KR20160032107A - Method for producing copolymer - Google Patents

Abstract

An ether dimer of a 2- (hydroxyalkyl) acrylic acid ester such as an ether dimer of 4-t-butylcyclohexyl-? - (hydroxymethyl) acrylate, and other monomers such as (meth) In the presence of a Lewis acid such as propoxide, to obtain a copolymer having a tetrahydropyran ring in the main chain.

Description

[0001] METHOD FOR PRODUCING COPOLYMER [0002]

The present invention relates to a process for producing a copolymer. More particularly, the present invention relates to a method for producing a copolymer having a high glass transition temperature and excellent transparency, bending strength and moldability.

Since the methacrylic polymer mainly having methyl methacrylate units has high transparency and is excellent in molding processability, the molded articles are used for optical materials, lighting materials, signboards, decorative members and the like. However, since a typical methacrylic polymer has a low glass transition temperature, the molded article tends to undergo dimensional changes or deformation due to heat. Thus, in order to increase the glass transition temperature, various copolymers obtained by copolymerizing methyl methacrylate and other polymerizable monomers have been studied.

For example, a copolymer formed by copolymerizing methyl methacrylate and methacrylic alicyclic hydrocarbon ester is known (see Patent Document 1). However, this copolymer has not yet sufficiently increased the glass transition temperature, and the bending strength and the like are low.

Further, a copolymer comprising a copolymer of methyl methacrylate and maleimide is known (see Patent Document 2). However, the copolymer tends to be easily colored, and transparency tends to decrease.

Further, a copolymer having improved heat resistance by introducing a cyclic skeleton into the polymer main chain is known. For example, a copolymer having a repeating unit represented by the formula (3), which is obtained by copolymerizing methyl methacrylate and a diester represented by the formula (1) (hereinafter referred to as monomer (1)) in the presence of a peroxide, (See Patent Documents 3, 4 and 5).

[Chemical Formula 1]

(2)

(Of the formulas (1) and (3)

R ¹ and R ² each independently represent a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms and having a cyclic structure.

However, in the above-mentioned copolymerization, it is difficult to suppress the side reaction that the monomer (1) crosses between the molecules, and since the crosslinking increases with increasing the copolymerization ratio of the monomer (1), the moldability There is a tendency to decrease.

Japanese Patent No. 2513081 Japanese Patent Application Laid-Open No. 61-095011 Japanese Patent Application Laid-Open No. 2000-178317 Japanese Patent Application Laid-Open No. 2000-256480 Japanese Laid-Open Patent Publication No. 2012-082317

 Polymer, Vol. 35, No. 15, p3317 (1994).

The object of the present invention is to provide a method for producing a copolymer which has a high glass transition temperature and is excellent in transparency, bending strength and moldability.

The present inventors have conducted intensive studies in order to achieve the above object. As a result, the present invention has been completed including the following aspects.

[1] A process for producing a copolymer, which comprises polymerizing a monomer (1) represented by the formula (1) and another polymerizable monomer (hereinafter referred to as a monomer (2)) in the presence of a Lewis acid.

(3)

(In the formula (1)

R ¹ and R ² each independently represent a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms and having a cyclic structure.

[2] The process according to [1], wherein the monomer (2) is a (meth) acrylate ester.

[3] The production method of the above-mentioned [1] or [2], wherein the Lewis acid is at least one selected from the aluminum compounds represented by formula (2).

[Chemical Formula 4]

(In the formula (2)

R ³ represents an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 3;

R ⁴ represents an alkyl group having 1 to 5 carbon atoms. and b represents an integer of 0 to 3.

R ⁵ represents a phenyl group substituted by 1 to 4 alkyl groups. and c represents an integer of 0 to 3.

Also, the sum of a, b, and c is 3.)

[4] The production method according to any one of [1] to [3], wherein the copolymer has a molecular weight distribution measured by gel permeation chromatography of 3.2 or less.

[5] The production method according to any one of [1] to [4] above, wherein the monomer (1) and the monomer (2) are polymerized using a mass ratio of 2: 98 to 60:40.

According to the production process of the present invention, a copolymer having a tetrahydropyran ring in the main chain having a high glass transition temperature and excellent transparency, bending strength and moldability can be obtained. The copolymer obtained in the production process of the present invention having a high glass transition temperature and a thermoplasticity suitable for moldability means that the crosslinking reaction of the monomer (1) is suppressed during the polymerization and the cyclization reaction of the monomer (1) This is because it is a priority.

1 is a ¹ H-NMR chart of the copolymer obtained in Synthesis Example 1. Fig.

The process for producing a copolymer according to the present invention comprises polymerizing the monomer (1) and the monomer (2) in the presence of a Lewis acid.

[Chemical Formula 5]

The monomer (1) used in the present invention is a compound represented by the formula (1). In formula (1), R ¹ and R ² each independently represent a linear chain hydrocarbon group having 1 to 20 carbon atoms, a branched chain hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms having a cyclic structure .

Examples of the linear hydrocarbon group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, , an n-decyl group, a stearyl group, a lauryl group, an ethenyl group, a propenyl group, and a butenyl group.

Examples of the branched-chain hydrocarbon group having 1 to 20 carbon atoms include an isopropyl group, an s-butyl group, a t-butyl group, and a 2-ethylhexyl group.

Examples of the hydrocarbon group having 3 to 20 carbon atoms having a cyclic structure include a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a t-butylcyclohexyl group, an adamantyl group, a tricyclodecanyl group, a cyclopentadienyl group, , t-butylphenyl group, 2-benzethyl group, benzyl group, phenyl group and the like.

Of these, a branched-chain hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 3 to 20 carbon atoms having a cyclic structure is preferable.

Specific examples of the monomer (1) include dimethyl 2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl 2,2' - [oxybis Di (n-propyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate, di - propenoate, distearyl 2,2 '- [oxybis (methylene)] bis-2-propenoate, dilauryl 2,2' - [oxybis (methylene)] bis-2-propenoate;

Di (isopropyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate, di (s-butyl) 2,2' - [oxybis (methylene)] bis- Bis (2-ethylhexyl) 2,2 '- [oxybis (methylene)] bis (2-ethylhexyl) Propenoate;

Di (4-t-butylcyclohexyl) 2,2 '- [oxybis (methylene)] bis-2-propyl ester of dicyclohexyl 2,2' - [oxybis Bis (2-propenesulfonyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) Diisobornyl 2,2 '- [oxybis (methylene)] bis-2- (2-methoxyphenyl) propionate, di (cyclopentadienyl) Bis (methylene)] bis-2-propenoate, diorobornyl 2,2 '- [oxybis (methylene)] bis-2 -Propenoate;

(Benzyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate, diphenyl 2 , 2 '- [oxybis (methylene)] bis-2-propenoate, dinaphthyl 2,2' - [oxybis (methylene)] bis-2-propenoate.

These monomers (1) may be used singly or in combination of two or more.

Among them, dicyclohexyl 2,2 '- [oxybis (methylene)] bis-2 from the viewpoint that the obtained copolymer has a high glass transition temperature and that the obtained copolymer has a low intermolecular crosslinking structure and a narrow molecular weight distribution. Propeneate, diisobornyl 2,2 '- [oxybis (methylene)] bis-2-propenoate, ditbutyl 2,2' - [oxybis (4-t-butylcyclohexyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate are preferable.

Examples of the monomer (2) used in the present invention include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methallyl acid, Isoamyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2- Propyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, Methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, methoxydiethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxypolyethyleneglycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxyhexaethylene glycol methacrylate, meta Glycolic acid glycerol, meta Methacrylic acid diacrylate, methacrylic acid dipentaerythritol, methacrylic acid dipentaerythritol methacrylate, methacrylic acid caprolactone modified tetrahydrofurfuryl methacrylate, caprolactone methacrylate, methacrylic acid caprolactone Methacrylic acid esters such as modified di-pentaerythritol, caprolactone-modified methacrylic acid-modified 2-hydroxyethyl; Propyl acrylate, isopropyl acrylate, isobutyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, lauryl acrylate, tridecyl acrylate, Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, phenyl acrylate, benzyl acrylate, cyclohexyl acrylate, glycidyl acrylate, acrylate-3,4- Acrylic acid methoxyethylene glycol, acrylic acid methoxypolyethylene glycol, acrylic acid phenoxy ethyleneglycol, acrylic acid phenoxyhexaethylene glycol, acrylic acid glycerol, acrylic acid tetrahydrofurfuryl acrylate, acrylic acid dicyclopentaerythritol acrylate, Chloropentenyl, isobornyl acrylate, pentaerythritol acrylate Tall, acrylic, di pentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, caprolactone-modified dipentaerythritol, acrylic acid esters such as acrylate, caprolactone-modified 2-hydroxyethyl; Vinyl aromatic compounds such as styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene and 1-vinylnaphthalene; Ethylenically unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid; Acrylonitrile, methacrylonitrile; N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, Nt-butylmaleimide, maleimide; Acrylamide, methacrylamide; Ethylene, propylene, norbornene; Vinyl acetate, vinyl pivalate, vinyl benzoate; Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like.

These monomers (2) may be used singly or in combination of two or more.

Among them, (meth) acrylic acid ester is preferable from the viewpoints of transparency and weather resistance, more preferable is methyl methacrylate, cyclohexyl methacrylate or methyl acrylate, and methyl methacrylate is more preferable.

The mass ratio of the monomer (1) to the monomer (2) is not particularly limited, but is preferably 2:98 to 60:40, more preferably 15:85 to 50:50, : 60. If the mass ratio of the monomer (1) is too low, the resulting copolymer will have a low glass transition temperature, while if too large, the moldability will deteriorate.

The Lewis acid used in the present invention is not particularly limited as long as it is a material having an empty orbit capable of receiving an electron pair.

As an example of Lewis acid, M (X) _d (where M is B, Al, Si, Ti, Zr, Sb, Cd, Fe, Sn, Mg, Cu, In, La, Zn, V, X represents a halogen atom, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group; an alkoxy group, an aryloxy group, or a trifluoro group; And d represents the number of moles of X with respect to M).

Specific examples include trimethoxyborane, triethoxyborane, trifluoroborane, tribromoboran, boron trifluoride-ether complex, boron trifluoride-acetonitrile complex; There may be mentioned aluminum chloride, aluminum bromide, aluminum iodide, trimethoxy aluminum, chlorodimethoxy aluminum, chlorodiethoxy aluminum, triethyl aluminum, chlorodiethyl aluminum, dichloro (ethyl) aluminum, triisobutyl aluminum, trichlorotriethyl aluminum, Ethoxy (diethyl) aluminum; (IV), tetraethoxy titanium (IV), tetraisopropoxy titanium (IV), chlorotriisopropoxy titanium (IV), titanium tetrachloride, titanium tetrachloride, IV); Iron (III) chloride, iron (II) chloride, iron ditrifluoromethanesulfonate; (II) chloride, tin chloride (IV), tetramethyltin, tetraethyltin, tetrabutyltin, chloro (tributyl) tin, dimethyldichlorotin, dimethyldibromtin, dibutyldichlorotin, ditrifluoromethane Tin sulfonate; Tungsten hexachloride, molybdenum contaminated, antimony contaminated, tellurium chloride; Trifluoroethanesulfonic acid; Copper (II) chloride, ditrifluoromethanesulfonic acid copper; Zinc chloride, zinc ditrifluoromethanesulfonate; Zirconium (IV) chloride, tetramethoxyzirconium (IV), tetraethoxyzirconium (IV); Scandium dithrifluoromethanesulfonate, scandium chloride, scandium bromide, trimethoxy scandium, triethoxy scandium; Yttrium chloride, yttrium bromide, yttrium bromide, trimethoxy yttrium, triethoxy yttrium, yttrium trifluoromethanesulfonate (III); Hafnium trifluoromethanesulfonate (IV); Neodymium trifluoromethanesulfonate (III); Thiuram trifluoromethanesulfonate (III); Lanthanum chloride, lanthanum bromide, trimethoxy lanthanum, triethoxy lanthanum, lanthanum trifluoromethanesulfonate (III); Cerium chloride, cerium bromide, trimethoxy cerium, triethoxy cerium, cerium (III) trifluoromethanesulfonate; Samarium (III) chloride, samarium (III) bromide, trimethoxy samarium (III), triethoxy samarium (III), samarium (III) trifluoromethanesulfonate; Europium chloride, europium bromide, trimethoxy europium, triethoxy europium, europium trifluoromethanesulfonate; Gadolinium chloride, gadolinium bromide, trimethoxy gadolinium, triethoxy gadolinium, gadolinium trifluoromethanesulfonate; (6-t-butyl-4-methylphenoxy)] thiophene, trimethoxyetherbum, triethoxyetherbium, trifluoromethanesulfonic acid ytterbium (III), methoxy [ Aluminum, methoxy [2,2'-methylenebis (6-t-butylphenoxy)] aluminum, ethyl [2,2'-methylenebis (6-t-butylphenoxy)] aluminum, isobutyl [2,2'-methylenebis (6-t- (2-methylenebis (6-t-butylphenoxy)] aluminum, n-octyl [2,2'-methylenebis , 2'-methylenebis (6-t-butylphenoxy)] aluminum, ethoxy [2,2'-methylenebis (6-t-butylphenoxy)] aluminum, isopropoxy [2,2'-methylenebis (6-t- '-Methylene bis (6-t-butylphenoxy ) Aluminum, t-butoxy [2,2'-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, t-butoxy [2,2'- Phenoxy)] aluminum, and the like. These may be used singly or in combination of two or more kinds.

Among these Lewis acids, it is preferable to use at least one selected from the aluminum compounds represented by the formula (2).

[Chemical Formula 6]

In the formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. a represents the number of R < ³ > and is an integer of 0 to 3;

In the formula (2), R ⁴ represents an alkyl group having 1 to 5 carbon atoms. b represents the number of R ⁴ and is an integer of 0 to 3.

In the formula (2), R ⁵ represents a phenyl group which may be substituted with 1 to 3 alkyl groups. c represents the number of R < ⁵ > and is an integer of 0 to 3; Also, the sum of a, b, and c is 3.

Specific examples of the aluminum compound represented by the formula (2) include alkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, Aluminum alkoxides such as trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tributoxide, aluminum triisobutoxide and aluminum triphenolate, aluminum phenoxides, Ethyl aluminum diisopropoxide, ethyl aluminum diisopropoxide, isopropyl aluminum diisopropoxide, diethyl aluminum ethoxide, diethyl aluminum isopropoxide, diisopropyl aluminum isopropoxide, ethyl bis ( Di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-ditbutylphenoxy) aluminum, (2,6-di-t-butylphenoxy) aluminum, isobutylbis (2,6-di- t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-ditbutylphenoxy) aluminum, methoxybis (2,6-ditbutyl-phenoxy) aluminum, ethoxybis (2,6-ditbutyl-4-methylphenoxy) aluminum, ethoxybis (2,6-ditert-butylphenoxy) aluminum, isopropoxybis (2,6-ditbutyl-4-methylphenoxy) aluminum, isopropoxybis (2,6-di-t-butylphenoxy) aluminum, t-butoxybis (2,6- (2,6-di-t-butylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum, diethyl Methylphenoxy) aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum (2,6-di-t-butylphenoxy) aluminum, diisobutyl (2,6- -Butyl-4-methylphenoxy) aluminum, di-n-octyl (2,6-di-t-butylphenoxy) aluminum and the like and alkyl aluminum phenoxides. Of these, aluminum triethoxide, aluminum triisopropoxide, ethylbis (2,6-ditbutylphenoxy) aluminum and / or diethyl (2,6-ditertiaryphenoxy) aluminum desirable. When an aluminum compound represented by the formula (2) is used, a thermoplastic copolymer having no intermolecular crosslinking can be produced at a high yield by polymerization of the monomer (1) and the monomer (2).

The amount of the Lewis acid to be used is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 30 parts by mass, and still more preferably from 1 to 10 parts by mass, based on 100 parts by mass of the total monomers to be used. The Lewis acid is used in an amount of preferably 0.001 to 10 mol, more preferably 0.05 to 2 mol, and still more preferably 0.1 to 1 mol, based on 1 mol of the monomer (1). When the amount of the Lewis acid used is within this range, the crosslinking reaction of the monomer (1) is inhibited and the cyclization reaction proceeds predominantly, so that the moldability of the resulting copolymer tends to be increased. The mechanism of action of Lewis acid is not known precisely, but it is presumed as follows. First, Lewis acid is coordinated to the carbonyl oxygen of the monomer (1), and the monomer (1) is made into a bulk. The periphery of the carbon-carbon double bond of the monomer (1) is congested in three dimensions, and the crosslinking reaction does not occur well. As a result, it is presumed that the cyclization reaction of the monomer (1) proceeds preferentially and the crosslinking is reduced.

In the polymerization of the monomer (1) and the monomer (2), a polymerization initiator is usually used. Such a polymerization initiator is not particularly limited and includes, for example, cumene hydroperoxide, dicumyl peroxide, acetyl peroxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide, Butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethyl hexanoate, t-butyl peroxy-2-ethyl hexanoate, t-hexyl peroxyisopropyl carbonate, Monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate , t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethyl butyl peroxyneodecanoate, 1,1-di (t-butyl peroxy ) Cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as; Azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) Azo compounds such as 2'-azobis (2-methylbutyronitrile) and dimethyl 2,2'-azobis (2-methylpropionate); And persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate. Further, a redox-type initiator in which an oxidizing agent such as hydroperoxide, dialkylperoxide, diacylperoxide and the like is combined with a tertiary amine, a naphthenate, mercaptan, or other reducing agent may be used. These polymerization initiators may be used alone or in combination of two or more. Of these polymerization initiators, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), di- 1,1-di (t-butylperoxy) cyclohexane is preferable from the viewpoint of obtaining a copolymer which is inexpensive and smoothly has a high glass transition temperature.

The amount of the polymerization initiator to be used may be suitably set according to the combination of the monomers to be used, the reaction conditions, the molecular weight of the target copolymer, and the like, and is not particularly limited. The amount of the polymerization initiator to be used is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.2 part by mass based on 100 parts by mass of the total monomers to be used from the viewpoint of obtaining a copolymer having high moldability.

For the purpose of adjusting the molecular weight of the copolymer or the like, a chain transfer agent may be used if necessary. Such chain transfer agent is not particularly limited, and examples thereof include halogen compounds such as carbon tetrachloride and carbon tetrabromide; Alcohols such as isopropyl alcohol and isobutyl alcohol; Dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, methyl mercaptoacetate, 1,4-butanedithiol, 1,6-dodecyl mercaptan, Butanediol bis-thioglycolate, hexanediol bis-thioglycolate, hexanediol bis-thiophthalate, trimethylolpropane tris- (beta -thio Propionate), pentaerythritol tetrakisthiopropionate, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, thioglycolic acid, ethyldisulfide, sec-butyldisulfide, Mercaptans such as hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan, and phenethyl mercaptan; ? -methylstyrene dimer; And terpinolene.

Of these, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable. These chain transfer agents may be used singly or in combination of two or more kinds.

The amount of the chain transfer agent to be used can be suitably set according to the combination of the monomers to be used, the reaction conditions, the molecular weight of the target copolymer, and the like, and is not particularly limited. However, Preferably from 0.01 to 1 part by mass, more preferably from 0.2 to 0.8 part by mass, and still more preferably from 0.2 to 0.6 part by mass, based on 100 parts by mass of the total monomers to be used.

The radical polymerization in the presence of a Lewis acid can be carried out by a solution polymerization method or a bulk polymerization method. Particularly, the solution polymerization is preferable from the viewpoint of producing a copolymer having high moldability.

When the polymerization reaction is carried out by the solution polymerization method, a solution prepared by dissolving the monomer (1) and the monomer (2) in an organic solvent is prepared and carried out. The concentration of the monomer in such a solution is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 10 to 50% by mass.

The organic solvent used for the solution polymerization is not particularly limited as long as it is an organic solvent having a small effect of inhibiting the polymerization reaction. Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene and anisole; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane and decalin; Ketones such as acetone and methyl ethyl ketone; Alcohols such as methanol, ethanol and isopropanol; And ethers such as tetrahydrofuran and diethyl ether. Of these, toluene, xylene, and methyl ethyl ketone are preferable from the viewpoint of easy dissolution of the monomers and the like.

The temperature in the reaction in the solution polymerization method is preferably -40 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and still more preferably 20 ° C to 140 ° C. The reaction time in the solution polymerization method is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.2 to 20 hours from the viewpoint of economy and the like. The solution polymerization is preferably carried out in an inert gas atmosphere such as nitrogen gas.

When the polymerization reaction is carried out by the bulk polymerization method, the polymerization conversion rate of the monomer mixture obtained by mixing the monomer (1) and the monomer (2) is preferably from 1 to 90% by mass, more preferably from 10 to 80% by mass %, More preferably from 10 to 50 mass%.

The temperature during the reaction in the bulk polymerization method is preferably 300 占 폚 or lower, more preferably 250 占 폚 or lower. The reaction time in the bulk polymerization method is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 2 to 200 hours from the viewpoint of economy and the like. The bulk polymerization is preferably carried out in an inert gas atmosphere such as nitrogen gas.

The polymerization reaction may be carried out in a batch reactor in a molding reactor or in a continuous flow reactor in a molding reactor or a tubular reactor. The reaction system can be appropriately set in terms of production amount, production cost, and the like.

The copolymer produced by the polymerization reaction can be isolated by a known technique.

The solution polymerization method includes a method in which a copolymer is precipitated by contacting the resulting copolymer solution with a poor solvent, a method in which a solvent is volatilized and removed from the resulting copolymer solution under reduced pressure to isolate the copolymer, A method of blowing water vapor into the copolymer solution to remove the solvent to isolate the copolymer, and the like.

Examples of the bulk polymerization method include a method of precipitating a copolymer by contacting the resultant copolymer composition with a poor solvent, a method of volatilizing and removing the unreacted monomer from the resulting copolymer composition under reduced pressure to isolate the copolymer, and the like have.

As a method of removing the unreacted monomers and the solvent, it is preferable to remove the unreacted monomer and the solvent by the flash method or the adiabatic flash method. The temperature of devolatilization in the adiabatic flash system is preferably 200 to 300 占 폚, more preferably 220 to 270 占 폚. If it is less than 200 ° C, it takes time for devolatilization, and it is liable to become insufficient in devolatilization. When the defoaming is insufficient, appearance defects such as silver may be caused in the molded article. If it exceeds 300 ° C, the composition tends to be colored by oxidation, soot, or the like.

The glass transition temperature of the copolymer obtained by the production method of the present invention is preferably 110 to 180 占 폚, more preferably 130 to 165 占 폚. When the glass transition temperature is low, the heat resistance tends to decrease. If the glass transition temperature is high, the moldability tends to decrease.

The weight average molecular weight (hereinafter abbreviated as Mw) of the copolymer obtained by the production method of the present invention is preferably 10,000 to 500,000, more preferably 30,000 to 300,000, It is 20 million. When the Mw is too small, the impact resistance and toughness of the molded article obtained from the copolymer tends to decrease. When the Mw is too large, the flowability of the copolymer is lowered and the moldability tends to decrease.

The Mw, the number average molecular weight (hereinafter referred to as Mn) and the molecular weight distribution of the resulting copolymer can be controlled depending on the type and amount of the polymerization initiator and chain transfer agent. In the present specification, the molecular weight distribution means a value of Mw / Mn.

In the present specification, Mw and Mn are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The molecular weight distribution of the copolymer obtained by the production method of the present invention is preferably 1.0 to 3.0, more preferably 1.1 to 3.0. If the molecular weight distribution is small, the moldability of the copolymer tends to decrease. If the molecular weight distribution is large, the impact resistance of the molded article obtained from the copolymer tends to decrease, and the molded article tends to retreat.

The copolymers obtained by the present invention can be used effectively for a wide range of applications such as molding materials, adhesives, paints, and various treating agents, by taking advantage of their properties and performing various molding, processing, post- have.

The copolymer obtained by the present invention may be used alone or in combination with one or more of polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene- Styrene block copolymers, and other thermoplastic polymers.

When the copolymer of the present invention is molded, various additives and the like may be added to the copolymer as required. Examples of additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, impact resistance modifiers, organic pigments, light diffusers, antistatic agents, phosphors, antistatic agents, flame retardants, plasticizers, , Fibers and the like. The amount of such various additives to be blended can be appropriately determined within a range that does not impair the effect of the present invention. The blending amount of each additive is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the copolymer and the other polymer to be added as required.

The antioxidant is effective in preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, hindered phenol antioxidants, thioether antioxidants and the like. These antioxidants may be used singly or in combination of two or more kinds. Among them, a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable from the viewpoint of an effect of preventing deterioration of optical characteristics due to coloring, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant are more preferably used in combination.

When the phosphorus-based antioxidant and the hindered phenol-based antioxidant are used in combination, the ratio is not particularly limited, but preferably in the range of 1/5 to 2/1, and more preferably in the range of 1/5 to 2/1, in terms of mass ratio of the phosphorus-based antioxidant / hindered phenol- Is 1/2 to 1/1.

Examples of the phosphorus antioxidant include 2,2-methylenebis (4,6-dit butylphenyl) octyl phosphite (trade name: Adekastab HP-10 manufactured by ADEKA), tris -Butylphenyl) phosphite (trade name: IRUGAFOS 168 manufactured by BASF).

Examples of the hindered phenol antioxidant include pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name IRGANOX1076, manufactured by BASF).

The heat deterioration inhibitor can prevent the thermal degradation of the copolymer by capturing polymer radicals generated when exposed to high heat under substantially anaerobic conditions.

Examples of the thermal deterioration preventing agent include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (SumilTomo Chemical Co., , 4-di-t-amyl-6- (3 ', 5'-di-t-amyl-2'-hydroxy- alpha -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., .

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. Ultraviolet absorbers are compounds known to have a function of mainly converting light energy into heat energy.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, anilides of oxalic acid, malonic acid esters and formamidines. Triazoles, and anilides. These may be used singly or in combination of two or more kinds.

Examples of the benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name: TINUVIN 329, manufactured by Ciba Specialty Chemicals) - (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name: TINUVIN 234 manufactured by BASF).

Examples of anilides include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd., product name: Sandu Boa VSU).

Among these ultraviolet absorbers, benzotriazoles are most preferably used from the viewpoint of effectively suppressing deterioration of the copolymer due to ultraviolet exposure.

The light stabilizer is a compound known to have a function of capturing a radical, which is generated mainly by oxidation by light. Preferable examples of the light stabilizer include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

Examples of the lubricant include stearic acid, behenic acid, stearoamidic acid, methylenebisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.

The release agent is a compound having a function of facilitating release of a molded article from a mold. Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; Stearic acid monoglyceride, stearic acid monoglyceride, and stearic acid diglyceride. In the present invention, it is preferable to use a combination of a higher alcohol and a glycerin fatty acid monoester as a release agent. When the higher alcohols and the glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but the mass ratio of the higher alcohol / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1, more preferably 2.8 / 1 to 3.2 / 1.

The polymer processing aid is a compound which exerts an effect on the thickness precision and thinning of the copolymer when the copolymer is molded. The polymer processing aid is usually a polymer particle having a particle diameter of 0.05 to 0.5 탆 which can be produced by an emulsion polymerization method.

The polymer particles may be single-layer particles composed of a polymer having a single composition ratio and a single intrinsic viscosity, or may be multilayer particles composed of two or more polymers having different composition ratios or intrinsic viscosities. Of these, particles having a two-layer structure having a polymer layer having an intrinsic viscosity of less than 5 dl / g in the inner layer and a polymer layer having an intrinsic viscosity of 5 dl / g or more in the outer layer are preferably used. The polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g as a whole.

Examples of the impact resistance modifier include a core-shell type modifier including an acrylic rubber or a diene rubber as a core layer component; A modifier containing a plurality of rubber particles, and the like.

As the organic dye, a compound having a function of converting ultraviolet rays, which are regarded as harmful to the copolymer, to visible light is preferably used.

Examples of the light diffusing agent and the gloss removing agent include glass fine particles, polysiloxane crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.

Examples of the fluorescent substance include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent whitening agent.

Examples of the antistatic agent include stearoamidopropyl dimethyl-beta-hydroxyethylammonium nitrate and the like.

Examples of the flame retardant include organic halogen-based flame retardants such as tetrabromobisphenol A, decabromodiphenyloxide, and brominated polycarbonate; Halogen-based flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, and tricresyl phosphate.

Examples of the plasticizer include, for example, tricresyl phosphate, trioryanyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenylcresyl phosphate, monophenyl dicresyl phosphate, diphenyl monoallylenyl phosphate, Phosphoric acid triester plasticizers such as phenyldimethylenyl phosphate, tributylphosphate and triethylphosphate; Phthalic acid ester plasticizers such as dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, octyldecyl phthalate and butylbenzyl phthalate; Fatty acid monobasic acid ester plasticizers such as butyl oleate and glycerin monooleic acid ester; Divalent alcohol ester plasticizers; An oxyacid ester plasticizer and the like can be used.

As the plasticizer, squalane (C30H62, Mw = 422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO VG32, ISO VG68, ISO VG100, ISO VG8 and ISO VG21 specified in JIS- Polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like may be used. Among them, squalane, liquid paraffin and polyisobutene are preferable.

Examples of the inorganic filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like.

Examples of the fiber include glass fiber and carbon fiber.

In addition, the copolymer of the present invention can be made into a polymer composition by mixing with other polymers within the range not hindering the effect of the present invention. These other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene and the like; Ethylenic ionomers; Styrene resins such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin and MBS resin; Methyl methacrylate-based polymers, methyl methacrylate-styrene copolymers; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Nylon 6, nylon 66, and polyamide elastomers; Polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; Acrylic rubber, silicone rubber; Styrene-based thermoplastic elastomers such as SEPS, SEBS and SIS; And olefin rubbers such as IR, EPR and EPDM.

The polymer composition comprising the copolymer of the present invention or the copolymer of the present invention can be produced by a known method such as injection molding (including insert molding, two-color molding, pressing, core backing, sandwich molding, etc.), compression molding, Various molding products can be obtained by molding by a conventionally known method such as molding, blow molding, inflation molding and calender molding.

Examples of the molded article made of the copolymer of the present invention or the polymer composition containing the copolymer of the present invention include a signboard such as a billboard, a stand signboard, an extruded signboard, a railway signboard, a rooftop signboard, and the like; Display parts such as showcase, partition plate, and store display; Lighting parts such as fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, bricks and chandeliers; Interior parts such as pendants and mirrors; Architectural components such as doors, domes, safety glass windows, partitions, stair planks, balcony boards, and roofs of leisure buildings; Transportation system components such as aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shields, automotive side visors, rear visors, head wings and headlight covers; Electronic device parts such as nameplates for acoustic images, stereo covers, television protective masks, vending machines; Parts of medical devices such as nurseries and rental parts; Machine-related parts such as machine covers, instrument covers, experimental equipment, rulers, letter glasses, and observation windows; Optical related parts such as a liquid crystal protective plate, a light guide plate, a light guide film, a polarizer protective film, a Fresnel lens, a lenticular lens, a front plate of various displays, Traffic-related parts such as road signs, guide plates, curved mirrors, soundproof walls; A film member such as an automobile interior surface material, a surface material of a cellular phone, a marking film, or the like; Housings for home appliances such as canopies of washing machines, control panel, top panel of an electric cooker; Other examples include a greenhouse, a large water tank, a box water tank, a watch panel, a stub, a sanitaryware, a desk mat, an organic part, a toy, and a mask for face protection at the time of welding.

Example

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples. The present invention is not limited to the following examples. Further, the present invention includes all aspects in which the technical characteristics such as the characteristic value, the form, the preparation method, the use, and the like described above are arbitrarily combined.

Measurement of the physical properties in the examples and comparative examples were carried out by the following methods.

(Polymerization conversion rate of methyl methacrylate)

Device: ULTRA SHIELD 400 PLUS manufactured by Bruker

Solvent: Chloroform

0.05 ml of the polymerization solution was mixed with 1 ml of deuterated chloroform, and the solution was subjected to ¹ H-NMR measurement by adding 64 times at room temperature. In the obtained ¹ H-NMR spectrum, the peak of TMS was set to 0 ppm. From the hydrogen (3.4 to 3.9 ppm, 3H) of the methoxy group contained in the methyl methacrylate unit in the copolymer and the hydrogen (6.26 ppm, 1H) of the olefin of the methyl methacrylate monomer remaining in the polymerization solution, The polymerization conversion rate was calculated.

(Mw and molecular weight distribution)

The Mw and the molecular weight distribution are obtained in terms of polystyrene on the basis of measurement by gel permeation chromatography (GPC). As the GPC apparatus, HLC-8320 manufactured by Tosoh Corporation was used, and two columns of TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 were connected in series.

Eluent: tetrahydrofuran

Flow rate of the eluent: 0.6 ml / min

Column temperature: 40 DEG C

Calibration curve: using standard polystyrene 10 points

(Analysis of Composition of Copolymer)

Device: ULTRA SHIELD 400 PLUS manufactured by Bruker

Solvent: Chloroform

10 mg of the synthesized copolymer was mixed with 1 ml of deuterated chloroform, and the resultant was subjected to ¹ H-NMR measurement by adding 64 times at room temperature.

The analytical method of the obtained chart will be described as an example of a copolymer of an ether dimer of dicyclopentanyl-? - (hydroxymethyl) acrylate and methyl methacrylate.

Formula (I) represents an ether dimer of cyclized dicyclopentanyl-a- (hydroxymethyl) acrylate.

The formula (II) shows that the ether dimer of the noncyclic dicyclopentanyl-? - (hydroxymethyl) acrylate is not crosslinked.

The formula (III) indicates that the monomer is crosslinked with the ether dimer of the noncyclic dicyclopentyl-? - (hydroxymethyl) acrylate.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

1 shows an example of a ¹ H-NMR chart.

The peak of TMS was set to 0 ppm.

The integrated value of the peak at 3.6 ppm attributed to the hydrogen of the methoxy group contained in the methyl methacrylate unit in the copolymer was 3.0.

A peak of 4.1 ppm attributed to the methylene group hydrogen (-CH ₂ -O-CH ₂ -) adjacent to the ether oxygen of the ether dimer of the non-cyclic dicyclopentyl-α- (hydroxymethyl) acrylate in the copolymer And the integral value of X is X.

A peak at 4.5 ppm is also found in the methylene group hydrogen (-CH ₂ -O-CH (CH _{3) 2)} adjacent to the ether oxygen in the tetrahydropyran ring structure of the ether dimer of the cyclized dicyclopentanyl-α- (hydroxymethyl) ₂ -) and is attributed to the dicyclopentanyl -α- (hydroxymethyl) dicyclopentanyl group hydrogen methine group (-C (= O of the ester group of the ether dimer acrylate) OCH-). It was also considered that, even in the ringing state and the ringing state, the ringing of the peak of 4.5 ppm did not change. Here, the integral value of the peak of 4.5 ppm is defined as Y.

In addition, the above-mentioned attribution of the peak can be applied without considering the influence of the crosslinking of the polymer.

When the number of moles of ether dimer units of dicyclopentanyl- alpha - (hydroxymethyl) acrylate in the copolymer is 1, the number of moles of methyl methacrylate units is

A = {(X + Y) / 6}

.

The introduction ratio W (% by mass) of the ether dimer of dicyclopentanyl-? - (hydroxymethyl)

W = A x 454.66 / (A x 454.66 + 1 x 100.14) x 100

.

(Glass transition temperature)

The DSC curve was measured by a differential scanning calorimetry method under the condition that the temperature was raised once up to 230 占 폚, then cooled to room temperature, and then the temperature was raised from room temperature to 230 占 폚 at 10 占 폚 / min in accordance with the JIS K7121 test method. The midpoint glass transition temperature determined from the DSC curve measured at the time of the second temperature rise was adopted as the glass transition temperature in the present invention. Here, DSC-50 manufactured by Shimadzu Corporation was used as a measuring apparatus.

(Transparency)

In accordance with JIS K7361-1, the total light transmittance was measured using HR-100 manufactured by Murakami Color Research Laboratory. The transparency was evaluated by the following index.

AA: Total light transmittance 85% or more

BB: Total light transmittance less than 85%

(Moldability)

Using a mold having a long side of 150 mm and a short side of 70 mm, the copolymer was fed so as to have a thickness of 3.2 mm and hot pressed at 230 캜 for 5 minutes. Thereafter, it was naturally cooled at an outside temperature of 23 캜 for one hour. The molded body taken out from the mold was rated AA for no cracks, and rated BB for cracks. Also, in the case where molding was not possible, the evaluation was made as BB.

(Absorbency)

A test piece of 150 mm x 10 mm x 3.2 mm was dried for 3 days under an environment of 50 캜 and 5 mm Hg to obtain a satisfactory test piece. The mass W0 of the test piece was measured. Thereafter, the full-bodied test piece was immersed in water having a temperature of 23 DEG C and left for 2 months. After taking out from the water, the mass W1 of the test piece was measured. The saturation absorption rate (%) was calculated by the following formula.

Saturated absorption rate = {W1 - W0} / W0 100

The absorbency was evaluated by the following index.

AA: Saturation absorption rate is 2% or less

BB: Saturation rate is higher than 2%

(Bending strength)

A test piece of 80 mm x 13 mm x 3.2 mm was measured according to ASTM D790.

AA: Bending fracture strength of 50 MPa or more

BB: Bending fracture strength less than 50 MPa

(Synthesis Example 1)

260.3 g (1.0 mol) of dicyclopentyl acrylate (manufactured by TOKYO KASEI KOGYO KABUSHIKI KAISHA), 30.3 g (1.0 mol) of paraformaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) and 1,4-diazabicyclo , 120 mg of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 14.9 g (0.13 mol) of [2.2.2] octane (manufactured by Wako Pure Chemical Industries, , And the mixture was reacted at 85 캜 for 24 hours while air bubbling was carried out, followed by reaction at 90 캜 for 7 hours. Thereafter, the obtained reaction solution was poured into 1 L of methanol and stirred for 30 minutes. Thereafter, the mixture was allowed to stand still overnight at 5 캜 to obtain an ether dimer of a dicyclopentyl-? - (hydroxymethyl) acrylate (also called di (tricyclodecanyl) 2,2 '- [oxy Bis (methylene)] bis-2-propenoate (Compound A) was obtained in an amount of 114 g (yield: 50%).

[Chemical formula 10]

(Synthesis Example 2)

Α- (hydroxymethyl) propyl acrylate was obtained in the same manner as in Synthesis Example 1, except that 260.3 g (1.0 mol) of dicyclopentanyl acrylate was replaced by 208.3 g (1.0 mol) of isobornyl acrylate (manufactured by Tokyo Kasei Kogyo Co., (Yield: 25%) of an ether dimer (trade name: di (isobornyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate of formula

(11)

(Synthesis Example 3)

128.0 g (1.0 mol) of t-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 30.3 g (1.0 mol) of paraformaldehyde and 1,4-diazabicyclo [2.2.2] g (0.13 mol) of p-methoxyphenol, 120 mg of p-methoxyphenol and 60 g of t-butyl alcohol were charged and reacted at 85 캜 for 24 hours while air bubbling was carried out. To the resulting reaction solution was added 20 ml of methylene chloride. This solution was separated and washed with an aqueous dilute hydrochloric acid solution, and further washed with ion-exchanged water. The solution was distilled under reduced pressure to obtain an ether dimer (also referred to as di (t-butyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate of t-butyl- (Chemical structure C) was obtained as 58 g (yield: 38%).

[Chemical Formula 12]

(Synthesis Example 4)

Butylcyclohexyl acrylate was obtained in the same manner as in Synthesis Example 1 except that 260.3 g (1.0 mol) of dicyclopentanyl acrylate was changed to 210.3 g (1.0 mol) of 4-t-butylcyclohexyl acrylate (Sigma Aldrich) di (t-butylcyclohexyl) 2,2 '- [oxybis (methylene)] bis-2-propenoate having the formula: g (yield: 60%).

[Chemical Formula 13]

(Example 1)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of an ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 2 parts by mass of azobisisobutyronitrile (AIBN , Manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 8.5 parts by mass (1.7% by mass) of aluminum triisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.).

After the pressure vessel was sufficiently replaced with nitrogen gas, the temperature was raised to 80 캜 while stirring. And polymerization was carried out at 80 DEG C for 2 hours while stirring. Thereafter, 0.05 parts by mass of AIBN was added, and the mixture was further polymerized for 2 hours. 200 parts by mass of a 5 mass% citric acid aqueous solution was added to the obtained polymerization solution, and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out, and then washed with ion-exchanged water until it became neutral to remove aluminum triisopropoxide. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid was separated by filtration and sufficiently dried to obtain 70 parts by mass of the copolymer (A1). As a result of ¹ H-NMR measurement of the copolymer (A1), it was found that the content of the structural unit derived from methyl methacrylate was 80% by mass and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 20 mass%. The copolymer (A1) had a weight average molecular weight (Mw) of 121,000 and a molecular weight distribution (Mw / Mn) of 2.74.

The copolymer (A1) was fed to a twin-screw extruder controlled at 230 占 폚, and volatile components such as residual solvent and unreacted monomer were separated and removed, and then the resin component was extruded to form strands. The strand was cut into a pelletizer to obtain a pellet-like copolymer. The glass transition temperature of the pellet-like copolymer was measured. Further, the pellet-like copolymer was hot-pressed at 230 占 폚 to obtain a sheet-like molded article having a thickness of 3.2 mm. The moldability at this time was confirmed. The test piece was cut from the obtained sheet-like molded article to measure transparency, absorbency and bending strength. The results are shown in Table 1.

(Example 2)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of an ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 1,1-di (t (Butylperoxy) cyclohexane (Ferhexa C, manufactured by Nippon Oil and Fats Co., Ltd.) and 8.5 parts by mass (1.7% by mass) of aluminum triisopropoxide.

After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 100 占 폚 while stirring. And polymerization was carried out at 100 DEG C for 2 hours while stirring. Thereafter, 0.05 part by mass of perhexa C was added, and the mixture was further polymerized for 2 hours. To the resulting polymerization solution was added 200 parts by mass of a 5 mass% citric acid aqueous solution, and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out, and then washed with ion-exchanged water until it became neutral to remove aluminum triisopropoxide. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid was separated by filtration and sufficiently dried to obtain 50 parts by mass of the copolymer (A2). As a result of ¹ H-NMR measurement of the copolymer (A2), it was found that the content of the structural unit derived from methyl methacrylate was 83% by mass and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 17% by mass. The copolymer (A2) had a weight average molecular weight (Mw) of 213,000 and a molecular weight distribution (Mw / Mn) of 2.46. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. Table 1 shows the evaluation results of the obtained sheet-like molded article.

(Example 3)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of an ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 10 parts by mass of di-t-butyl peroxide (Manufactured by Nippon Oil & Fats Co., Ltd., perbutyl D) and 4.2 parts by mass (1.7% by mass) of aluminum triisopropoxide.

After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 140 占 폚 with stirring. And polymerization was carried out at 140 DEG C for 2 hours while stirring. To the resulting polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5 mass% citric acid aqueous solution were added, and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out, and then washed with ion-exchanged water until it became neutral to remove aluminum triisopropoxide. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid was separated by filtration and sufficiently dried to obtain 50 parts by mass of the copolymer (A3). As a result of ¹ H-NMR measurement of the copolymer (A3), it was found that the content of the structural unit derived from methyl methacrylate was 89% by mass and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 11 mass%. The copolymer (A3) had a weight average molecular weight (Mw) of 99,000 and a molecular weight distribution (Mw / Mn) of 2.97. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. Table 1 shows the evaluation results of the obtained sheet-like molded article.

(Example 4)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 0.05 parts by mass of AIBN, And 4.2 parts by mass (1.7% by mass) of butyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum were added.

After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 캜 while stirring. And polymerization was carried out at 80 DEG C for 2 hours while stirring. To the resulting polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5 mass% citric acid aqueous solution were added, and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out and then washed with ion-exchanged water until it became neutral to remove isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid was separated by filtration and sufficiently dried to obtain 30 parts by mass of the copolymer (A4). As a result of ¹ H-NMR measurement of the copolymer (A4), the content of the structural unit derived from methyl methacrylate was 86 mass%, and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 14 mass%. The copolymer (A4) had a weight average molecular weight (Mw) of 98,000 and a molecular weight distribution (Mw / Mn) of 1.83. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. Table 1 shows the evaluation results of the obtained sheet-like molded article.

(Example 5)

And 45 parts by mass of the copolymer (A5) was obtained in the same manner as in Example 1 except that the addition amount of aluminum triisopropoxide was changed to 5.0 parts by mass (1.0% by mass). As a result of ¹ H-NMR measurement of the copolymer (A5), the content of the structural unit derived from methyl methacrylate was 82 mass%, and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 18 mass%. The copolymer (A5) had a weight average molecular weight (Mw) of 107,000 and a molecular weight distribution (Mw / Mn) of 2.06. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. Table 1 shows the evaluation results of the obtained sheet-like molded article.

(Example 6)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 0.05 parts by mass of AIBN, And 4.2 parts by mass (1.7% by mass) of triisopropoxide.

After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 캜 while stirring. And polymerization was carried out at 80 DEG C for 2 hours while stirring. To the resulting polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5 mass% citric acid aqueous solution were added, and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out, and then washed with ion-exchanged water until it became neutral to remove aluminum triisopropoxide. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid component was separated by filtration and sufficiently dried to obtain 48 parts by mass of the copolymer (A6). As a result of ¹ H-NMR measurement of the copolymer (A6), it was found that the content of the structural unit derived from methyl methacrylate was 86% by mass and the content of the structural unit derived from the ether dimer of dicyclopentanyl-? - (hydroxymethyl) The content of the structural unit was 14 mass%. The copolymer (A6) had a weight average molecular weight (Mw) of 91,000 and a molecular weight distribution (Mw / Mn) of 3.19. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. Table 1 shows the evaluation results of the obtained sheet-like molded article.

(Example 7)

The inside of the pressure-resistant container equipped with the sufficiently dried stirring device was replaced with nitrogen. 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of ether dimer of dicyclopentyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 1, 0.09 parts by mass of AIBN, And 5.0 parts by mass (1.0% by mass) of triisopropoxide.

After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 캜 while stirring. And polymerization was carried out at 80 DEG C for 2 hours while stirring. To the obtained polymerization solution, 200 parts by mass of a 5 mass% citric acid aqueous solution was added and the mixture was stirred at 80 캜 for 30 minutes. Thereafter, the water layer was taken out, and then washed with ion-exchanged water until it became neutral to remove aluminum triisopropoxide. The solution thus obtained was poured into 8000 parts by mass of methanol to precipitate a solid. The precipitated solid was separated by filtration and sufficiently dried to obtain 30 parts by mass of the copolymer (A7). As a result of ¹ H-NMR measurement of the copolymer (A7), it was found that the content of the structural unit derived from methyl methacrylate was 66% by mass, and the content of the structural unit derived from the ether dimer of dicyclopentanyl-alpha- (hydroxymethyl) The content of the structural unit was 34 mass%. The copolymer (A7) had a weight average molecular weight (Mw) of 185,000 and a molecular weight distribution (Mw / Mn) of 2.99. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded article are shown in Table 2.

(Example 8)

Except that the ether dimer of dicyclopentanyl-? - (hydroxymethyl) acrylate was replaced by the ether dimer of isobornyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 2, To obtain 70 parts by mass of the copolymer (A8). As a result of ¹ H-NMR measurement of the copolymer (A8), it was found that the content of the structural unit derived from methyl methacrylate was 90% by mass, and the content of the structural unit derived from the ether dimer of isobornyl-alpha- (hydroxymethyl) The content of the structural unit was 10% by mass. The copolymer (A8) had a weight average molecular weight (Mw) of 121,000 and a molecular weight distribution (Mw / Mn) of 2.71. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded article are shown in Table 2.

(Example 9)

Except that the ether dimer of dicyclopentanyl-? - (hydroxymethyl) acrylate was replaced by the ether dimer of t-butyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 3, To obtain 67 parts by mass of the copolymer (A9). As a result of ¹ H-NMR measurement of the copolymer (A9), the content of the structural unit derived from methyl methacrylate was 86% by mass, and the content of the structural unit derived from the ether dimer of t-butyl -? - (hydroxymethyl) The content of the structural unit was 14 mass%. The copolymer (A9) had a weight average molecular weight (Mw) of 133,000 and a molecular weight distribution (Mw / Mn) of 2.71. In the same manner as in Example 1, a pellet-like copolymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded article are shown in Table 2.

(Comparative Example 1)

46 parts by weight of the copolymer (B1) was obtained in the same manner as in Example 6 except that aluminum triisopropoxide was not added. As a result of ¹ H-NMR measurement of the copolymer (B1), it was found that the content of the structural unit derived from methyl methacrylate was 86% by mass and the content of the structural unit derived from the ether dimer of dicyclopentanyl -? - (hydroxymethyl) The content of the structural unit was 14 mass%. The copolymer (B1) had a weight average molecular weight (Mw) of 127,000 and a molecular weight distribution (Mw / Mn) of 3.84. Also, a sheet-like molded article having a thickness of 3.2 mm was tried to be made in the same manner as in Example 1, but a part of the sheet was cracked. The test pieces were cut from the sheet-shaped molded article without cracking to measure transparency, water absorbency and bending strength. The results are shown in Table 2.

(Comparative Example 2)

61 parts by mass of the polymer (B2) was obtained in the same manner as in Example 6 except that the ether dimer of dicyclopentanyl-? - (hydroxymethyl) acrylate was not added. The polymer (B2) had a weight average molecular weight (Mw) of 65,000, a molecular weight distribution (Mw / Mn) of 1.88 and a glass transition temperature of 120 占 폚. In the same manner as in Example 1, a pellet polymer was obtained. The pellet-like copolymer was hot-pressed at 230 DEG C to obtain a sheet-like molded article having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded article are shown in Table 2.

(Comparative Example 3)

150 parts by mass of methyl methacrylate, 50 parts by mass of an ether dimer of 4-t-butylcyclohexyl-? - (hydroxymethyl) acrylate obtained in Synthesis Example 4, 50 parts by mass of di-t-butyl peroxide D), 0.94 parts by mass of n-octylmercaptan, 450 parts by mass of water, 1.22 parts by mass of a copolymer of a sodium salt of methacrylic acid and 2-sulfoethyl methacrylate and 1.13 parts by mass of sodium sulfate, A suspension was obtained.

The pressure vessel was sufficiently replaced with nitrogen gas, and then the temperature was raised to 150 캜 while stirring. Followed by suspension polymerization at 150 캜 for 2 hours while stirring. The polymerization solution was gelled and the polymerization was stopped because the stirring torque became large. When the obtained gel was immersed in toluene, it swelled and did not dissolve. The gel was washed with water, followed by washing with methanol and sufficiently dried to obtain a copolymer (B3). Since the copolymer (B3) was not melted at 230 占 폚, a molded article could not be obtained.

As can be seen from the evaluation results of Table 1 and Table 2, in Comparative Example 1 in which Lewis acid is not present, degradation of moldability is confirmed. In Comparative Example 2, which is a polymer comprising only the monomer represented by the formula (1) but not the other monomer, a decrease in the glass transition temperature is confirmed.

On the other hand, in Examples 1 to 7, it was confirmed that a copolymer having a high glass transition temperature and excellent transparency, moldability and bending strength and low water absorption was obtained.

Claims (5)

A process for producing a copolymer, which comprises polymerizing a monomer represented by the formula (1) and another polymerizable monomer in the presence of a Lewis acid.

(In the formula (1)
R ¹ and R ² each independently represent a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms and having a cyclic structure. The method according to claim 1,
Wherein the other polymerizable monomer is a (meth) acrylic acid ester. 3. The method according to claim 1 or 2,
Wherein the Lewis acid is selected from an aluminum compound represented by the formula (2).

(In the formula (2)
R ³ represents an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 3;
R ⁴ represents an alkyl group having 1 to 5 carbon atoms. and b represents an integer of 0 to 3.
R ⁵ represents a phenyl group which may be substituted with 1 to 4 alkyl groups. and c represents an integer of 0 to 3.
Also, the sum of a, b, and c is 3.) 4. The method according to any one of claims 1 to 3,
Wherein the copolymer has a molecular weight distribution measured by gel permeation chromatography of 3.2 or less. 5. The method according to any one of claims 1 to 4,
Polymerizing the monomer represented by the formula (1) and the other polymerizable monomer at a mass ratio of 2: 98 to 60:40.

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