JP6438882B2 - Method for producing copolymer - Google Patents

Description

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

  A methacrylic polymer mainly having a methyl methacrylate unit has high transparency and is excellent in molding processability. Therefore, the molded product is used for applications such as optical materials, lighting materials, signboards, and decorative members. Yes. However, since a normal methacrylic polymer has a low glass transition temperature, the molded product is likely 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 obtained by copolymerizing methyl methacrylate and methacrylic acid alicyclic hydrocarbon ester is known (see Patent Document 1). However, this copolymer has not yet sufficiently increased the glass transition temperature and has low bending strength and the like.

  A copolymer obtained by copolymerizing methyl methacrylate and maleimide is known (see Patent Document 2). However, this copolymer tends to be colored and its transparency tends to decrease.

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

(In Formula (1) and Formula (3),
R ¹ and R ² are each independently 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 having a ring structure. Indicates. )

  However, in the above copolymerization, it is difficult to suppress the side reaction in which the monomer (1) crosslinks between molecules, and the crosslinking increases as the copolymerization ratio of the monomer (1) is increased. The moldability of the resulting copolymer tends to be reduced.

Japanese Patent No. 2513081 JP 61-095011 A JP 2000-178317 A JP 2000-256480 A JP 2012-082317 A

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

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

  The present inventors have intensively studied to achieve the above object. As a result, the present invention including the following aspects has been completed.

[1] The monomer (1) represented by the formula (1) is polymerized with another polymerizable monomer (hereinafter referred to as the monomer (2)) in the presence of a Lewis acid. A process for producing a copolymer.

（式（１）中、
Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜２０の直鎖状炭化水素基、炭素数１〜２０の分岐鎖状炭化水素基または環構造を有する炭素数３〜２０の炭化水素基を示す。）

(In the formula (1),
R ¹ and R ² are each independently 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 having a ring structure. Indicates. )

[2] The production method of the above [1], wherein the monomer (2) is a (meth) acrylic acid ester.

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

（式（２）中、
Ｒ³は炭素数１〜１０のアルキル基を示す。ａは０〜３の整数を示す。
Ｒ⁴は炭素数１〜５のアルキル基を示す。ｂは０〜３の整数を示す。
Ｒ⁵は１〜４個のアルキル基で置換されたフェニル基を示す。ｃは０〜３の整数を示す。
また、aとbとcとの合計は３である。）

(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. b shows the integer of 0-3.
R ⁵ represents a phenyl group substituted with 1 to 4 alkyl groups. c shows the integer of 0-3.
The sum of a, b, and c is 3. )

[4] The production method according to any one of the above [1] to [3], wherein the copolymer has a molecular weight distribution measured by gel permeation chromatography of 3.2 or less.
[5] Any one of the above [1] to [4], comprising polymerizing the monomer (1) and the monomer (2) using a mass ratio of 2:98 to 60:40 The manufacturing method as described in.

  According to the production method of the present invention, a copolymer having a high glass transition temperature and excellent transparency, bending strength and moldability and having a tetrahydropyran ring in the main chain can be obtained. The copolymer obtained in the production method of the present invention has thermoplasticity suitable for moldability while having a high glass transition temperature because the crosslinking reaction of the monomer (1) during polymerization is suppressed, It is assumed that the cyclization reaction of the monomer (1) proceeds preferentially.

2 is a ¹ H-NMR chart of a copolymer obtained in Synthesis Example 1. FIG.

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

The monomer (1) used in the present invention is a compound represented by the formula (1). In formula (1), R ¹ and R ² are each independently a straight-chain hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 1 to 20 carbon atoms, or a carbon number 3 having a ring structure. -20 hydrocarbon groups are shown.
Examples of the straight chain hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-nonyl group, n-decyl group, stearyl group, lauryl group, ethenyl group, propenyl group, butenyl group and the like.
Examples of the branched chain hydrocarbon group having 1 to 20 carbon atoms include isopropyl group, s-butyl group, t-butyl group, 2-ethylhexyl group and the like.
Examples of the hydrocarbon group having 3 to 20 carbon atoms having a ring structure include a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a t-butylcyclohexyl group, an adamantyl group, a tricyclodecanyl group, a cyclopentadienyl group, an isobornyl group, Examples include t-butylphenyl group, 2-benzethyl group, benzyl group, phenyl group and the like.
Of these, a branched hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 3 to 20 carbon atoms having a ring structure is preferable.

  Specific examples of the monomer (1) include dimethyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) 2,2 ′-[oxybis (methylene)] bis-2-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-2-propenoate, di (t-butyl) 2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) 2,2'-[oxybis (methylene)] bis-2-propenoate;

  Dicyclohexyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (4-t-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) ) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (cyclopentadienyl) 2,2 ′-[ Oxybis (methylene)] bis-2-propenoate, diisobornyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tetracyclododecenyl) 2,2 ′-[oxybis (methylene)] bis -2-propenoate, dinorbornyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate;

Dibenzyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (benzethyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl 2,2 ′-[oxybis (methylene) Bis-2-propenoate, dinaphthyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like.
These monomers (1) may be used individually by 1 type, or may be used in combination of 2 or more type.

  Of these, dicyclohexyl 2,2 ′-[oxybis (methylene) is preferred from the viewpoint that the obtained copolymer has a high glass transition temperature and that the resulting copolymer has a small intermolecular cross-linking structure and a narrow molecular weight distribution. Bis-2-propenoate, diisobornyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di-t-butyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (4- t-Butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate is preferred.

As the monomer (2) used in the present invention, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methallylic acid 2-ethylhexyl, isoamyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylic acid Glycidyl, methacrylic acid-3,4-epoxycyclohexyl, tetrahydrofurfuryl methacrylate, allyl methacrylate, 2-ethoxyethyl methacrylate, methoxydiethylene glycol methacrylate Methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxyhexaethylene glycol methacrylate, glycerol methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, isobornyl methacrylate, pentaerythritol methacrylate, Methacrylic acid esters such as dipentaerythritol methacrylate, caprolactone methacrylate modified tetrahydrofurfuryl, caprolactone methacrylate modified dipentaerythritol, caprolactone methacrylate modified 2-hydroxyethyl; methyl acrylate, ethyl acrylate, n-propyl acrylate, Isopropyl acrylate, n-butyl acrylate, a Isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid Phenyl, benzyl acrylate, cyclohexyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexyl acrylate, tetrahydrofurfuryl acrylate, allyl acrylate, 2-ethoxyethyl acrylate, methoxydiethylene glycol acrylate, methoxytetraacrylate Ethylene glycol, methoxypolyethylene glycol acrylate, phenoxydiethylene glycol acrylate, phenoxyhexaethylene glycol acrylate, glycero acrylate , Tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, isobonyl acrylate, pentaerythritol acrylate, dipentaerythritol acrylate, caprolactone acrylate modified tetrahydrofurfuryl, caprolactone acrylate modified dipentaerythritol, caprolactone acrylate modified Acrylic esters such as 2-hydroxyethyl; vinyl aromatic compounds such as styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene; Ethylenically unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid; acrylonitrile, methacrylonitrile; N-phenylmaleimide; -Cyclohexylmaleimide, N-methylmaleimide, Nt-butylmaleimide, maleimide; acrylamide, methacrylamide; ethylene, propylene, norbornene; vinyl acetate, vinyl pivalate, vinyl benzoate; vinyl chloride, vinylidene chloride, allyl chloride, allyl Examples include alcohol.
These monomers (2) may be used alone or in combination of two or more.
Among these, (meth) acrylic acid ester is preferable from the viewpoint of transparency and weather resistance, methyl methacrylate, cyclohexyl methacrylate or methyl acrylate is more preferable, and methyl methacrylate is more preferable.

  The mass ratio of the monomer (1) and the monomer (2) is not particularly limited, but is preferably 2:98 to 60:40, more preferably 15:85 to 50:50, and still more preferably 25:75. ~ 40: 60. When the mass ratio of the monomer (1) is too small, the glass transition temperature of the resulting copolymer is lowered, and when it is too large, the moldability is lowered.

The Lewis acid used in the present invention is not particularly limited as long as it is a substance having an empty orbit that can accept an electron pair.
As an example of a Lewis acid, M (X) _d (M is B, Al, Si, Ti, Zr, Sb, Cd, Fe, Sn, Mg, Cu, In, La, Zn, V, Nb, W, Ag. , Yb, Sc, Hf, Ce, Nd, or Tm, X is 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 trifluoromethanesulfonic acid, and d represents the number of moles of X with respect to M.).

  Specifically, trimethoxyborane, triethoxyborane, trifluoroborane, tribromoborane, boron trifluoride-ether complex, boron trifluoride-acetonitrile complex; aluminum chloride, aluminum bromide, aluminum iodide, trimethoxyaluminum, Chlorodimethoxyaluminum, chlorodiethoxyaluminum, triethylaluminum, chlorodiethylaluminum, dichloro (ethyl) aluminum, triisobutylaluminum, trichlorotriethyldialuminum, ethoxy (diethyl) aluminum; titanium chloride (IV), titanium bromide (IV), Titanium iodide (IV), tetramethoxy titanium (IV), tetraethoxy titanium (IV), tetraisopropoxy titanium (IV), chlorotriisopropoxy titanium (I V); iron (III) chloride, iron (II) chloride, iron ditrifluoromethanesulfonate; tin (II) chloride, tin (IV) chloride, tetramethyltin, tetraethyltin, tetrabutyltin, chloro (tributyl) tin, Dimethyldichlorotin, dimethyldibromotin, dibutyldichlorotin, ditrifluoromethanesulfonate tin; tungsten hexachloride, molybdenum pentachloride, antimony pentachloride, tellurium chloride; silver trifluoroethanesulfonate; copper (II) chloride, ditrifluoro Copper romethanesulfonate; zinc chloride, zinc ditrifluoromethanesulfonate; zirconium chloride (IV), tetramethoxyzirconium (IV), tetraethoxyzirconium (IV); scandium ditrifluoromethanesulfonate, scandium chloride, scandium bromide, tri Methoxyscandium, trie YX, yttrium bromide, trimethoxy yttrium, triethoxy yttrium, yttrium trifluoromethanesulfonate (III); hafnium trifluoromethanesulfonate (IV); neodymium (III) trifluoromethanesulfonate; thulium trifluoromethanesulfonate (III); lanthanum chloride, lanthanum bromide, trimethoxy lanthanum, triethoxy lanthanum, lanthanum trifluoromethanesulfonate (III); cerium chloride, cerium bromide, trimethoxycerium, triethoxycerium, cerium trifluoromethanesulfonate (III ); Samarium (III) chloride, samarium (III) bromide, trimethoxy samarium (III), triethoxy samarium (III), samarium trifluoromethanesulfonate (III); europium chloride, europium bromide, trimethoxy europium, triethoxy europium, europium trifluoromethanesulfonate; gadolinium chloride, gadolinium bromide, trimethoxy gadolinium, triethoxy gadolinium, gadolinium trifluoromethanesulfonate; ytterbium chloride Ytterbium bromide, trimethoxy ytterbium, triethoxy ytterbium, ytterbium trifluoromethanesulfonate (III), methoxy [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, methoxy [2,2 '-Methylenebis (6-t-butylphenoxy)] aluminum, ethyl [2,2'-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, ethyl [2, '-Methylenebis (6-t-butylphenoxy)] aluminum, isobutyl [2,2'-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, isobutyl [2,2'-methylenebis (6-t- Butylphenoxy)] aluminum, n-octyl [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, n-octyl [2,2′-methylenebis (6-t-butylphenoxy)] Aluminum, ethoxy [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, ethoxy [2,2′-methylenebis (6-t-butylphenoxy)] aluminum, isopropoxy [2,2 '-Methylenebis (6-tert-butyl-4-methylphenoxy)] aluminum, isopropo Ci [2,2′-methylenebis (6-t-butylphenoxy)] aluminum, t-butoxy [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, t-butoxy [2, 2'-methylenebis (6-t-butylphenoxy)] aluminum, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

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

In formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. a is an integer of and 0 to 3 indicates the number of R ^3.
In formula (2), R ⁴ represents an alkyl group having 1 to 5 carbon atoms. b is an integer of and 0 to 3 indicates the number of R ^4.
In formula (2), R ⁵ represents a phenyl group which may be substituted with 1 to 3 alkyl groups. c is an integer of and 0 to 3 indicates the number of R ^5. The sum of a, b, and c is 3.

  Specific examples of the aluminum compound represented by the formula (2) include trimethylaluminum, triethylaluminum, tri-n-propylaniminium, tri-n-butylaluminum, triisobutylaluminum, alkylaluminums such as tri-n-decylaluminum, Aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tributoxide, aluminum triisobutoxide, aluminum triphenolate, aluminum phenoxide, ethyl aluminum diethoxy Ethyl aluminum diisopropoxide, isopropyl aluminum diisopropoxide, diethyl aluminum ethoxide, di Tyl aluminum isopropoxide, diisopropyl aluminum isopropoxide, ethyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethyl bis (2,6-di-t-butylphenoxy) aluminum, isobutyl bis (2,6 -Di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-t-butylphenoxy) aluminum, n-octylbis (2,6-dit-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-dit-butylphenoxy) aluminum, methoxybis (2,6-dit-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-dit-butyl-phenoxy) aluminum, ethoxybis (2,6-di-t-butyl-4-methylpheno Xyl) aluminum, ethoxybis (2,6-di-t-butylphenoxy) aluminum, isopropoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isoporoxybis (2,6-di-t-) Butylphenoxy) aluminum, t-butoxybis (2,6-dit-butyl-4-methylphenoxy) aluminum, t-butoxybis (2,6-dit-butylphenoxy) aluminum, tris (2,6-dit- Butyl-4-methylphenoxy) aluminum, tris (2,6-di-t-butylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum, diethyl (2,6-di-t-butyl-4-methylphenoxy) Aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum, diiso Til (2,6-di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, di-n-octyl (2,6-di-t-butyl-4-methylphenoxy) ) Alkyl aluminum alkoxides such as aluminum and di-n-octyl (2,6-di-t-butylphenoxy) aluminum and alkylaluminum phenoxides. Of these, aluminum triethoxide, aluminum triisopropoxide, ethyl bis (2,6-di-t-butylphenoxy) aluminum and / or diethyl (2,6-di-t-butylphenoxy) aluminum are preferred. When the aluminum compound represented by the formula (2) is used, a high yield of a thermoplastic copolymer without intermolecular crosslinking is obtained by polymerization of the monomer (1) and the monomer (2). Can be manufactured.

  The amount of Lewis acid used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and even more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total monomers used. . In addition, the amount of Lewis acid used is preferably 0.001 to 10 mol, more preferably 0. 1 mol per mol of monomer (1). 05 to 2 mol, more preferably 0.1 to 1 mol. When the amount of Lewis acid used is within such a range, the crosslinking reaction of the monomer (1) is suppressed, and the cyclization reaction proceeds predominantly, so that the moldability of the resulting copolymer is improved. It becomes a trend. Although the mechanism of action of Lewis acid is not exactly known, it is presumed that it is as follows. First, the Lewis acid coordinates to the carbonyl oxygen of the monomer (1) to make the monomer (1) bulky. The area around the carbon-carbon double bond of the monomer (1) is sterically crowded, and the crosslinking reaction is difficult to occur. As a result, it is presumed that the cyclization reaction of the monomer (1) proceeds preferentially and crosslinking is reduced.

In the polymerization of the monomer (1) and the monomer (2), a polymerization initiator is usually used. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, dicumyl peroxide, acetyl peroxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide, and lauroyl peroxide. Benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t- Hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t Butyl peroxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-di (t-butylperoxy) Organic peroxides such as cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 3,5,5-trimethylhexanoyl peroxide; 1,1′-azobis (cyclohexanecarbonitrile), 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis ( Azo compounds such as 2-methylpropionate); and persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate. Moreover, you may use the redox type | system | group initiator which combined oxidizing agents, such as a hydroperoxide, a dialkyl peroxide, and a diacyl peroxide, and tertiary amine, a naphthenate, mercaptan, and another reducing agent. These polymerization initiators may be used alone or in combination of two or more. Among these polymerization initiators, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), di-t-butyl peroxide, 1 , 1-di (t-butylperoxy) cyclohexane is preferable from the viewpoint of obtaining a copolymer having a high glass transition temperature at low cost and smoothly.
The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers to be used, reaction conditions, the molecular weight of the target copolymer, and the like. From the viewpoint of obtaining a copolymer with high moldability, the amount of the polymerization initiator used is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0 parts per 100 parts by mass of the total monomer used. .2 parts by mass.

A chain transfer agent can be used as needed for the purpose of adjusting the molecular weight of the copolymer. Such a 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; ethanethiol, butanethiol, n-octyl mercaptan, and n-dodecyl mercaptan. , T-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, methyl mercaptoacetate, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiol Propionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakisthiopro Onate, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, thioglycolic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan, phenethyl mercaptan Such as mercaptans; α-methylstyrene dimer; terpinolene and the like.
Of these, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferred. These chain transfer agents may be used alone or in combination of two or more.
The amount of chain transfer agent used can be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target copolymer, etc., and is not particularly limited, but suppresses gelling and is a weight average. From the viewpoint that the molecular weight can be easily adjusted in the range of several thousand to several tens of thousands, it is preferably 0.01 to 1 part by mass, more preferably 0.2 to 0.8 part with respect to 100 parts by mass of all monomers used. Part by mass, more preferably 0.2 to 0.6 part by mass.

  The radical polymerization in the presence of a Lewis acid can be performed by a solution polymerization method or a bulk polymerization method. In particular, the solution polymerization method is preferable from the viewpoint of producing a copolymer with high moldability.

  When the polymerization reaction is performed by a solution polymerization method, a solution in which the monomer (1) and the monomer (2) are dissolved in an organic solvent is prepared. The concentration of the monomer in the 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 organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and anisole; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, and decalin; acetone, methyl ethyl ketone, and the like Ketones; alcohols such as methanol, ethanol and isopropanol; 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 monomer.

  The temperature during the reaction in the solution polymerization method is preferably −40 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C., and further 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 performed in an inert gas atmosphere such as nitrogen gas.

When the polymerization reaction is performed by a bulk polymerization method, the polymerization conversion rate of the monomer mixture obtained by mixing the monomer (1) and the monomer (2) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, more preferably 10 to 50% by mass.
The temperature during the reaction in the bulk polymerization method is preferably 300 ° C. or lower, more preferably 250 ° C. 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 performed in an inert gas atmosphere such as nitrogen gas.

  The polymerization reaction may be performed in a batch system in a tank reactor, or may be performed in a continuous flow system in a tank reactor or a tube reactor. The reaction system can be appropriately set from the viewpoint of production volume, production cost, and the like.

The copolymer produced by the polymerization reaction can be isolated by a known method.
In the solution polymerization method, the produced copolymer solution is brought into contact with a poor solvent to precipitate the copolymer, and the solvent is volatilized and removed from the produced copolymer solution under reduced pressure to isolate the copolymer. And a method of isolating the copolymer by removing the solvent by blowing water vapor into the resulting copolymer solution.
In the bulk polymerization method, the produced copolymer composition is brought into contact with a poor solvent to precipitate the copolymer, and unreacted monomers are volatilized and removed from the produced copolymer composition under reduced pressure. The method of isolating a polymer etc. are mentioned.

  As a method for removing unreacted monomer and solvent, devolatilization by an equilibrium flash method or an adiabatic flash method is preferable. The devolatilization temperature in the adiabatic flash method is preferably 200 to 300 ° C, more preferably 220 to 270 ° C. Below 200 ° C., it takes time for devolatilization, and devolatilization tends to be insufficient. When devolatilization is insufficient, appearance defects such as silver may occur in the molded product. If it exceeds 300 ° C., the composition tends to be colored due to oxidation, burning, or the like.

  The glass transition temperature of the copolymer obtained by the production method of the present invention is preferably 110 to 180 ° C, more preferably 130 to 165 ° C. When the glass transition temperature is low, the heat resistance and the like tend to decrease. When the glass transition temperature is high, moldability and the like tend 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, still more preferably 50,000 to 20 Ten thousand. When Mw is too small, the impact resistance and toughness of the molded product obtained from the copolymer tend to decrease. When Mw is too large, the fluidity of the copolymer is lowered and the moldability tends to be lowered.
The Mw, number average molecular weight (hereinafter referred to as Mn) and molecular weight distribution of the obtained copolymer can be adjusted by the kind and amount of the polymerization initiator and the chain transfer agent. In addition, in this specification, molecular weight distribution means the value of Mw / Mn.
Moreover, in this specification, Mw and Mn are molecular weights of standard polystyrene conversion 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. More preferably, it is 1.1-3.0. If the molecular weight distribution is small, the moldability of the copolymer tends to decrease. When the molecular weight distribution is large, the impact resistance of the molded product obtained from the copolymer tends to be lowered, and it tends to be brittle.

  The copolymer obtained by the present invention can smoothly perform various molding processes, processing processes, post-modification processes, and the like by taking advantage of these properties, such as molding materials, adhesives, paints, various processing agents, etc. It can be used effectively for a wide range of applications.

  The copolymer obtained by the present invention can be used alone, or polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, It can also be used as a composition comprising another thermoplastic polymer such as a styrene block copolymer.

  When molding the copolymer of the present invention, various additives may be added to the copolymer as necessary. Additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, impact modifiers, organic dyes, light diffusing agents, matte Agents, phosphors, antistatic agents, flame retardants, plasticizers, inorganic fillers, fibers and the like. The compounding amount of such various additives can be appropriately determined within a range not impairing the effects of the present invention. The blending amount of each additive is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the copolymer and other polymers added as necessary. 1 part by mass.

The antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants may be used alone or in combination of two or more. Among these, from the viewpoint of preventing the deterioration of optical properties due to coloring, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
In the case where a phosphorus antioxidant and a hindered phenol antioxidant are used in combination, the ratio is not particularly limited, but is preferably a mass ratio of phosphorus antioxidant / hindered phenol antioxidant, preferably 1/5. ˜2 / 1, more preferably ½ to 1/1.

  As the phosphorus-based antioxidant, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-t -Butylphenyl) phosphite (manufactured by BASF; trade name: IRUGAFOS168).

  As the hindered phenol-based antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX 1010), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076).

The thermal degradation inhibitor can prevent thermal degradation of the copolymer by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
As the thermal degradation inhibitor, 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy-α-methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) Can be mentioned.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
Examples of ultraviolet absorbers include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines, and the like. Benzotriazoles, anilides Is preferred. These may be used individually by 1 type, or may be used in combination of 2 or more type.

As benzotriazoles, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234) and the like.
Examples of the anilides include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan; trade name Sundebore VSU).
Of 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 that is said to have a function of capturing radicals generated mainly by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

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

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

The polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when a copolymer is formed. The polymer processing aid is polymer particles having a particle diameter of 0.05 to 0.5 μm, which can be usually produced by an emulsion polymerization method.
The polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be. Among 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 preferable. The polymer processing aid as a whole preferably has an intrinsic viscosity of 3 to 6 dl / g.

  Examples of the impact modifier include a core-shell type modifier containing acrylic rubber or 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 light, which is considered harmful to the copolymer, into visible light is preferably used.
Examples of the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
Examples of the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightener, and a fluorescent bleach.

  Examples of the antistatic agent include stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate.

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

  Examples of the plasticizer include tricresyl phosphate, trixylenyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, diphenyl monoxylenyl phosphate, Phosphoric acid triester plasticizers such as monophenyldixylenyl phosphate, tributyl phosphate, triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-phthalate Phthalate plasticizers such as ethylhexyl, diisononyl phthalate, octyldecyl phthalate, and butylbenzyl phthalate; fatty acid monobasic acid esters such as butyl oleate and glycerol monooleate Plasticizers; dihydric alcohol ester-based plasticizers; etc. oxyacid ester-based plasticizer can be used.

  As plasticizers, squalane (C30H62, Mw = 422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO VG32, ISO VG68, ISO VG100, ISO VG8 and ISO VG8 as defined in JIS-K-2231) ISO VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like can also be used. Of these, squalane, liquid paraffin, and polyisobutene are preferable.

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

  Moreover, the copolymer of this invention can be mixed with another polymer and can be set as a polymer composition in the range which does not impair the effect of this invention. Examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, and high impact polystyrene. , AS resins, ABS resins, AES resins, AAS resins, ACS resins, MBS resins and other styrene resins; methyl methacrylate polymers, methyl methacrylate-styrene copolymers; polyester resins such as polyethylene terephthalate and polybutylene terephthalate Polyamides such as nylon 6, nylon 66 and polyamide elastomer; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyaceta Rubber, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; acrylic rubber, silicone rubber; styrene thermoplastic elastomer such as SEPS, SEBS, SIS; olefin rubber such as IR, EPR, EPDM, etc. Can be mentioned.

  Such a copolymer of the present invention or a polymer composition containing the copolymer of the present invention is injection-molded (including insert method, two-color method, press method, core back method, sandwich method, etc.), compression molding Various molded products can be obtained by molding by a conventionally known method such as extrusion molding, vacuum molding, blow molding, inflation molding, and calendar molding.

  Examples of the molded article made of the copolymer of the present invention or the molded article made of the polymer composition containing the copolymer of the present invention include, for example, billboard parts such as advertising towers, stand signs, sleeve signs, bamber signs, and roof signs Display parts such as showcases, partition plates, store displays; fluorescent lamp covers, mood lighting covers, lamp shades, lighting parts such as light ceilings, light walls, chandeliers; interior parts such as pendants and mirrors; doors, domes, safety Architectural parts such as window glass, partitions, staircase slats, balcony slats, roofs for leisure buildings; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading boards, automotive side visors, rear visors, head wings, Parts related to transport equipment such as headlight covers; name plates for audio visuals, stereo covers Electronic equipment parts such as TV protective masks and vending machines; Medical equipment parts such as incubators and X-ray parts; Equipment-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, and observation windows; LCD protective plates, Optical components such as light guide plates, light guide films, polarizer protective films, Fresnel lenses, lenticular lenses, front plates of various displays, diffusion plates; traffic-related components such as road signs, guide plates, curved mirrors, sound barriers, etc. Surface materials for interiors, surface materials for mobile phones, film members such as marking films; members for household appliances such as canopy materials and control panels for washing machines, top panels for rice cookers; other greenhouses, large tanks, box tanks, Watch panels, bathtubs, sanitary, desk mats, game parts, toys, masks for face protection when welding, etc.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example. In addition, the present invention includes all aspects that are obtained by arbitrarily combining the above-described items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses.

  The measurement of physical property values in Examples and Comparative Examples was performed by the following method.

(Polymerization conversion of methyl methacrylate)
Equipment: ULTRA SHIELD 400 PLUS manufactured by Bruker
Solvent: 0.05 ml of deuterated chloroform Polymerization solution was mixed with 1 ml of deuterated chloroform, and accumulated 64 times at room temperature to measure ¹ H-NMR. In the obtained ¹ H-NMR spectrum, the TMS peak was defined as 0 ppm. Hydrogen of methoxy group (3.4 to 3.9 ppm, 3H) contained in methyl methacrylate unit in copolymer and hydrogen of olefin of methyl methacrylate monomer remaining in polymerization solution (6.26 ppm, 1H) ) To calculate the polymerization conversion rate of methyl methacrylate.

(Mw and molecular weight distribution)
Mw and molecular weight distribution are calculated | required by the polystyrene conversion value based on the measurement by a gel permeation chromatography (GPC). Here, an HLC-8320 manufactured by Tosoh Corporation was used as the GPC apparatus, and a TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 were connected in series as the column.
Eluent: Tetrahydrofuran Eluent flow rate: 0.6 ml / min Column temperature: 40 ° C
Calibration curve: Created using 10 standard polystyrene points

(Composition analysis of copolymer)
Equipment: ULTRA SHIELD 400 PLUS manufactured by Bruker
Solvent: Deuterated chloroform 10 mg of the copolymer obtained by synthesis was mixed with 1 mL of deuterated chloroform, integrated 64 times at room temperature, and ¹ H-NMR was measured.
The method for analyzing the obtained chart will be described with reference to an example of a copolymer of dicyclopentanyl-α- (hydroxymethyl) acrylate ether dimer and methyl methacrylate.

Formula (I) represents an ether dimer of cyclized dicyclopentanyl-α- (hydroxymethyl) acrylate.
Formula (II) represents an uncyclized dicyclopentanyl-α- (hydroxymethyl) acrylate ether dimer that is not crosslinked.
Formula (III) represents that which is crosslinked with an ether dimer of non-cyclized dicyclopentanyl-α- (hydroxymethyl) acrylate.

FIG. 1 shows an example of a ¹ H-NMR chart.
The TMS peak was set to 0 ppm.
The integrated value of the peak at 3.6 ppm attributed to hydrogen of the methoxy group contained in the methyl methacrylate unit in the copolymer was set to 3.0.
_3. Assigned to the methylene group hydrogen (—CH ₂ —O—CH ₂ —) adjacent to the ether oxygen of the ether dimer of uncyclized dicyclopentanyl-α- (hydroxymethyl) acrylate in the copolymer. The integrated value of the 1 ppm peak was taken as X.

In addition, the peak at 4.5 ppm indicates a methylene group hydrogen (—CH ₂ —) adjacent to the ether oxygen in the tetrahydropyran ring structure of the ether dimer of cyclized dicyclopentanyl-α- (hydroxymethyl) acrylate in the copolymer. O-CH _2- ) and dicyclopentanyl-α- (hydroxymethyl) acrylate ether dimer attributed to methine group hydrogen (—C (═O) OCH—) in the ester group in the dicyclopentanyl group. The In addition, even if it was the state which is cyclized, and it is the state which is not cyclized, it was thought that assignment of this 4.5 ppm peak did not change. Here, the integrated value of the peak at 4.5 ppm was defined as Y.
In addition, the above-described peak assignment can be applied without taking into consideration the influence of crosslinking of the polymer.
When the number of moles of ether dimer units of dicyclopentanyl-α- (hydroxymethyl) acrylate in the copolymer is 1, the number of moles of methyl methacrylate units is A = {(X + Y) / 6}
Is calculated by
The introduction rate W (mass%) of the ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate in the copolymer is:
W = A × 454.66 / (A × 454.66 + 1 × 100.14) × 100
Is calculated by

(Glass-transition temperature)
In accordance with JIS K7121 test method, the DSC curve was measured by differential scanning calorimetry under the condition that the temperature was raised once to 230 ° C., then cooled to room temperature, and then raised from room temperature to 230 ° C. at 10 ° C./min. Was measured. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention. Here, DSC-50 manufactured by Shimadzu Corporation was used as a measuring device.

(transparency)
According to JIS K7361-1, the total light transmittance was measured using HR-100 made by Murakami Color Research Laboratory. Transparency was evaluated using the following indicators.
AA: Total light transmittance of 85% or more BB: Total light transmittance of less than 85%

(Formability)
Using a mold having a long side of 150 mm and a short knitting of 70 mm, the copolymer was added so as to have a thickness of 3.2 mm and hot-pressed at 230 ° C. for 5 minutes. Thereafter, it was naturally cooled at an outside air temperature of 23 ° C. for 1 hour. The case where there was no crack in the molded body taken out from the mold was evaluated as AA, and the case where there was a crack was evaluated as BB. Moreover, it was set as evaluation BB also when it cannot shape | mold.

(Water absorption)
A test piece of 150 mm × 10 mm × 3.2 mm was dried in an environment of 50 ° C. and 5 mmHg for 3 days to obtain an absolutely dry test piece. The mass W0 of the absolutely dry test piece was measured. Thereafter, the absolutely dry test piece was immersed in water at a temperature of 23 ° C. and left for 2 months. After lifting from the water, the mass W1 of the test piece was measured. The saturated water absorption (%) was calculated from the following formula.
Saturated water absorption = {W1-W0} / W0 × 100
Water absorption was evaluated using the following indices.
AA: Saturated water absorption is 2% or less BB: Saturated water absorption is higher than 2%

(Bending strength)
An 80 mm × 13 mm × 3.2 mm test piece was measured according to ASTM D790.
AA: Bending breaking strength is 50 MPa or more BB: Bending breaking strength is less than 50 MPa

(Synthesis Example 1)
In a flask with a capacity of 500 ML, dicyclopentanyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 260.3 g (1.0 mol), paraformaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) 30.3 g (1.0 mol), 1 , 4-diazabicyclo [2,2,2] octane (Wako Pure Chemical Industries, Ltd.) 14.9 g (0.13 mol), p-methoxyphenol (Wako Pure Chemical Industries, Ltd.) 120 mg, and t-butyl alcohol 60 g (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and reacted at 85 ° C. for 24 hours while performing air bubbling, and subsequently reacted at 90 ° C. for 7 hours. Thereafter, the reaction solution obtained was poured into 1 L of methanol and stirred for 30 minutes. Then, this liquid mixture was allowed to stand at 5 ° C. overnight, and an ether dimer (also known as di (tricyclodecanyl) 2,2 ′-[oxybis) of white crystalline dicyclopentanyl-α- (hydroxymethyl) acrylate. 114 g (yield 50%) of (methylene)] bis-2-propenoate; chemical structural formula A) were obtained.

(Synthesis Example 2)
Isobornyl-α was synthesized in the same manner as in Synthesis Example 1, except that 260.3 g (1.0 mol) of dicyclopentanyl acrylate was changed to 208.3 g (1.0 mol) of isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). 57.4 g (yield 25%) of ether dimer of-(hydroxymethyl) acrylate (also known as di (isobornyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate; chemical structural formula B) was obtained. .

(Synthesis Example 3)
In a 500 mL flask, t-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 128.2 g (1.0 mol), paraformaldehyde 30.3 g (1.0 mol), 1,4-diazabicyclo [2,2, 2] 14.9 g (0.13 mol) of octane, 120 mg of p-methoxyphenol, and 60 g of t-butyl alcohol were charged and reacted at 85 ° C. for 24 hours while performing air bubbling, and subsequently reacted at 90 ° C. for 7 hours. 20 mL of methylene chloride was added to the resulting reaction solution. This solution was separated and washed with dilute aqueous hydrochloric acid, and further washed with ion-exchanged water. By distilling the solution under reduced pressure, the ether dimer of t-butyl-α- (hydroxymethyl) acrylate (also known as di (t-butyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate; chemical structure 58 g (38% yield) of formula C) were obtained.

(Synthesis Example 4)
The same procedure 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 (manufactured by Sigma-Aldrich). , 4-t-butylcyclohexyl-α- (hydroxymethyl) acrylate ether dimer (also known as di (t-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate; ) Was obtained (yield 60%).

Example 1
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In the pressure vessel, 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of the ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate obtained in Synthesis Example 1, azobisisobutyronitrile (AIBN) , Tokyo Chemical Industry Co., Ltd.) 0.05 parts by mass, and aluminum triisopropoxide (Wako Pure Chemical Industries, Ltd.) 8.5 parts by mass (1.7% by mass) were charged.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 ° C. with stirring. The polymerization was carried out at 80 ° C. for 2 hours with stirring. Thereafter, 0.05 part by weight of AIBN was added and polymerization was further performed for 2 hours. 200 mass parts of 5 mass% citric acid aqueous solution was added to the obtained polymerization liquid, and it stirred at 80 degreeC for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until 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 filtered off and sufficiently dried to obtain 70 parts by mass of copolymer (A1). When ¹ H-NMR of the copolymer (A1) was measured, the content of structural units derived from methyl methacrylate was 80% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The content of the unit was 20% by 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 supplied to a twin-screw extruder controlled at 230 ° C. to separate and remove volatile components such as residual solvent and unreacted monomers, and then the resin component was extruded into a strand. . The strand was cut with a pelletizer to obtain a pellet-shaped copolymer. The glass transition temperature of the pellet-shaped copolymer was measured. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm. The moldability at this time was confirmed. A test piece was cut out from the obtained sheet-like molded product, and the transparency, water absorption, and bending strength were measured. The results are shown in Table 1.

(Example 2)
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In the pressure vessel, 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate obtained in Synthesis Example 1, 1,1-di (t -Butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa C) 0.05 parts by mass and aluminum triisopropoxide 8.5 parts by mass (1.7% by mass) were charged.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 100 ° C. with stirring. Polymerization was conducted at 100 ° C. for 2 hours with stirring. Thereafter, 0.05 part by mass of perhexa C was added, and polymerization was further performed for 2 hours. 200 mass parts of 5 mass% citric acid aqueous solution was added to the obtained polymerization solution, and it stirred at 80 degreeC for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until neutrality 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 filtered off and sufficiently dried to obtain 50 parts by mass of copolymer (A2). When ¹ H-NMR of the copolymer (A2) was measured, the content of structural units derived from methyl methacrylate was 83% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The content of units 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. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 1.

Example 3
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In this pressure vessel, 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of dicyclopentanyl-α- (hydroxymethyl) acrylate ether dimer obtained in Synthesis Example 1, di-t-butyl peroxide (Nippon Yushi Co., Ltd., Perbutyl D) 0.05 mass part and aluminum triisopropoxide 4.2 mass part (1.7 mass%) were prepared.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 140 ° C. with stirring. Polymerization was carried out at 140 ° C. for 2 hours with stirring. To the obtained polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5% by mass citric acid aqueous solution were added and stirred at 80 ° C. for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until neutrality 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 filtered and sufficiently dried to obtain 50 parts by mass of copolymer (A3). As a result of measuring ¹ H-NMR of the copolymer (A3), the content of structural units derived from methyl methacrylate was 89% by mass, and a structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 11% by weight. The copolymer (A3) had a weight average molecular weight (Mw) of 99,000 and a molecular weight distribution (Mw / Mn) of 2.97. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 1.

(Example 4)
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In the pressure vessel, 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of the ether dimer of dicyclopentanyl-α- (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 isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum was added.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 ° C. with stirring. The polymerization was carried out at 80 ° C. for 2 hours with stirring. To the obtained polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5% by mass citric acid aqueous solution were added and stirred at 80 ° C. for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until neutral, to remove isobutylbis (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 filtered off and sufficiently dried to obtain 30 parts by mass of copolymer (A4). When ¹ H-NMR of the copolymer (A4) was measured, the content of structural units derived from methyl methacrylate was 86% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 14% by weight. The copolymer (A4) had a weight average molecular weight (Mw) of 98,000 and a molecular weight distribution (Mw / Mn) of 1.83. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 1.

(Example 5)
45 parts by mass of copolymer (A5) was obtained in the same manner as in Example 1 except that the amount of aluminum triisopropoxide added was changed to 5.0 parts by mass (1.0% by mass). When ¹ H-NMR of the copolymer (A5) was measured, the content of structural units derived from methyl methacrylate was 82% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 18% by weight. The copolymer (A5) had a weight average molecular weight (Mw) of 107,000 and a molecular weight distribution (Mw / Mn) of 2.06. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 1.

(Example 6)
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In the heat-resistant container, 150 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of the ether dimer of dicyclopentanyl-α- (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 aluminum triisopropoxide was charged.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 ° C. with stirring. The polymerization was carried out at 80 ° C. for 2 hours with stirring. To the obtained polymerization solution, 250 parts by mass of toluene and 200 parts by mass of a 5% by mass citric acid aqueous solution were added and stirred at 80 ° C. for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until 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 48 parts by mass of copolymer (A6). When ¹ H-NMR of the copolymer (A6) was measured, the content of structural units derived from methyl methacrylate was 86% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 14% by weight. The copolymer (A6) had a weight average molecular weight (Mw) of 91,000 and a molecular weight distribution (Mw / Mn) of 3.19. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 1.

(Example 7)
The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. In the pressure vessel, 400 parts by mass of toluene, 77 parts by mass of methyl methacrylate, 23 parts by mass of the ether dimer of dicyclopentanyl-α- (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 aluminum triisopropoxide was charged.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 80 ° C. with stirring. The polymerization was carried out at 80 ° C. for 2 hours with stirring. 200 mass parts of 5 mass% citric acid aqueous solution was added to the obtained polymerization solution, and it stirred at 80 degreeC for 30 minutes. Thereafter, the aqueous layer was extracted, and then washed with ion-exchanged water until neutrality 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 filtered off and sufficiently dried to obtain 30 parts by mass of the copolymer (A7). When ¹ H-NMR of the copolymer (A7) was measured, the content of structural units derived from methyl methacrylate was 66% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 34% by weight. The copolymer (A7) had a weight average molecular weight (Mw) of 185,000 and a molecular weight distribution (Mw / Mn) of 2.99. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 2.

(Example 8)
In the same manner as in Example 3, except that the ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate was changed to the ether dimer of isobornyl-α- (hydroxymethyl) acrylate obtained in Synthesis Example 2. , 70 parts by mass of copolymer (A8) was obtained. When ¹ H-NMR of the copolymer (A8) was measured, the content of structural units derived from methyl methacrylate was 90% by mass, and the content of structural units derived from the ether dimer of isobornyl-α- (hydroxymethyl) acrylate. 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. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 2.

Example 9
The same procedure as in Example 3 except that the ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate was changed to the ether dimer of t-butyl-α- (hydroxymethyl) acrylate obtained in Synthesis Example 3. Thus, 67 parts by mass of the copolymer (A9) was obtained. When ¹ H-NMR of the copolymer (A9) was measured, the content of the structural unit derived from methyl methacrylate was 86% by mass, and the structural unit derived from the ether dimer of t-butyl-α- (hydroxymethyl) acrylate. The content of was 14% by mass. The copolymer (A9) had a weight average molecular weight (Mw) of 133,000 and a molecular weight distribution (Mw / Mn) of 2.71. Moreover, the pellet-shaped copolymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 2.

(Comparative Example 1)
46 parts by mass of copolymer (B1) were obtained in the same manner as in Example 6 except that aluminum triisopropoxide was not added. As a result of measuring ¹ H-NMR of the copolymer (B1), the content of structural units derived from methyl methacrylate was 86% by mass, and the structure derived from an ether dimer of dicyclopentanyl-α- (hydroxymethyl) acrylate. The unit content was 14% by weight. The copolymer (B1) had a weight average molecular weight (Mw) of 127,000 and a molecular weight distribution (Mw / Mn) of 3.84. Further, an attempt was made to produce a sheet-like molded product having a thickness of 3.2 mm by the same method as in Example 1, but a part of the sheet was broken. A test piece was cut out from the sheet-like molded product of the unbroken portion, and the transparency, water absorption, and bending strength were measured. The results are shown in Table 2.

(Comparative Example 2)
61 parts by mass of the polymer (B2) were obtained in the same manner as in Example 6 except that the ether dimer of dicyclopentanyl-α- (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 ° C. Moreover, the pellet-like polymer was obtained by the same method as Example 1. The pellet-shaped copolymer was hot press molded at 230 ° C. to obtain a sheet-shaped molded product having a thickness of 3.2 mm without cracking. The evaluation results of the obtained sheet-like molded product are shown in Table 2.

(Comparative Example 3)
150 parts by mass of methyl methacrylate, 50 parts by mass of ether dimer of 4-t-butylcyclohexyl-α- (hydroxymethyl) acrylate obtained in Synthesis Example 4, di-t-butyl peroxide (Nippon Yushi Fatty Perbutyl D) 0 0.1 part by mass, 0.94 part by mass of n-octyl mercaptan, 450 parts by mass of water, 1.22 parts by mass of a copolymer of sodium salt of methacrylic acid and 2-sulfoethyl methacrylate, and 1.13 parts by mass of sodium sulfate A pressure vessel was charged to obtain a suspension.
After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 150 ° C. with stirring. Suspension polymerization was carried out at 150 ° C. for 2 hours with stirring. Since the polymerization solution gelled and the stirring torque increased, the polymerization was stopped. When the obtained gel was immersed in toluene, it swelled and did not dissolve. The gel was washed with water, then with methanol, and sufficiently dried to obtain a copolymer (B3). Since the copolymer (B3) did not melt at 230 ° C., a molded product could not be obtained.

  As mentioned above, when the evaluation result of Table 1 and Table 2 is seen, the fall of a moldability is confirmed in the comparative example 1 in which a Lewis acid does not exist. Moreover, the fall of a glass transition temperature is confirmed in the comparative example 2 which is a polymer which does not contain another monomer and consists only of the monomer represented by Formula (1).

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

Claims (4)

In the presence of 0.1 to 1 mol of Lewis acid, the monomer represented by the formula (1) and other polymerizable monomer are added to 1 mol of the monomer represented by the formula (1). in, to suppress crosslinking, see containing a polymerizing and cyclization,
The Lewis acid is at least one selected from aluminum compounds represented by the formula (2);
The other polymerizable monomer is a (meth) acrylic acid ester ,
A method for producing a copolymer having a tetrahydropyran ring in the main chain.

(In the formula (1),
R ¹ and R ² are each independently 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 having a ring structure. Indicates. )

(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. b shows the integer of 0-3.
R ⁵ represents a phenyl group which may be substituted with 1 to 4 alkyl groups. c shows the integer of 0-3.
The sum of a, b, and c is 3. ) The production method according to claim 1, wherein the other polymerizable monomer is methyl methacrylate . The manufacturing method of Claim 1 or 2 whose molecular weight distribution measured by the gel permeation chromatography of the said copolymer is 3.2 or less. The polymerization according to any one of claims 1 to 3 , comprising polymerizing the monomer represented by the formula (1) and the other polymerizable monomer at a mass ratio of 2:98 to 60:40. 2. The production method according to item 1.

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