuum distillation using a thin film distillation device, centrifugal molecular distillation device, etc.
It may be further purified. Further, depending on the case, it is also possible to distill off the compound of general formula [1] without removing the catalyst, and then obtain a fluorine-containing acrylic ester by distillation.

The fluorine-containing acrylic ester of the present invention synthesized by the above method can be optically used as a homopolymer or a copolymer of the fluorine-containing acrylic ester of the present invention and other polymerizable unsaturated monomers. It can be used for applications such as materials, adhesives, paints, fiber treatment agents, mold release agents, resin modifiers, optical fiber protection agents, and selective transmission 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 dipolymerization initiator. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, and di-t-7'tylperoxyhexahydrophthalate.

t-7” methylperoxy-2-ethylhexanony)
, organic peroxides such as 1,1-di-t-butylperoxy-3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone -1
-Azo compounds such as carbonitrile and azodibenzoyl,
Any water-soluble catalyst typified by potassium persulfate or ammonium persulfate, or a redox catalyst using a combination of a peroxide or a persulfate and a reducing agent, etc.9, which can be used in normal radical polymerization, can 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. Mercaptan compounds, thioglycol, carbon tetrabromide as polymerization regulators,
α-methylstyrene dimer or the like may be added as necessary to adjust the molecular weight.

The polymerization temperature is preferably selected appropriately within the range of 0 to 200°C, particularly preferably 50 to 120°C. Benzene is used as a solvent in solution polymerization.

Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate.

Dichloroethylene etc. can be used. Suspension polymerization.

It is carried out in an aqueous medium, and suspending agents and, if necessary, suspension aids are added. Suspending agents include polyvinyl alcohol,
Examples include water-soluble polymers such as methylcellulose and polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium birophosphate.

The water-soluble polymer is 0.03 to 1% by weight based on the total amount of monomers, and the slightly soluble inorganic substance is 0.0% by weight based on the total amount of monomers.
Preferably, it is used in an amount of 5 to 0.5% by weight.

Suspension aids include anionic surfactants such as sodium dodecylbenzenesulfonate, and when a sparingly soluble inorganic substance is used as the R1 agent, it is preferable to use an M rinse aid in combination. The suspension aid is o, o based on the total amount of monomers.
It is preferable to use the weight side of oi to 0.02 weight.

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, tricyclo(5,2,
1,02.6]dec-8-yl.

Acrylic acid cycloalkyl esters such as inbornyl 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[5,2,1,02.6]dec-8-yl methacrylate.

cycloalkyl methacrylates such as inbornyl methacrylate and norbornyl methacrylate;

Examples include aromatic methacrylic esters such as phenyl methacrylate and benzyl methacrylate, and methacrylic esters such as glycidyl methacrylate.

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 methachloronitrile.

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

Alicyclic N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylyareimide, N-, 'tylphenylmaleimide, N-chlorophenylmaleimide, N-
Examples include aromatic N-substituted maleimides such as methoxyphenylmaleimide.

In order to obtain a copolymer resin that is excellent in heat resistance, transparency, moldability, and moisture absorption resistance, it is preferable to contain a fluorine-containing acrylic ester represented by -Momona[, IJ] in a ratio of 5 times or more. If it is less than 5% by weight.

The above effects are likely to be insufficient.

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

Synthesis Example 1 <Synthesis of norbornenyl acetate> 51 In an autoclave, dicyclopentadiene 5289,
1032 G of vinyl acetate and 0.789 g of hydroquinone were charged, and the reaction was carried out at 180° C. for 8 hours with stirring (gauge pressure cuff ~10 kg/cm”).

Under these conditions, dicyclopentadiene was thermally decomposed to form cyclopentadiene/L, and then reacted with vinyl acetate to form norbornenyl acetate. After cooling the reaction solution, excess vinyl acetate was distilled off under reduced pressure and the boiling point was 73-74°C.
/16 mmHg norbornenyl acetate (gas chromatography purity, 99.7%) 4959 was obtained.

Synthesis Example 2 <Synthesis of fluorinated norbornyl acetate> 500ml!
A 70% by weight pyridine solution of hydrogen fluoride was charged into a Teflon reaction vessel, and a solution of 30.49 of norbornenylacetate synthesized in Synthesis Example 1 dissolved in 40% of tetrahydrofuran was added to the solution at 0°C for 15 minutes. dripped. After the reaction solution was left to stand for 1 hour, it was poured onto ice chips and the separated organic layer was thoroughly washed with water, and distilled under reduced pressure to obtain a solution with a boiling point of 60-65".
A fraction 21.59 of C10.5 mmHg was obtained. The obtained fraction was analyzed by gas chromatography and gas chromatography.
Mass spectrometry revealed that fluorinated norbornyl acetate 9
2% by weight and 8% by weight of norborneol fluoride.

Example 1 Fluorinated norbornyl acetate obtained in Synthesis Example 2 (1) was placed in a 11-glass 4-hole flask equipped with a stirrer, a thermometer, an air inlet tube, and a rectification column (Sneader, 5 stages) with a reflux condenser. (contains norborneol fluoride) 1729. Methyl methacrylate 4009° Hydroquinone monomethyl ether 0.040g and titanium tetraisopropoxide 1.
Prepare 5g.

The temperature was raised while blowing dry air at a rate of 100 rnl/min, and methyl acetate (and a small amount of methanol) and a small amount of methyl methacrylate, which were produced as by-products under heating and reflux, were removed by distillation out of the system through a rectification column. I reacted while doing so. 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
It's ℃. 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 completion of the reaction, the excess methyl methacrylate was distilled off from the reaction solution under reduced pressure.
Then, 5 g of fluorinated norbornyl methacrylate 16Z having a boiling point of 83 to 84°C and 10.7 mmHg was obtained.

As a result of mass spectrometry, this fraction had a molecular weight of 9 and 198.

The molecular weight was consistent with that of fluorinated norbornyl methacrylate.

The results of two-element analysis were as follows.

Theoretical value Measured value C66,65chi 66.73% H7,63967,61ts F 9.58% The 'H-NMR spectrum and infrared absorption spectrum of the 9.52% Kono fraction are shown in Figures 1 and 2, respectively. Indicated.

The above identification data confirmed that the fraction was fluorinated norbornyl methacrylate.

Example 2 Norbornyl fluoride methacrylate 10 obtained in Example 1 above was placed in a 500-cm Erlenmeyer flask equipped with a three-sided active frame.
09. After charging, mixing and dissolving 0.4 g of lauroyl peroxide and 0.29 g of lauroyl mercaptan, the inside of the flask was purged with nitrogen gas.

It was immersed in a constant temperature water bath at 60° C. while stirring and shaking, and polymerized for 30 minutes under a nitrogen stream to obtain a partially polymerized product.

Subsequently, this partially polymerized product was injected into a glass cell, and 65
C. for 5 hours, and then at 100.degree. C. for 2 hours to obtain a transparent sheet-like polymer [Al].

Example 3 In the same Erlenmeyer flask as in Example 2, fluorinated norbornyl methacrylate 309. Methyl methacrylate 70g
, 4 g of lauroyl peroxide O, and 2 g of lauroyl mercaptan O were charged, and the same operation as in Example 2 was carried out to obtain 9 polymers (E).

Example 4 Into the same Erlenmeyer flask as in Example 2, methyl methacrylate 100 B, lauroyl peroxide 0.49, and lauroyl mercaptan o, zgf were charged, and the same operation as in Example 2 was carried out to obtain 9 polymer (C). Obtained.

Example 5 Inbornyl methacrylate 1009. 4 g of lauroyl peroxide Q and 0.29 g of lauroyl mercaptan were charged, and the same operation as in Example 2 was carried out to obtain Polymer 1 (D).

Between the polymers obtained as above, (B), (C
The water absorption rate (1° and tD), glass transition temperature, and thermal decomposition properties were measured by the following methods. The results are shown in Table 1.

Measurement method: Water absorption rate: Approximately 7 mm x 30 x 3 mm test piece
It was immersed in water at 0°C, and the water absorption rate when it reached a saturated state was measured by the gravimetric method.

Glass transition temperature (℃) Polymer 1009 was dissolved in 200 g of tetrahydrofuran, and the resulting solution was stirred and poured into methanol 51 to precipitate and precipitate 9 polymers. A polymer was obtained. The glass transition temperature (° C.) (mid point) of this polymer was measured using a differential scanning calorimeter (DSC).

Thermal decomposition: Using a thermogravimetric analyzer [(TGA).

In order to measure the above glass transition temperature, The polymer prepared by was used for measurement. In air, 40℃/ Raise the temperature to 260℃ at min. Weight when kept at 260℃ for 120 minutes The volume reduction rate (%) was measured.

Glass transition temperature and thermal decomposition measuring device 'I'? to F'
(Effects of the Invention) The fluorine-containing acrylic ester of the present invention is a new compound that can be easily polymerized by a conventional radical polymerization method, and the polymer obtained using the same has excellent heat resistance and thermal decomposition resistance. sex,
It exhibits water absorption resistance and is useful as optical materials, adhesives, paints, and other resin modifiers.

[Brief explanation of drawings]

Figure 1 shows "H-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. A fluorine-containing acrylic ester represented by the general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 in the formula represents hydrogen or methyl group) 2. Compounds represented by general formula (II) and ▲Mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_2 represents hydrogen or an acetyl group) General formula (I
II) with the compound represented by ▲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 a fluorine-containing acrylic 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) 3. A polymer characterized by polymerizing a fluorine-containing acrylic ester represented by the general formula (I) manufacturing method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents hydrogen or a methyl group) 4. Fluorine-containing acrylic ester represented by general formula (I) and others that can be polymerized with the acrylic ester A method for producing a copolymer, which comprises polymerizing a polymerizable unsaturated monomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 in the formula represents hydrogen or methyl group)