JPS62507A - Methacrylimide-containing polymer - Google Patents

Abstract

PURPOSE:To contrive to improve the heat resistance and heat decomposition resistance of a fluorine-containing polymer, by forming the polymer from a specified methacrylimide structural unit, a specified structural unit derived from a fluoroalkyl methacrylate monomer and a specified structural unit derived from a vinyl monomer so that these units may be present at a specified ratio. CONSTITUTION:A methacrylimide-containing (fluoroalkyl methacrylate) polymer formed from 98-100wt% methacrylimide structure units (A) of formula I (wherein R is H, a 1-20C aliphatic, aromatic or alicyclic hydrocarbon group), 2-0wt% structural units (B) derived from a fluoroalkyl methacrylate monomer and 0-50wt% structural units (C) derived from a vinyl monomer copolymerizable with fluoroalkyl methacrylate monomer (B).

Description

[Detailed description of the invention] [Field of abuseful use] The present invention relates to novel methacrylimide-containing polymers.

[Conventional technology]

In addition to being heat-resistant, corrosion-resistant materials, and high-performance electrolyte materials, fluorine-containing polymers have characteristic surface properties, optical properties, radiation sensitivity,
Based on its selective permeability, properties, electrical properties, and properties as a medical material, it is functionally applied in various fields and is in demand! ! The power is growing.

However, it is currently expensive, and compared to general-purpose resins, its manufacturing and molding methods are not fully established.

Among fluorine-containing polymers, methacrylic fluoroalkyl polymer resins are transparent, have low refraction, and have water- and oil-repellent surface properties, as well as radiation sensitivity due to the characteristic solubility of the polymer. It is positioned as a special resin with excellent hygroscopicity and dimensional stability.

One of these characteristics is that it has a low refractive index, and it is used to construct optical transmission rods as a sheath material for a core material such as polystyrene, polymethyl methacrylate, or polycarbonate resin.

In addition, fluoroalkyl methacrylate polymers are used as resin molding materials.

However, fluoroalkyl methacrylate polymers have inferior thermal decomposition resistance compared to corresponding alkyl methacrylate polymers, and are thermally decomposed during high-temperature molding processing to generate volatile public metals. Therefore, defects such as jetting silver occur in the molded product, and it is difficult to say that the resin has excellent thermoplasticity. In addition, when compared with the corresponding alkyl methacrylate polymer, the double bond electron density having radical polymerization ability is sparse, resulting in a molecular structure that is susceptible to radical depolymerization. Therefore, the properties imparted during production deteriorate as heat shaping is repeated during molding, the degree of polymerization decreases, and the properties significantly decrease due to the plasticizing effect of monomers produced by depolymerization.

Regarding heat resistance, polymethacrylic acid 2,2
．． Although 2-trifluoroethyl has the best heat resistance, it still has a glass transition temperature of 83°C. Even 2'-hexafluoroisoglobil has a low temperature of 95°C, which is inferior to 100°C for polymethyl methacrylate. .

10,000 Fluorine-containing polymers, as typified by polytetrafluoroethylene, have water- and oil-repellent surface properties derived from their molecular structures, and surfaces that do not get wet with water or oil. This property is also an excellent feature of fluoropolymers, which are currently widely used as industrial materials. Further, the fluoroalkyl methacrylate polymer has excellent properties such as very little absorption and scattering and is transparent.

[Problems to be solved by the invention]

The present invention has been made to provide a novel polymer that can improve heat resistance and thermal decomposition resistance while maintaining the above-mentioned excellent properties of fluorine-containing polymers, particularly fluoroalkyl methacrylate polymers. be.

[Means for solving problems]

That is, the methacrylimide-containing polymer of the present invention, which was discovered as a preliminary means to solve the above problems, has the following formula: represents an aliphatic, aromatic or alicyclic hydrocarbon group.) 98-100% by weight of methacrylimide structural units represented by CB) 2-0% by weight of structural units that can be formed from fluoroalkyl methacrylate monomers , and (C) C
It is characterized by comprising 0 to 50% by weight of a structural unit that can be formed from a monomer copolymerizable with the fluoroalkyl methacrylate monomer of B).

[Detailed description and examples of the invention]

In the methacrylimide structural unit of ((trans)), R in the general formula (I) is a hydrogen atom, or a saturated or unsaturated (having a bond) hydrocarbon group having 1 to 20 μ carbon atoms, Represents a group selected from aromatic hydrocarbon groups and alicyclic hydrocarbon groups (these hydrocarbon groups may have a substituent such as a halogen atom or an organic group other than a hydrocarbon group).Representative. Specific examples include hydrogen atom, methyl group, ethyl group, n-propyl group, isoprohy/l/ group, n-7'thyl group, isobutyl group, tart;-butyl group, phenyl group, substituted phenyl group, cyclohexyl group. group, bornyl group, etc.

Particularly preferred are a hydrogen atom, a methyl group, and a cyclohexyl group from the viewpoint of heat resistance, moldability, and the like.

Containing methacrylimide of the present invention (methacrylic acid 7 and 0
The (furkyl) polymer may contain only one kind of the above-mentioned (Al methacrylimide structural unit), or may contain all two or more kinds.

Examples of the structural unit that can be formed from the fluoroalkyl methacrylate monomer (B) include structural units represented by the following general formula [11] and general formula [■].

H3 -OH2-0- O-(OH2) (OF2)y ZI (wherein, X is 1 or 1-c2, y is 0 or an integer from 1 to 10, and zl represents a hydrogen atom or a fluorine atom.) General Formula [■] H3 -OH2-0- (In the formula, L, m and n are each 0 or an integer of 1 to 10, and 22.23 and 24 represent a hydrogen atom or a fluorine atom, respectively. However, t, m and n are 0 at the same time, and z2 + zl and Z4 do not represent hydrogen atoms at the same time.) The methacrylimide-containing (fluoroalkyl methacrylate) polymer of the present invention contains only one type of structural unit of the above (B). ? or may contain two or more types.

Representative examples of fluoroalkyl methacrylate monomers that can form all of these structural units include 2,2.2-trifluoroethyl methacrylate), 2.2.3.3-tetrafluoropropyl methacrylate, 2, 2, 3, 3
．． 3-pentafluoropropyl methacrylate), 2.2
．． 4&4.4-hexafluorobutyl methacrylate),
2,2. &mu 4.4.4-Heptafluorobutyl methacrylate, to 2.2.4 4.4.5.5.4 Hessus 8.
Il! , 9.9.9-Hebutadecafluorononane methacrylate, 2.2.2.2: 2: 2'-monohexafluoroisoglobil methacrylate, 2, 2.2
．． i 2'-pentafluoroisopropyl methacrylate and the like.

The structural unit (C) (which can be formed from a vinyl monomer copolymerizable with the fluoroalkyl methacrylate monomer) is desirably absent if only heat resistance is desired; Since it acts as a regulator, it is added as necessary in relation to the resin properties.

Preferred vinyl monomers include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, styrene and substituted styrene.

Among these, acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-acrylate.
Ert-butyl, cyclohexyl acrylate, norbornyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, etc. can be used.

Examples of methacrylic esters include methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, methacrylic! In-butyl, isobutyl methacrylate, tθrt-butyl methacrylate, cyclohexyl methacrylate,
Norbornyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, etc. can be used.

Among these vinyl monomers, methacrylic acid,
Methyl methacrylate and styrene are preferred.

Furthermore, the methacrylimide-containing (fluoroalkyl methacrylate) polymer of the present invention may contain only 1'm of structural units that can be formed from these vinyl monomers, or may contain two or more units. .

In the methacrylimide-containing (fluoroalkyl methacrylate) polymer of the present invention, the structural unit (B) is an essential component for exhibiting all the excellent properties of the fluorine-containing polymer. Therefore, in order to balance heat resistance and thermal decomposition resistance with these excellent properties, it is necessary to select the blending amount and molecular structure of the methacrylimide structural unit of Shu and the structural unit of (B). .

The intrinsic viscosity of the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention, measured by the measuring method described below, is preferably in the range of α01 to 5 odt7t. If the intrinsic viscosity is less than α01, the mechanical strength will be poor, and if it exceeds 5 ot, it will be difficult to shape.

As a method for producing the methacrylimide-containing (fluoroalkyl methacrylate) polymer of the present invention, the method described above (AJ
A monomer capable of forming a methacrylimide structural unit, a fluoroalkyl methacrylate monomer capable of forming the same structural unit, and, if necessary, a vinyl monomer capable of forming a structural unit of the above (C). However, a method of copolymerizing a fluoroalkyl methacrylate monomer that can form the structural unit (B) and, if necessary, a vinyl monomer that can form the structural unit (C), can also be adopted. Ammonia or a primary amine (hereinafter referred to as (referred to as an imidizing agent) in the presence of a heating medium at -1100 to 350°C and in the presence of an inert gas to cause a combination reaction between polymer side chains (hereinafter referred to as an imidizing agent).
It is also possible to adopt a manufacturing method in which volatile substances, mainly solvents, are separated and removed from the reaction product (hereinafter referred to as a separation step).

The intrinsic viscosity of the fluoroalkyl methacrylate-containing polymer used in this production method is preferably 101 to 50 dt7t, as measured by the measuring method described below. 111 or 21 g!U of a methacrylic fluoroalkyl monomer capable of forming all the structural units of (B)
A polymer using only the above is preferable.

In the condensation reaction step, the fluoroalkyl methacrylate-containing polymer is preferably dissolved in a t-solvent and reacted with an imidizing agent in this solution. The solvent used at this time is one that does not inhibit the imidization reaction, which is a condensation reaction between polymer side chains, and does not change the fluoroalkyl methacrylate or methacrylic dispersion ester segment in the case of a partial imidization reaction. It is necessary that The solvent used is not particularly limited as long as it does not impede the purpose of the present invention, but preferably the solubility parameter δ value (Polymer Hand'book, 8e
coni Fid, , ,T, Branarap,
F, H.

John Wiley & 5on
s, New York.

1975) is 14 to 19.5 (cat/i) > 4, and the solubility parameter δ value is a5 to 1 m9 with a solvent that is difficult to dissolve the fluoroalkyl methacrylate-containing polymer at room temperature (hereinafter referred to as a poor solvent). (…fcm”)
A mixed solvent with y2 (referred to as a bath medium-like solvent) that can dissolve the fluoroalkyl methacrylate-containing polymer at room temperature is preferable.

Examples of the poor solvent used in the present invention include methanol, ethylene glycol, and chrycerol, with methanol being particularly preferred.

Examples of good solvents used in the present invention include alcohols such as ethyl alcohol, isopropyl alcohol, and methyl alcohol, aromatic hydrocarbon compounds such as benzene, toluene, and xylene, methyl ethyl ketone, glyme, diglyme, dioxane, and tetrahydrofuran. Examples include ketone-ether compounds, dimethylformamide, dimethylsulfoxide, dimethylacetamide, etc. Among these, those selected from benzene, toluene and dioxane are preferred.

The imidizing agent can be easily diffused between the fluoroalkyl methacrylate-containing polymers in the solvent used in the present invention to quickly perform a uniform imidizing reaction, and the imidizing agent can be used to control heat generation and heat removal of the reaction. In order to bring about the dissolution effect and the viscosity adjustment effect of the dissolved polymer, it becomes possible to produce a methacrylimide-containing (fluoroalkyl methacrylate) polymer that is transparent, has a low refractive index, and has excellent heat resistance as a desired optical material. . As for the amount of the solvent used in the method of the present invention, a small amount is preferable from a physiological point of view, but if the amount is too small, the effect of the solvent described above will be reduced. The range is preferably 10 to 1000 parts by weight.

In the method of the present invention, when a mixed solvent of a poor solvent and a good solvent is used, the quantitative ratio is not limited.

Specific examples of the imidizing agent represented by the general formula: R-NH8 used in the method of the present invention include primary amines such as methylamine, ethylamine, and propylamine;
Examples include compounds that generate primary amines when heated, such as 3-dimethylurea, 1.3-diethylurea, and 1.5-dipropylurea, ammonia, and urea.

Examples of aromatic amines include aniline, toluidine, and trifluoroaniline.

Furthermore, examples of the alicyclic amine include cyclohexylamine and bornylamine.

The amount of these compounds to be used cannot be absolutely limited depending on the amount to be imidized, but is 1 to 250 parts by weight based on 100 parts by weight of the raw material, fluoroalkyl methacrylate-containing polymer. If the amount is less than 1 part by weight, no obvious improvement in heat resistance can be expected.

If it exceeds 250 parts by weight, it is not preferred from an economic standpoint.

In order to achieve a low refractive index, it is not preferable that the methacrylimide structural unit (A) accounts for a large proportion in the polymer. Therefore, the ratio of the methacrylimide structural unit (()) to the structural unit (B) is important.

The reaction between the raw material fluoroalkyl methacrylate-containing polymer and the imidizing agent is carried out at 100 to 350°C in the reactor.
, preferably 150 to 300°C.

If the reaction temperature is less than 100°C, the imidization reaction will be delayed, and if it exceeds 350°C, a decomposition reaction of the raw resin will occur.

The reaction time is not particularly limited, but the shorter the better from the viewpoint of bioformability, and is in the range of about 30 minutes to 5 hours. Hydrolysis with water occurs as a side reaction in the imidization condensation reaction process, and as a result, methacrylic acid is produced, making it difficult to obtain a methacrylimide-containing polymer having the desired amount of imidization, which is the object of the present invention. Therefore, in this reaction, it is preferable to carry out the reaction under substantially no water-containing conditions, that is, under conditions where the water content is 1 weight or less, preferably under anhydrous conditions.

Furthermore, from the viewpoint of the coloring property of the resulting polymer, the reaction system is preferably carried out under an inert gas having a low oxygen content, such as nitrogen, helium, or argon gas. The amount of imidization of the raw material resin in the present invention can be arbitrarily determined, but from the viewpoint of heat resistance and low refractive index, (98 to 100% by weight of methacrylimide structural units of N, 0 structural units of (B) A polymer comprising 0 to 50% by weight of the structural unit (C) is more preferable.

The heat resistance of a polymer containing 98 to 100% by weight of methacrylimide structural units as in the present invention is improved compared to a case where the methacrylimide structural units of component (A) are less than 98%.

In the present invention, the reaction apparatus used to carry out the network reaction step may be any one that does not impede the purpose of the present invention.
Examples include, but are not limited to, a plug flow type reactor, a screw extrusion type reactor, a column reactor, a duct reactor, a seed reactor, etc. In addition, in order to obtain a uniform methacrylimide-containing polymer 1, it is preferable to use a tank-like reactor equipped with a stirring device and a stirring device provided with a supply port and a discharge port, which has a mixing function throughout the inside of the reactor.

In the volatile substance separation step, most of the volatile substances are separated and removed from the reaction product containing the intermolecular condensation reaction product by the reaction between the fluoroalkyl methacrylate-containing polymer and the imidizing agent.

The content of residual volatile substances in the final polymer is less than 1% by weight,
Preferably it is 0.1 weight or less.

Removal of volatile substances can be carried out using conventional vent extrusion methods, devolatizers, etc., or by other methods, such as diluting the reaction product with a solvent, precipitating it in a large amount of insoluble medium, and filtering it. The drying method can be done using sound.

The methacrylimide-containing fluoroalkyl methacrylate polymer obtained by the above method has excellent transparency with little color discoloration, low refractive index, and heat resistance, but it develops discoloration during repeated molding processes. There are things that come to mind. For this purpose, an antioxidant can also be added to the obtained polymer in the present invention.

Examples of the hindered phenol antioxidant that can be added include 2,6-tert-butyl-p-cresol.

Also, examples of phosphite-based antioxidants include tetrakis (4-di-tart-butylphenol) 4,4'-biphenylene phosphonite. Examples of thioether antioxidants include dilaurylthiodipropionate.

The amount of antioxidant used is 101 to 100 parts by weight of the methacrylimide-containing fluoroalkyl methacrylate polymer.
5 parts by weight.

Furthermore, due to performance requirements, plasticizers, lubricants, ultraviolet absorbers,
Other additives such as colorants and pigments can also be used.

In the present invention, the fluoroalkyl methacrylate-containing polymer can be produced either continuously or batchwise.

In the polymerization of the fluoroalkyl methacrylate-containing polymer, which is the raw material resin in the present invention, a common radical polymerization initiator can be used as a polymerization catalyst, and specific examples include di-tert-butyl peroxide,
Examples include organic peroxides such as dicumyl peroxide and methyl ethyl ketone peroxide, and azo compounds such as methyl 2,2'-azobisisobutyrate and 2,2'-azobisisobutyronitrile.

During polymerization, an alkyl mercaptan, which is usually used as a polymerization degree regulator, is used as well as a chain transfer agent.

Examples of the polymerization method include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization, but bulk polymerization is preferred for obtaining high-purity polymer gold.

The present invention will be explained in more detail with reference to Examples below.

All parts and percentages used in the examples are by weight.

In these Examples, the following method was used to measure the properties of the polymer.

(1) The infrared absorption spectrum was measured by the KBr disk method using an infrared spectrometer (manufactured by Tadate Seisakusho, Model 285).

(2) The intrinsic viscosity of the polymer is Dee-Bishop (Dee)
The flow time (ts) of a dimethylformamide solution with a sample polymer concentration of 05% by weight and the flow time (to
) was measured at a temperature of 25°C ± α1°C, the relative viscosity yreL of the polymer was determined from the ts/lo value, and the value was then calculated from the following formula.

Intrinsic viscosity = (tn ηret)/O(at/f)(
where C represents grams of polymer per 100 - of solvent. ) (3) Heat distortion temperature is American Materials Testing Standard A8TM D6
Measured based on 48.9.

(4) The melt index of the polymer was determined using the American Materials Testing Standard A8TM D 125B (grams per 10 minutes at 230° C. and 8 load cycles).

(5) Imidization of polymer f
Nitrogen content and proton NMR at TNM-FX-10
0 (JKOL) spectrum oil-tar 100 MHz.

(6) Evaluation of thermal decomposition property The obtained polymer sound was heated at 270° C. in an air atmosphere for 120 minutes to obtain a heating loss value (1), which was used as the thermal decomposition evaluation result.

(7) Evaluation of transparency Molded into a thickness of 3 m + slope, ASTM D 1003
Transparency was evaluated by total transparency value according to the following.

Example 1 100 parts of 2,2.3,3.5-pentafluoropropyl methacrylate, 05 parts of polymerization initiator 2,2'-azobisisobutyronitrile α, n-dodecyh-mercaptan CL1
After mixing and dissolving the parts, the mixture was charged into a 2 L autoclave for bulk polymerization, and the mixture was sealed after repeated deaeration and nitrogen replacement. 50
℃ reaction temperature, 10F! React for # and then further at 70℃ for 5
After 9 hours of heating polymerization, the peak due to the exothermic polymerization was completed, and the polymerization was completely completed to obtain a transparent polymer. The polymerization conversion rate was 99%. The obtained polymer was crushed with a crusher and J
Separated into 16 mesh units and 32 mesh units according to SZ 8801 standard. The refractive index of the obtained polymer was 1.4
j 5, and the intrinsic viscosity Q was 75 dL/l.

A raw material consisting of 100 parts of the obtained 90 minutes dried polymer, washed with sulfuric acid, water, dried with calcium chloride, 90 parts of toluene purified by distillation, and 10 parts of methanol purified by distillation after dehydration and drying. After putting it into an autoclave equipped with a stirrer and thoroughly replacing it with nitrogen, the stirring speed was set to 9 Orpm.
The mixture was dissolved and stirred.

Thereafter, 20 parts of dried methylamine was added, and the reaction vessel was heated and stirred at 250° C. for 2 hours. Internal pressure 45
The pulp at the bottom of the reaction tank was opened to obtain a produced polymer.The produced polymer was vacuum dried under heating at 100°C to obtain a white powder polymer.

The infrared absorption spectrum of the thus obtained polymer was measured and found to be 1665 cm-'' and 750 ty.
Absorption characteristic of s-" K N-methylmethacrylimide polymer was observed. Also, in the nuclear magnetic resonance spectrum, a signal indicating a methacrylimide ring structure was confirmed, and the imidization rate was 100% based on the signal intensity. (Bacteriolytic Banzen 5% by weight, measurement temperature 70°C, internal standard tetramethylsilane) Elemental analysis showed that A4 had a nitrogen content of 0% and a fluorine content.The obtained polymer had an imidization rate of 100%.
It is a methacrylimide-containing polymer with a refractive index (
nD! s) was 1.550.

Furthermore, when the physical properties of this polymer were evaluated, the following values were shown.

Intrinsic viscosity α81 dt/f Melt index NOP 710 minutes Heat deformation temperature 175°C When this polymer was subjected to a heating test at 270°C for 120 minutes in an air atmosphere, the heating loss value was α05%. A molded specimen with a thickness of 3 cm was made and the transparency was evaluated after 9 days, and it was found that AST
Financial luck 95To when evaluated according to MD 1003
It showed good transparency.

Example 2 100 parts of 2,2.2-)lifluoroethyl methacrylate, 2.2'-azobisisobutyronitrile 1 part of polymerization initiator
After mixing and dissolving 0.5 parts of n-dodecyl mercaptan and 11 parts of n-dodecyl mercaptan, the autoclave was charged into a 2-ton bulk polymerization autoclave, and the autoclave was repeatedly degassed and replaced with a furnace, followed by sealing. 1 at 50℃ reaction temperature
After the reaction was carried out for 0 hour, and the polymerization was further carried out by heating at 70° C. for 5 hours, the peak due to the exothermic polymerization was completed, and the polymerization was completed to obtain a transparent polymer.

The polymerization conversion rate was 99 yen. The obtained polymer was pulverized using a crusher and separated into J-tech 5zaa01 standard, 16 mesh bath, and 32 mesh.

The obtained polymer had a refractive index L of 415 and an intrinsic viscosity α of 51.

100 parts of the sufficiently dried polymer thus obtained were washed with sulfuric acid, washed with water, dried over calcium chloride, and then mixed with 90 parts of toluene purified by distillation and 10 parts of methanol purified by distillation after dehydration and drying. The raw material consisting of was charged into an autoclave equipped with a stirrer, and after sufficient phoneme replacement, it was dissolved and stirred at a stirring rotation speed of 9 Orpm. Then, after adding 20 parts of dried methylamine, the inside of the reaction tank was heated to 230 parts.
The reaction was heated at ℃ for 2 hours. The internal pressure became 45 Kll/cm''G, and the lower part of the reaction tank was opened to obtain the produced polymer.The produced polymer Q was heated and vacuum dried at 100°C to obtain a white powdery polymer.

When the infrared absorption spectrum of the polymer thus obtained was measured, 166 S tya-'' and 75 G
Absorption peculiar to methylmethacrylimide polymer was observed in Cl11-'.

Further, in the nuclear magnetic resonance spectrum, a signal indicating a methacrylimide ring structure was observed, and the imidization rate was 100% based on the signal intensity.

From the elemental analysis values, the nitrogen content was +4 and the fluorine content was 0. The obtained polymer is a polymer containing O methacrylimide with an imidization rate of 100%, and its refractive index (n♂)
was 1.530.

When the physical properties of this polymer were evaluated, the following values were obtained.

Intrinsic viscosity: n, so at 7t Melt index: 2-5 t710 minutes Heat deformation temperature: 175°C When this polymer tube was subjected to a heating test at 270°C for 120 minutes in an air atmosphere, the heating loss value was α02%.

After creating a molded specimen with a thickness of 3 mm, transparency was evaluated.

However, when evaluated according to ASTM D 1003, it was found to have a financial score of 93%, indicating good transparency.

Examples 3 to 15 Methacrylimide-containing polymers were produced and evaluated using the same formulations as in Examples 1 and 2. The results are summarized in Table-1.

Comparative examples 1 to 3 The monomers listed in Table 1 were used.

Comparative Example 1 The raw material polymer used in Example 2 was evaluated and was found to be extremely easily thermally decomposed, with a heat distortion temperature of 70° C. and a 2-hour heating loss of 93 inches.

Comparative example 2 The raw material polymer used in Example 3 was evaluated.

The results are shown in Table-1.

Comparative Example 3 The raw material polymer used in Example 4 was evaluated and the results are shown in Table-
As per 1.

In addition, the abbreviations in the composition of the fluoroalkyl methacrylate-containing polymer shown in Table 1 mean the following monomers.

5IFM Methacrylic Acid 2.2. 3.3-Pentafluoropropyl MMA Methyl methacrylate MAA St methacrylate Styrene 3IFM 2.2.2-Trifluoroethyl methacrylate, 6IFM Methacrylic acid 2.2,2.2! '2-2'
-hexafluoroisopropyl 17 XPM methacrylic acid λ2.3.44.4.5
．． 5.6. Hez y, a, a, cp, q, t
p -herpfcafluorononane t -BMA tart-butyl methacrylate [Summary of the invention] According to the present invention, the excellent properties of fluorine-containing polymers including conventional fluoroalkyl methacrylate polymers can be maintained and exhibited. At the same time, it is possible to provide a methacrylimide-containing fluoroalkyl methacrylate polymer having excellent heat resistance and heat decomposition resistance.

Claims (4)

[Claims] (1) (A) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. 98 to 100% by weight of methacrylimide structural units represented by Structural units 0 to 10 that can be formed from vinyl monomers that can be conjugated with alkyl monomers
50% by weight of a methacrylimide-containing polymer. (2) R in the general formula [I] is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a phenyl group,
The methacrylimide polymer according to claim (1), which is a substituted phenyl group, cyclohexyl group, or bornyl group. (3) The structural unit that can be formed from the fluoroalkyl methacrylate monomer in (B) is represented by the following general formula [II] or general formula [III], or The methacrylimide-containing polymer according to item (2). [Note] General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, x is 1 or 2, y is 0 or an integer from 1 to 10, Z
_1 represents a hydrogen atom or a fluorine atom. ) General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, l, m and n are each 0 or an integer from 1 to 10, and Z_2, Z_3 and Z_4 each represent a hydrogen atom or a fluorine atom. However, l, m, and n will not be 0 at the same time, and Z_2, Z_3, and Z_4 will not represent hydrogen atoms at the same time.) (4) The monomer (C) is acrylic acid, methacrylic acid,
The methacrylate according to any one of claims (1) to (3), which is one or more monomers selected from acrylic esters, methacrylic esters, styrene, and substituted styrenes. Imide-containing polymer.