JP2018159010A - Macromonomer copolymer and molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the thermostable decomposition property of an acrylic macromonomer copolymer. A macromonomer copolymer (Y) composed of a unit derived from a macromonomer (A) represented by the formula (1) and a unit derived from a comonomer (B) copolymerizable with the macromonomer (A). The macromonomer copolymer (Y) has a 5% weight loss temperature of 340 ° C. or higher as measured under the condition of a temperature rise rate of 10 ° C./min under a nitrogen stream. (R and R1 to Rn are H, alkyl group, cycloalkyl group, aryl group or heterocyclic group, respectively; X1 to Xn are independent, H or methyl group; Z is a terminal group; n is 2 to 10, Natural number of 000) [Selection diagram] None

Description

The present invention relates to a macromonomer copolymer and a molding material containing the macromonomer copolymer.
In particular, the present invention relates to a copolymer of an acrylic macromonomer and a comonomer produced by catalytic chain transfer polymerization (abbreviated as CCTP).

  Many of the monomers having reactively active unsaturated bonds can be polymerized by reacting under appropriate conditions using a catalyst that causes chain transfer. When a polymer is used industrially, a homopolymer using one kind of monomer cannot meet various requirements of materials, and therefore, a method of mixing different kinds of polymers is used. However, by simply mixing different types of polymers, the polymers are not compatible with each other and phase separation with a relatively large size domain (called macro phase separation) is performed. In many cases, it is difficult to express the characteristics possessed together.

  As a method for solving the above problem, a method using a block copolymer in which two or more polymer segments are chemically bonded is known. As described above, a mixture of dissimilar polymers has phase separation due to low compatibility between the polymers.However, since the polymer segments of the block polymer are linked to each other by chemical bonds, the phase separation structure has a nanometer size. (Referred to as microphase separation). Therefore, the characteristics of each polymer segment can be expressed together. Among block copolymers, (meth) acrylic block copolymers have been tried to be applied in various applications that require transparency and weather resistance.

For example, an acrylic resin molded article is excellent in transparency, but has a problem of being hard and brittle.
An acrylic resin molded article using a (meth) acryl block copolymer in which two or more polymer segments are chemically bonded is known. Since the (meth) acryl block copolymers are connected to each other by chemical bonds, the phase separation structure is a micro phase separation structure. Therefore, by exhibiting the characteristics of each polymer segment, it can be expected that an acrylic resin molded article having excellent transparency and excellent impact resistance and flexibility can be obtained.

As a method for producing such a (meth) acryl block copolymer, for example, an atom transfer radical polymerization (ATRP) method described in Patent Documents 1 and 2 is known. However, since the ATRP method uses a metal catalyst, the production process of the polymer becomes complicated, and there are problems of cost increase and productivity reduction. In addition, as a method not using a metal catalyst, for example, reversible addition-fragmentation chain transfer (RAFT) polymerization methods described in Patent Documents 3 and 4 have been proposed. However, there have been problems such as residual sulfur atoms lowering the weather resistance and coloring of the obtained polymer moldings.
In order to solve these problems, acrylic macromonomers are produced in advance using a very small amount of a cobalt complex called catalytic chain transfer polymerization, which has an extremely high chain transfer constant, and the acrylic macromonomer and other acrylic monomers are prepared. A method for producing a (meth) acrylic block / graft copolymer by copolymerization of styrene is known (for example, see Patent Document 5).
A macromonomer is a polymer having a functional group capable of undergoing a polymerization reaction, and is also called a macromer.

  Furthermore, as a method for obtaining a (meth) acryl block / graft copolymer which is a copolymer of an acrylic macromonomer and an acrylic monomer, methods by suspension polymerization described in Patent Documents 6 and 7 are known. Patent Document 6 mentions a method in which two or more kinds having different solubility parameters are used in combination as a comonomer to be combined with an acrylic macromonomer. In Patent Document 7, a non-metal chain transfer agent is used to prevent crosslinking of the copolymer.

Japanese Patent No. 3040172 Japanese Patent Laid-Open No. 8-41117 Japanese Patent No. 2553134 Special Table 2000-515181 Special Table 2000-514845 International Publication No. 2014/098141 International Publication No. 2015/056668

Since the refractive index of the refractive index of the segment derived from the macromonomer made of polymethylmethacrylate is different from that of the segment made of the comonomer polymer, there is a disadvantage that the transparency is poor. In particular, when a macromonomer copolymer is added to a polymer composed of polymethyl methacrylate, the problem that transparency is lowered is remarkable.
In addition, the macromonomer and comonomer copolymer produced by CCTP does not always have sufficient thermal decomposition resistance, which may cause molding failure when used in melt molding.

  An object of the present invention is to improve transparency when a copolymer of a macromonomer and a comonomer made of polymethyl methacrylate is added to polymethyl methacrylate, and to improve the thermal decomposition resistance of an acrylic macromonomer copolymer. And

The present invention has the following embodiments.
[1] Macromonomer copolymer (Y) composed of a unit derived from a macromonomer (A) represented by the following general formula (1) and a unit derived from a comonomer (B) copolymerizable with the macromonomer (A) A 5% weight loss temperature of the macromonomer copolymer (Y) measured at 10 ° C./min under a nitrogen stream at 340 ° C. or higher. Polymer (Y).

(In the formula, R and R ^{1 to} R ⁿ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group or heterocyclic group. X _{1 to} X _n are each independently a hydrogen atom or methyl. Z is a terminal group, and n is a natural number of 2 to 10,000.)

[2] Macromonomer copolymer (Y) composed of a unit derived from the macromonomer (A) represented by the general formula (1) and a unit derived from the comonomer (B) copolymerizable with the macromonomer (A) The macromonomer copolymer (Y), wherein the comonomer (B) includes an alkyl acrylate (B1) and an aromatic acrylate (B2).
[3] The alkyl acrylate (B1) is methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, The macromonomer copolymer (Y) according to [2], which is at least one selected from the group consisting of tridecyl acrylate and i-stearyl acrylate.
[4] The macromonomer copolymer (Y) according to [2] or [3], wherein the aromatic acrylate (B2) is at least one selected from the group consisting of benzyl acrylate, phenoxyethyl acrylate, and phenyl acrylate. .
[5] The absolute value of the difference between the refractive index of the polymer composed only of the comonomer (B) and the refractive index of the macromonomer (A) is 0.05 or less, [1] to The macromonomer copolymer (Y) according to any one of [4].
[6] A molding material containing the macromonomer copolymer (Y) of any one of [1] to [5] and polymethyl methacrylate (Z), wherein the polymethyl methacrylate (Z) is a methyl methacrylate unit. 80% by mass or more, and the macromonomer (A) contains 80% by mass or more of methyl methacrylate units.

  The macromonomer copolymer (Y) of the present invention has a high 5% weight loss temperature and excellent thermal decomposition resistance. Moreover, transparency when mixed with polymethyl methacrylate is good. Therefore, in addition to being suitable for imparting impact resistance and flexibility to polymethylmethacrylate, it can be used as a modifier for resins with high molding and use temperatures that could not be applied with conventional macromonomer copolymers. it can.

Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated in detail, this invention is not limited to the following description, In the range of the summary Various modifications can be made.
Hereinafter, the monomer component before polymerization is referred to as “˜monomer”, and “monomer” may be omitted. The monomer unit constituting the polymer is referred to as “˜derived unit” or “˜unit”. Moreover, (meth) acrylate shows a methacrylate or an acrylate.
Moreover, polymethylmethacrylate may be abbreviated as PMMA. PMMA is a homopolymer of a methyl methacrylate monomer or a copolymer containing units other than methyl methacrylate units.

  The macromonomer copolymer (Y) according to the present invention is a macromonomer (A) represented by the following general formula (1) and another polymerizable monomer copolymerizable with the macromonomer (A). It is obtained by copolymerizing the comonomer (B).

(In the formula, R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
X _{1 to} X _n are each independently a hydrogen atom or a methyl group.
Z is a terminal group.
n is a natural number of 2 to 10,000. )

[Macromonomer (A)]
The macromonomer (A) has a group having an unsaturated double bond capable of radical polymerization at one end of the poly (meth) acrylate segment. Here, the macromonomer is a polymer having a polymerizable functional group, and is also called a macromer.

[R · R ^{1 to} R ⁿ ]
In the general formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group or heterocyclic group can have a substituent.

The alkyl group of R and ^R 1 to R ^n, for example, branched or straight chain alkyl group having 1 to 20 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group and i-propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group. Among these, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl are preferred because they are easily available. A methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group are more preferable, and a methyl group is particularly preferable.

The cycloalkyl group of R and ^R 1 to R ^n, for example, a cycloalkyl group having 3 to 20 carbon atoms. Specific examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, t-butylcyclohexyl group, isobornyl group, adamantyl group, and the like. From the viewpoint of availability, a cyclopropyl group, a cyclobutyl group, and an adamantyl group are preferable.

The aryl group of R and ^R 1 to R ^n, for example, an aryl group having 6 to 18 carbon atoms. Specific examples include a phenyl group, a benzyl group, a naphthyl group, and the like.

Examples of the heterocyclic group for R and R ^{1 to} R ⁿ include a heterocyclic group having 5 to 18 carbon atoms. Examples of the hetero atom contained in the heterocyclic ring include an oxygen atom, a nitrogen atom, and a sulfur atom. Specific examples of the heterocyclic group include γ-lactone group, ε-caprolactone group, morpholine group, and the like.

As the substituent for R or R ^{1 to} R ⁿ , each independently represents an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (—COOR ′), a carbamoyl group (—CONR′R ″), or a cyano group. , A hydroxy group, an amino group, an amide group (—NR′R ″), a halogen atom, an allyl group, an epoxy group, an alkoxy group (—OR ′), and a group exhibiting hydrophilicity or ionicity. Group or atom. R ′ and R ″ are each independently the same group as R (except for a heterocyclic group).

Examples of the alkoxycarbonyl group as a substituent for R or R ^{1 to} R ⁿ include a methoxycarbonyl group.
Examples of the carbamoyl group as a substituent for R or R ^{1 to} R ⁿ include an N-methylcarbamoyl group and an N, N-dimethylcarbamoyl group.
Examples of the amide group as a substituent for R or R ^{1 to} R ⁿ include a dimethylamide group.
Examples of the halogen atom as the substituent of R or R ¹ to R ^n, for example, a fluorine atom, a chlorine atom, a bromine atom, and iodine atom.
The alkoxy group as the substituent for R or ^R 1 to R ^n, for example, an alkoxy group having 1 to 12 carbon atoms. Specific examples include a methoxy group.
Examples of the group exhibiting hydrophilicity or ionicity as a substituent of R or R ^{1 to} R ⁿ include, for example, poly (alkylene oxides) such as alkali salts of carboxy groups or alkali salts of sulfoxyl groups, polyethylene oxide groups, and polypropylene oxide groups. ) Groups and cationic substituents such as quaternary ammonium bases.

R and R ^{1 to} R ⁿ are preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group.
As the alkyl group, a methyl group, an ethyl group, an n-propyl group or an i-propyl group is preferable, and a methyl group is more preferable from the viewpoint of availability.

_[X 1 ~X n]
In the general formula (1), X _{1 to} X _n are each a hydrogen atom or a methyl group, and a methyl group is preferable. Furthermore, from the viewpoint of easy synthesis of the macromonomer (A), it is preferable that half or more of X _{1 to} X _n are methyl groups.

[Z]
In the general formula (1), Z is a terminal group of the macromonomer (A). Examples of the terminal group of the macromonomer (A) include a group derived from a hydrogen atom and a radical polymerization initiator, similarly to the terminal group of a polymer obtained by known radical polymerization.

  The number average molecular weight Mn of the macromonomer (A) is preferably 500 or more and 100,000 or less. The lower limit value of the number average molecular weight Mn of the macromonomer (A) is more preferably 1,000 or more, and further preferably 1,500 or more. Further, the upper limit value of the number average molecular weight Mn of the macromonomer (A) is more preferably 50,000 or less, and further preferably 20,000 or less. If the number average molecular weight Mn is not less than the lower limit value, the compatibility and physical properties derived from the macromonomer (A) can be imparted to the macromonomer copolymer (Y). When the number average molecular weight Mn is not more than the upper limit value, the macromonomer (A) and the comonomer (B) are easily copolymerized.

  The number average molecular weight Mn of the macromonomer (A) means a value calculated from a calibration curve of polymethyl methacrylate using gel permeation chromatography (GPC).

[Raw material monomer of macromonomer (A)]
As a monomer (raw material monomer) for obtaining the macromonomer (A), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate , Phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyl-containing (meth) acrylates such as glycerol (meth) acrylate; (meth) acrylic acid, 2 -(Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- ( (Meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, B Carboxy group-containing vinyl monomers such as conic acid, monomethyl maleate, and itaconic acid monomethyl; acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α- Epoxy group-containing vinyl monomers such as ethyl acrylate and 3,4-epoxybutyl (meth) acrylate; amino group-containing (meth) acrylate vinyl such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, Maleic acid amide, maleic Vinyl monomers containing an amide group such as styrene; vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate; divinylbenzene, ethylene Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri And polyfunctional vinyl monomers such as propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, N, N′-methylenebis (meth) acrylamide, and the like. One or more of these can be appropriately selected and used.

Among these, methacrylate (methacrylic acid ester) is preferable from the viewpoint of easy availability of the monomer.
As the methacrylate, methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate are preferable, methyl methacrylate, n-butyl methacrylate. And 2-ethylhexyl methacrylate is more preferred.

Moreover, the monomer for obtaining the macromonomer (A) contains the above-mentioned methacrylate or acrylate (atacrylic acid ester) from the viewpoint of heat resistance of the macromonomer copolymer (Y) and a molded article containing the macromonomer copolymer (Y). It is preferable.
Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and t-butyl acrylate. One or more of these can be appropriately selected and used. Among these, methyl acrylate is preferable in terms of availability.

The content of methacrylate in the total amount of monomers for obtaining the macromonomer (A) is 80% by mass from the viewpoint of heat resistance of the macromonomer copolymer (Y) as a product and a molded article containing the same. The content is preferably 100% by mass or less. The content of methacrylate is more preferably 82% by mass or more and 99% by mass or less, and still more preferably 84% by mass or more and 98% by mass or less.
Of all the units of the macromonomer (A), the methacrylate unit is preferably 80 to 100% by mass, more preferably 82 to 99% by mass, and still more preferably 84 to 98% by mass.

The content of acrylate in the total monomer for obtaining the macromonomer (A) is preferably 0% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 18% by mass or less, and 2% by mass or more and 16% by mass. % Or less is more preferable.
Among all the units of the macromonomer (A), the acrylate unit is preferably 0 to 20% by mass, more preferably 1 to 18% by mass, and further preferably 2 to 16% by mass.

[Method for producing macromonomer (A)]
The macromonomer (A) can be produced by a known method. As a method for producing a macromonomer, for example, a method using a cobalt chain transfer agent (US Pat. No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent ( WO 88/04304), a method of chemically bonding a polymerizable group (Japanese Patent Laid-Open No. 60-133007, US Pat. No. 5,147,952) and a method by thermal decomposition (Japanese Patent Laid-Open No. 11-240854). ) And the like.
Among these, as a method for producing the macromonomer (A), a method using a cobalt chain transfer agent is preferable in that a catalyst having a small number of production steps and a high chain transfer constant is used.

  Examples of the method for producing the macromonomer (A) using a cobalt chain transfer agent include an aqueous dispersion polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, the aqueous dispersion polymerization method is preferable from the viewpoint of simplifying the recovery process of the macromonomer (A).

  As the cobalt chain transfer agent used in the present invention, a cobalt chain transfer agent represented by the formula (2) can be used. For example, Japanese Patent No. 3585530, US Pat. Nos. 4,526,945 and 4,694,054 No. 4,886,861, No. 5,324,879, WO 95/17435, JP 9-510499, JP 2012-158696, etc. Can do.

[Wherein, R _{1 to} R ₄ each independently represents an alkyl group, a cycloalkyl group, and an aryl group; X represents each independently an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryl group; An oxy group, an alkyl group and an aryl group; ]

Specific examples of the cobalt chain transfer agent include bis (borondifluorodimethyldioxyiminocyclohexane) cobalt (II), bis (borondifluorodimethylglyoxymate) cobalt (II), and bis (borondifluorodiphenylglyoxymate). Cobalt (II), cobalt (II) complex of bicinalimino hydroxyimino compound, cobalt (II) complex of tetraazatetraalkylcyclotetradecatetraene, N, N′-bis (salicylidene) ethylenediaminocobalt (II) complex And cobalt (II) complexes of dialkyldiazadioxodialkyldodecadiene, cobalt (II) porphyrin complexes, and the like. Among these, bis (borondifluorodiphenylglyoxymate) cobalt (II) (R _{1 to} R ₄ : phenyl group, X: F atom) which is stably present in an aqueous medium and has a high chain transfer effect is preferable. One or more of these can be appropriately selected and used.

  The amount of the cobalt chain transfer agent used is preferably 20 ppm to 350 ppm with respect to 100 parts of the total amount of monomers for obtaining the macromonomer (A). If the amount of cobalt chain transfer agent used is less than 20 ppm, the molecular weight tends to be insufficiently reduced, and if it exceeds 350 ppm, the resulting macromonomer (A) tends to be colored.

[Copolymerization reaction mechanism of macromonomer (A) and comonomer (B)]
The copolymerization reaction mechanism between the macromonomer (A) and the comonomer (B) is described in detail in a report by Yamada et al. (Prog. Polym. Sci. 31 (2006) p835-877). Specifically, the terminal double bond group of the macromonomer (A) can be copolymerized by forming a branched structure in the copolymerization reaction with acrylate. However, it is difficult to form a branched structure by the reaction between the terminal double bond group of the macromonomer (A) and methacrylate, and the cleavage is mainly resumed to generate a radical at the terminal double bond group and the methacrylate growth terminal. When styrene is used as the comonomer (B), a branched structure can be formed, but the progress of the reaction is extremely slow, which is not industrially preferable. From this point, the comonomer (B) preferably contains acrylate as a main component.

[Comonomer (B)]
The comonomer (B) is not particularly limited as long as it can be copolymerized with the macromonomer (A), and various polymerizable monomers can be used as necessary. However, in view of the copolymerization reaction mechanism between the macromonomer (A) and the comonomer (B) described above, it is preferable to use acrylate as a main component. When making the polymer segment which consists of a comonomer (B) unit flexible, it is preferable that a comonomer (B) contains alkylacrylate (B1). Moreover, in order to achieve the improvement of the thermal decomposition resistance and the refractive index adjustment of the polymer segment comprising the comonomer (B) unit at the same time, the comonomer (B) preferably contains an aromatic acrylate (B2). By improving the heat decomposability of the polymer segment comprising the comonomer (B) unit, the heat decomposability of the macromonomer copolymer (Y) can be improved. In addition, by adjusting the refractive index of the polymer segment composed of the comonomer (B) unit, the transparency of the macromonomer copolymer (Y) can be improved, or between the other resin and the macromonomer copolymer (Y). The transparency of the mixture can be improved. Further, the comonomer (B) may contain another monomer (B3). The other monomer (B3) is used for imparting various functions to the macromonomer copolymer (Y).

[Alkyl acrylate (B1)]
Alkyl acrylate (B1) refers to an acrylate whose ester group is an alkyl group. Alkyl groups include linear alkyl groups, branched alkyl groups, cyclic alkyl groups, and the like. Of these, a linear alkyl group or a branched alkyl group is preferably used in that the polymer segment composed of the comonomer (B) unit is excellent in flexibility.

  Examples of the alkyl acrylate (B1) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, i-nonyl acrylate, n-decyl acrylate, i-decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl Acrylate, heptadecyl acrylate, n-stearyl acrylate, i-stearyl acrylate, behenyl Relate, cyclohexyl acrylate, t- butyl cyclohexyl acrylate, isobornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and the like. One or more of these can be appropriately selected and used. Among these, in terms of availability, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-octyl acrylate, i -Octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, i-nonyl acrylate, n-decyl acrylate, i-decyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, n-stearyl acrylate, i-stearyl acrylate are preferred , Methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate Relate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, i- stearyl acrylate, but more preferred.

  The proportion of the alkyl acrylate (B1) contained in the comonomer (B) is, for example, preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, with respect to 100 parts by weight of the comonomer (B). Is more preferable. When flexibility is not required for the polymer segment composed of the comonomer (B) unit, the alkyl acrylate (B1) may not be included. The proportion of the alkyl acrylate (B1) is appropriately determined depending on conditions such as flexibility, impact resistance, and toughness required for the macromonomer copolymer (Y) or a mixture of another resin and the macromonomer copolymer (Y). Adjusted.

[Aromatic acrylate (B2)]
By using the aromatic acrylate (B2), it is possible to achieve the improvement of the thermal decomposition resistance and the refractive index adjustment at the same time. Since the refractive index of the polymer consisting of the aromatic acrylate (B2) unit is higher than the refractive index of the polymer consisting of the alkyl acrylate (B1) unit, it is suitably used for adjusting the refractive index.
Furthermore, the thermal decomposition resistance of the macromonomer copolymer (Y) can be improved by copolymerizing the aromatic acrylate (B2). For example, the 5% weight reduction temperature of the macromonomer copolymer (Y) can achieve 340 ° C. or higher. The 5% weight loss temperature is more preferably 345 ° C. or higher, and further preferably 350 ° C. or higher.

  Examples of the aromatic acrylate (B2) include benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, phenoxypolyethylene glycol acrylate, biphenyl acrylate, nonylphenyl acrylate, nonylphenoxyethyl acrylate, nonylphenoxypolyethylene glycol acrylate, cumylphenol acrylate, Examples include milphenoxyethyl acrylate, cumylphenoxypolyethylene glycol acrylate, o-phenylphenol acrylate, ethoxylated o-phenylphenol acrylate, tribromophenyl acrylate, EO-modified tribromophenyl acrylate, and the like. One or more of these can be appropriately selected and used. Among these, benzyl acrylate and phenoxyethyl acrylate are preferable in terms of availability.

  The ratio of the aromatic acrylate (B2) contained in the comonomer (B) is appropriately adjusted depending on the refractive index of the polymer composed of the comonomer (B) unit and the high thermal decomposition resistance required for the macromonomer copolymer (Y). Is possible. The ratio of the aromatic acrylate (B2) contained in the comonomer (B) is, for example, preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, with respect to 100 parts by mass of the comonomer (B). Part is more preferred.

  When the comonomer (B) contains both the alkyl acrylate (B1) and the aromatic acrylate (B2), the mass ratio of the content expressed by the alkyl acrylate (B1) / aromatic acrylate (B2) is 60/40. -90/10 are preferable and 65 / 35-80 / 20 are more preferable.

[Other monomers (B3)]
The other monomer (B3) is used for imparting various functions to the macromonomer copolymer (Y). The other monomer (B3) can be selected without particular limitation as long as it is a polymerizable monomer copolymerizable with any of the macromonomer (A), alkyl acrylate (B1), and aromatic acrylate (B2). It is.
Examples of other monomers (B3) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl. Methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, phenoxyethyl methacrylate and other methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl Methacrylate, 4-hydroxybutyl methacrylate, glycerol methacrylate Hydroxyl group-containing methacrylates such as methacrylate; methacrylic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxypropylhexahydrophthalic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyl Carboxy group-containing methacrylates such as oxyethyl maleic acid, 2-methacryloyloxypropyl maleic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxypropyl succinic acid; glycidyl methacrylate, 3,4-epoxybutyl methacrylate, etc. Epoxy group-containing methacrylates; amino group-containing methacrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; ethylene glycol dimethacrylate 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. Polyfunctional methacrylate; carboxy group-containing vinyl monomers such as crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid; vinyl groups containing acid anhydride groups such as maleic anhydride and itaconic anhydride Monomer; (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylic Vinyl monomers containing amide groups such as rilamide, diacetone acrylamide, maleic acid amide, maleimide; styrene, α-methylstyrene, vinyl toluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate, etc. And vinyl monomers; multifunctional vinyl monomers such as divinylbenzene and N, N′-methylenebis (meth) acrylamide; One or more of these can be appropriately selected and used.

[Radical polymerization initiator]
When the copolymerization reaction of the macromonomer (A) and the comonomer (B) is performed in the presence of a radical polymerization initiator, an organic peroxide or an azo compound can be used as the radical polymerization initiator. Specific examples of the organic peroxide include, for example, 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide Examples thereof include oxide and di-t-butyl peroxide.
Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2,4-dimethyl). -4-methoxyvaleronitrile) and the like. Among these, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4) -Methoxyvaleronitrile) is preferred. These radical polymerization initiators can be used alone or in combination of two or more.
The radical polymerization initiator is preferably used within a range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the macromonomer (A) and the comonomer (B).
There is no restriction | limiting in particular about superposition | polymerization temperature, For example, it is -100-250 degreeC, Preferably it is the range of 0-200 degreeC.

[Macromonomer copolymer (Y)]
The macromonomer copolymer (Y) includes a block / graft copolymer (Y1) containing both a unit derived from the macromonomer (A) and a unit derived from the comonomer (B), and may include other components. For example, there is a possibility that the polymer (Y2) consisting only of the comonomer (B) unit and the unreacted macromonomer (A) are included. The content of the polymer (Y2) and the unreacted macromonomer (A) is preferably small.
“Block / graft copolymer” means one or both of a block copolymer and a graft copolymer.

The unreacted macromonomer (A) may hinder the control of the microphase separation structure when the macromonomer copolymer (Y) is used as an additive for various resins. Furthermore, since the macromonomer (A) has a property of being easily decomposed from the terminal double bond site, it may cause a decrease in heat resistance. Therefore, it is preferable that the amount of unreacted macromonomer (A) is small.
Specifically, the unreacted macromonomer (A) is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less with respect to 100% by mass of the macromonomer copolymer (Y). .
Further, the polymer (Y2) consisting only of the comonomer (B) unit is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 5% or less with respect to 100% by mass of the macromonomer copolymer (Y). Further preferred.

  The mass average molecular weight Mw of the macromonomer copolymer (Y) is preferably from 30,000 to 10,000,000, more preferably from 50,000 to 8,000,000, and from 100,000 to 6,000, 000 or less is more preferable. If the weight average molecular weight Mw is 30,000 or more, the mechanical strength and heat decomposability of the resin molded article are good, and if it is 10,000,000 or less, it is soluble in the matrix resin when used as an additive or additive. Property is improved.

In the macromonomer copolymer (Y), the absolute value of the difference between the refractive index of the polymer (Y2) consisting only of the comonomer (B) and the refractive index of the macromonomer (A) is 0.05 or less. Preferably, 0.02 or less is more preferable.
When the absolute value of the difference in refractive index is 0.05 or less, the macromonomer copolymer (Y) is excellent in transparency. Further, when the macromonomer copolymer (Y) is mixed with another resin, the transparency of the other resin is not easily lowered.
For example, when the macromonomer copolymer (Y) is mixed with polymethyl methacrylate having high transparency, the decrease in transparency is small.
Therefore, the macromonomer copolymer (Y) can be suitably used as a modifier for improving the impact resistance and flexibility of polymethyl methacrylate. In addition, since the macromonomer copolymer (Y) itself has high thermal decomposition resistance, it can be suitably used as a modifier for other resins having a high molding temperature and use temperature, which could not be applied with conventional macromonomer copolymers. .

The refractive index of the polymer (Y2) consisting only of the comonomer (B) in the macromonomer copolymer (Y) is the same as that for producing the macromonomer copolymer (Y) only from the comonomer (B). It can be considered that it is the same as the refractive index of the polymer polymerized in step (b).
Although the refractive index of the polymer which consists only of a comonomer (B) is not specifically limited, For example, it is preferable that the refractive index in wavelength 589nm is 1.44-0.54, and 1.47-1.51 are more preferable.
The refractive index of the macromonomer (A) is not particularly limited. For example, the refractive index at a wavelength of 589 nm is preferably 1.44 to 0.54, and more preferably 1.47 to 1.51.

[Production of Macromonomer Copolymer (Y)]
The macromonomer copolymer (Y) of the present invention is produced by solution polymerization, suspension polymerization or bulk polymerization. In solution polymerization, the obtained polymer solution can be used as it is as a raw material for paints and adhesives. Moreover, a solvent etc. can be removed by methods, such as deaeration extrusion, and it can also be used as a molding material and its additive. Bulk polymerization has a polymerization field equivalent to that of suspension polymerization, and a desired molded article can be obtained by injecting syrup into a mold for polymerization and curing. In suspension polymerization, since the macromonomer copolymer (Y) can be obtained as fine beads (particulate), it can be used as a molding material as it is for melt molding, or mixed with other resins and used as an additive, It can be used as a component of paints and adhesives.

The charging ratio of the macromonomer (A) and the comonomer (B) is preferably 10 to 90% by mass of the macromonomer (A) with respect to the total of the macromonomer (A) and the comonomer (B). 80 mass% is more preferable, and 30-70 mass% is further more preferable.
When the proportion of the macromonomer (A) is at least the lower limit of the above range, the macromonomer copolymer (Y) and the molding material (Z) described later can be improved in transparency and the microphase separation structure can be controlled. When it is below, the copolymerization reaction of the macromonomer (A) and the comonomer (B) is likely to proceed.

[Usage]
The macromonomer copolymer (Y) of the present invention may use the macromonomer copolymer (Y) as a main component, or may be used as an additive for other resins.
When the macromonomer copolymer (Y) is used as a main component, it can be used as various moldings such as sheets and films, various cases and covers, and a light guide as a molding material that can be melt-molded. In addition, it can be used as a paint or an adhesive by coating after dissolving in a solvent.
When the macromonomer copolymer (Y) is used as an additive for other resins, examples of the main resin include acrylic resins such as polymethyl methacrylate, polyolefins, polyamides, unsaturated polyesters, and polyethylene terephthalates. And saturated polyester such as polybutylene terephthalate, polycarbonate, polystyrene, ABS resin, AS resin, polyvinyl chloride, polylactic acid, and polyvinylidene fluoride.
The functions that the macromonomer copolymer (Y) imparts to other resins include flexibility, toughness, impact resistance, weather resistance, workability, releasability, scratch resistance, surface hardness, compatibility, and crystal size. Examples thereof include control and ductility.
Examples of the method of mixing with other resins include physical mixing, melt mixing, and a method of dissolving and dispersing before polymerization / curing.

[Molding materials]
A preferred embodiment of the molding material includes a molding material containing a macromonomer copolymer (Y) and polymethyl methacrylate (Z).
When the macromonomer copolymer (Y) is added to PMMA (polymethyl methacrylate (Z)) and used, the macromonomer (A) preferably contains a methyl methacrylate unit. The more methyl methacrylate units contained in the macromonomer (A), the better the compatibility with PMMA, which is preferable. In this case, the methyl methacrylate unit contained in the macromonomer (A) is preferably 50% by mass or more, and more preferably 80% by mass or more with respect to the macromonomer (A). Moreover, when PMMA to which the macromonomer copolymer (Y) is added contains units other than methyl methacrylate units, it is preferable that the monomer compositions of the macromonomer (A) and PMMA are close to each other.

  In particular, the polymethyl methacrylate (Z) preferably contains 80% by mass or more of methyl methacrylate units, and the macromonomer (A) contains 80% by mass or more of methyl methacrylate units. When the content of methyl methacrylate units in the polymethyl methacrylate (Z) and the macromonomer (A) is not less than the above lower limit value, the transparency is particularly excellent.

In the molding material of this embodiment, the content of the macromonomer copolymer (Y) is preferably 0.5 to 100% by mass with respect to the total of the macromonomer copolymer (Y) and the polymethyl methacrylate (Z). 1-60 mass% is more preferable, and 2-30 mass% is further more preferable.
The molding material may contain an optional component as long as the effects of the present invention are not impaired. For example, the total of the macromonomer copolymer (Y) and the polymethyl methacrylate (Z) is preferably 80 to 100% by mass and more preferably 90 to 100% by mass with respect to the molding material.

In the following, “part” which is a unit of blending amount means “part by mass”.
<Measurement method / Evaluation method>
[GPC measurement]
Mw and Mn were determined using gel permeation chromatography (GPC). The measurement conditions are shown below.
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK GUARD COLUMN SUPER H-H (4.6 × 35 mm, manufactured by Tosoh Corp.) and two TSK-GEL SUPER HM-H (6.0 × 150 mm, manufactured by Tosoh Corp.) connected in series Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 0.6 mL / min Mw (mass average molecular weight) and (Mn) number average molecular weight are polymethyl methacrylate (Mp (peak molecular weight) = 141,500, 55,600, 11,100 and 1, manufactured by Polymer Laboratories). 590 (4 types)) and a calibration curve prepared using The molecular weight distribution was calculated by the formula “molecular weight distribution = (mass average molecular weight) / (number average molecular weight)”.

[NMR measurement]
The reaction rate of the comonomer (B) is determined by ¹ H-NMR measurement. ¹ H-NMR measurement was performed using a nuclear magnetic resonance apparatus. The measurement conditions are shown below.
Apparatus: UNITY INOVA500 (manufactured by Varian)
Heavy solvent: Deuterated chloroform (manufactured by Sigma-Aldrich)
Sample preparation: Deuterated chloroform 1.2 was added to 0.225 g of the polymerization reaction solution.
Measurement conditions: 1000 times integration, measurement temperature 40 ° C

[Evaluation of thermal decomposition resistance (measurement of 5% weight loss temperature)]
The thermal decomposition resistance was evaluated by using a thermogravimetry / differential thermal analyzer and tracking the weight loss of the polymer to be measured. The measurement conditions are shown below.
Equipment: STA7300 manufactured by Hitachi High-Tech Science Co., Ltd.
Measurement conditions: Nitrogen stream 200 mL / min, 110 ° C. to 550 ° C., heating rate 10 ° C./min

[Evaluation of transparency (measurement of ΔHaze value)]
After a 2 mm thick molded plate was obtained by injection molding, the haze value was measured. The measurement conditions are shown below.
Equipment: NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.
Measurement conditions: The total light transmittance was evaluated according to JIS K7361-1, and the haze value (cloudiness value) was evaluated according to JIS K7316.
As a standard plate, a 2 mm thick plate made of VH001 (Mitsubishi Rayon Co., Ltd., a copolymer of methyl methacrylate and methyl acrylate, product name) was used. The absolute value of the difference from (unit:%) was calculated as a ΔHaze value. By comparing with the ΔHaze value, the internal haze value excluding the influence of the external haze can be compared.

<Production Example 1: Synthesis of Dispersant (1)>
In a reactor equipped with a stirrer, a condenser tube and a thermometer, 61.6 parts of a 17% by weight aqueous potassium hydroxide solution, 19.1 parts of methyl methacrylate and 19.3 parts of deionized water were charged. Next, the liquid in the reaction apparatus was stirred at room temperature, and after confirming an exothermic peak, the liquid was stirred for 4 hours. Thereafter, the reaction solution in the reaction apparatus was cooled to room temperature to obtain a potassium methacrylate aqueous solution.

  Next, in a polymerization apparatus equipped with a stirrer, a condenser tube and a thermometer, 900 parts of deionized water, 42 mass% 2-sulfoethyl sodium methacrylate aqueous solution (trade name: Acryester SEM-Na, manufactured by Mitsubishi Rayon Co., Ltd.) 70 parts, 16 parts of the above-mentioned potassium methacrylate aqueous solution and 7 parts of methyl methacrylate were added and stirred, and the temperature of the liquid in the reaction apparatus was raised to 50 ° C. while replacing the inside of the polymerization apparatus with nitrogen. In the polymerization apparatus, V-50 (2,2′-azobis (2-methylpropionamidine) dihydrochloride, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added in an amount of 0.053 part. The liquid was heated to 60 ° C. After the polymerization initiator was charged, 1.4 parts of methyl methacrylate was added in a total of 5 times (total amount of methyl methacrylate: 7 parts) every 15 minutes. Thereafter, the liquid in the polymerization apparatus was kept at 60 ° C. for 6 hours while stirring, and then cooled to room temperature to obtain a dispersant (1) having a solid content of 8% by mass as a transparent aqueous solution.

<Production Example 2: Synthesis of chain transfer agent (1)>
In a synthesizer equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt (II) acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) and diphenylglyoxime (Tokyo Kasei) were added in a nitrogen atmosphere. 3.86 g (16.1 mmol) manufactured by Eisai Co., Ltd. and 100 ml of diethyl ether previously deoxygenated by nitrogen bubbling were added and stirred at room temperature for 2 hours.

  Subsequently, 20 ml of boron trifluoride diethyl ether complex (Tokyo Kasei Co., Ltd., EP grade) was added and further stirred for 6 hours. The obtained product was filtered, the solid was washed with diethyl ether, dried at 100 MPa or less at 20 ° C. for 12 hours, and the brown solid chain transfer agent (1) 5.02 g (7.93 mmol, yield 99% by mass). )

<Production Example 3: Synthesis of Macromonomer (A-1)>
In a polymerization apparatus equipped with a stirrer, a condenser tube and a thermometer, 135 parts of deionized water, 0.1 part of sodium sulfate (Na ₂ SO ₄ ) and the dispersant (1) produced in Production Example 1 (solid content 10 (Mass%) 0.26 part was added and stirred to obtain a uniform aqueous solution. Next, 95 parts of methyl methacrylate, 5 parts of methyl acrylate, 0.0024 part of chain transfer agent (1) produced in Production Example 2, and perocta O (manufactured by NOF Corporation 1,1,3,3) -Tetramethylbutylperoxy 2-ethylhexanoate (trade name) 0.3 part was added to obtain an aqueous dispersion.

  Next, the inside of the polymerization apparatus was sufficiently purged with nitrogen, and the aqueous dispersion was heated to 80 ° C. and held for 3 hours, and then heated to 90 ° C. and held for 2 hours. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension of macromonomer. This aqueous suspension was filtered with a filter cloth, and the filtrate was washed with deionized water and dried at 40 ° C. for 16 hours to obtain a macromonomer (A-1). The average particle size of the macromonomer (A-1) was 95 μm, Mw was 23,700, and Mn was 12,600. In the macromonomer (A-1), the mass ratio of methyl methacrylate unit / methyl acrylate unit was 95/5. The introduction rate of the terminal double bond of the macromonomer (A-1) was almost 100%.

<Production Example 4: Synthesis of polymer (Z-1) consisting only of comonomer (B)>
In a separable flask equipped with a stirrer, a condenser tube and a thermometer, 200 parts of toluene (manufactured by Wako Pure Chemical Industries), 100 parts of n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation), V59 (AMBN made by Wako Pure Chemical Industries, Ltd.) (2,2-azobis (2-methylbutyronitrile), trade name) 0.3 part was added and stirred to obtain a homogeneous solution, and nitrogen bubbling was performed for 30 minutes to change the atmosphere in the separable flask. Then, the temperature was raised to 69 ° C. to initiate polymerization, and the reaction was allowed to proceed for 5 hours, followed by cooling to room temperature to obtain a polymer solution.

  After diluting 100 parts by mass of the obtained polymer solution with 200 parts of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), it was added to 3000 parts by mass of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) to produce a precipitate. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain a polymer (Z-1) composed of poly n-butyl acrylate. Mn of the polymer (Z-1) was 52,800, Mw was 134,000, and the 5% weight reduction temperature was 330 ° C.

<Production Examples 5 to 8: Synthesis of polymers (Z-2) to (Z-5) consisting only of comonomer (B)>
In Production Example 4, polymers (Z-2) to (Z-5) were obtained in the same manner except that the monomer used was changed from 100 parts of n-butyl acrylate to the monomer composition shown in Table 1. The evaluation results are shown in Table 1.

  From the results of Table 1, when Production Examples 4 to 8 are compared, the polymer (Z-2) to (Z-2) to (A-2) containing the aromatic acrylate (B2) is compared with the polymer (Z-1) consisting only of the alkyl acrylate (B1). It can be seen that Z-5) has higher thermal decomposition resistance.

<Example 1: Synthesis of macromonomer copolymer (Y-1)>
In a separable flask equipped with a stirrer, a condenser tube and a thermometer, 100 parts of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 30.0 parts of the macromonomer (A-1) produced in Production Example 3 were placed at 50 ° C. And stirred for 1 hour to obtain a uniform solution. Once cooled to room temperature, 49.0 parts of n-butyl acrylate (Mitsubishi Chemical Co.) as alkyl acrylate (B1) and 21.0 parts of benzyl acrylate (Osaka Organic Chemical Co., Ltd.) as aromatic acrylate (B2) , V59 (AMBN (2,2-azobis (2-methylbutyronitrile), trade name) manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain a uniform solution. Nitrogen bubbling was performed for 30 minutes. The atmosphere in the separable flask was replaced with nitrogen, and then the temperature was raised to 69 ° C. to initiate the polymerization, the reaction was allowed to proceed for 5 hours, and then cooled to room temperature to obtain a polymer solution.

  After diluting 100 parts by mass of the obtained polymer solution with 200 parts of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), it was added to 3000 parts by mass of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) to produce a precipitate. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain a macromonomer copolymer (Y-1). Mn of the macromonomer copolymer (Y-1) was 32,400, and Mw was 72,800. The thermal decomposition resistance was evaluated by the above method. The polymerization conditions and evaluation results are summarized in Table 2.

<Example 2 and Comparative Examples 1-2: Synthesis of Macromonomer Copolymers (Y-2) to (Y-4)>
In Example 1, the composition of the macromonomer (A1) and the comonomer (B) was changed to the contents shown in Table 2. Other than that carried out similarly to Example 1, Example 2 and Comparative Examples 1-2 were performed, and macromonomer (Y-2)-(Y-4) was obtained. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

As shown in the results of Table 2, the macromonomer copolymers (Y-1) and (Y-2) have a 5% weight loss temperature of 340 ° C. or higher, and are excellent in thermal decomposition resistance.
Specifically, the macromonomer copolymers (Y-1) and (Y-2) are respectively compared with the macromonomer copolymers (Y-3) and (Y-4) not containing the aromatic acrylate (B2). As a result, the 5% weight loss temperature increased by about 20 ° C.

<Example 3: Kneaded material of macromonomer copolymer (Y) and PMMA>
Using 14 parts of the macromonomer copolymer (Y-1) produced in Example 1 and 86 parts of VH001 (polymethyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd., trade name) using Labo Plast Mill (manufactured by Toyo Seiki Seisakusho) Melt kneading was carried out at 0 ° C. Using the obtained kneaded product, a 2 mm-thick molded plate was produced using a micro-kneading injection molding machine (manufactured by Imoto Seisakusho), and the transparency was evaluated by the above method. The ΔHaze values are shown in Table 3.

<Example 4 and Comparative Examples 3-4>
In the same manner as in Example 3, the macromonomer copolymer (Y) used was changed to that shown in Table 3, and melt kneading, injection molding plate production, and evaluation were performed. The results are shown in Table 3.

  From the results of Table 3, the kneaded materials of Examples 3 and 4 using the macromonomer copolymers (Y-1) and (Y-2) obtained in Examples 1 and 2 have small ΔHaze values and are transparent. Excellent. That is, it can be seen that the macromonomer copolymers (Y-1) and (Y-2) do not impair the transparency of polymethyl methacrylate when kneaded with polymethyl methacrylate.

  On the other hand, the kneaded materials of Comparative Examples 3 and 4 using the macromonomer copolymers (Y-3) and (Y-4) obtained in Comparative Examples 1 and 2 have ΔHaze values higher than those of Examples 3 and 4. large.

Claims (6)

A macromonomer copolymer (Y) comprising a unit derived from a macromonomer (A) represented by the following general formula (1) and a unit derived from a comonomer (B) copolymerizable with the macromonomer (A). The macromonomer copolymer (Y) has a 5% weight loss temperature of 340 ° C. or higher measured under conditions of a temperature increase rate of 10 ° C./min under a nitrogen stream.

(In the formula, R and R ^{1 to} R ⁿ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group or heterocyclic group. X _{1 to} X _n are each independently a hydrogen atom or methyl. Z is a terminal group, and n is a natural number of 2 to 10,000.) A macromonomer copolymer (Y) comprising a unit derived from a macromonomer (A) represented by the following general formula (1) and a unit derived from a comonomer (B) copolymerizable with the macromonomer (A). The macromonomer copolymer (Y) in which the comonomer (B) includes an alkyl acrylate (B1) and an aromatic acrylate (B2).

(In the formula, R and R ^{1 to} R ⁿ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group or heterocyclic group. X _{1 to} X _n are each independently a hydrogen atom or methyl. Z is a terminal group, and n is a natural number of 2 to 10,000.)   The alkyl acrylate (B1) is methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate And a macromonomer copolymer (Y) according to claim 2, which is at least one selected from the group consisting of i-stearyl acrylate.   The macromonomer copolymer (Y) according to claim 2 or 3, wherein the aromatic acrylate (B2) is at least one selected from the group consisting of benzyl acrylate, phenoxyethyl acrylate, and phenyl acrylate.   5. The absolute value of the difference between the refractive index of the polymer composed only of the comonomer (B) and the refractive index of the macromonomer (A) is 0.05 or less. The macromonomer copolymer (Y) according to claim 1.   It is a molding material containing the macromonomer copolymer (Y) as described in any one of Claims 1-5, and a polymethylmethacrylate (Z), Comprising: The said polymethylmethacrylate (Z) has a methylmethacrylate unit. A molding material containing 80% by mass or more, wherein the macromonomer (A) contains 80% by mass or more of methyl methacrylate units.