JP2018159024A - Method for producing macromonomer copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a macromonomer copolymer having a high reaction rate of a macromonomer and a small amount of residual macromonomer. SOLUTION: A monomer-containing composition containing a polymerizable component (X) composed of a macromonomer (a) represented by the formula (1) and a comonomer (b) copolymerizable with (a) is polymerized in a lump form or. A method for producing a macromonomer copolymer by subjecting it to a polymerization reaction by suspension polymerization, wherein (X) contains 3.0 mol% or more of (a). R and R1 to Rn are H, alkyl, cycloalkyl, aryl or heterocyclic groups, respectively; X1 to Xn are H or methyl groups, respectively; Z is the terminal group; n is 2 to 10,000. Natural number) [Selection diagram] None

Description

  The present invention relates to a method for producing a macromonomer copolymer.

  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.

For example, an acrylic resin molded article is excellent in transparency, but has a problem of being hard and brittle.
In the case of a (meth) acryl block copolymer in which two or more kinds of polymer segments are chemically bonded, the phase separation structure becomes a micro phase separation structure. Moreover, it can be expected that an acrylic resin molded article excellent in impact resistance and flexibility will be obtained.

As a method for producing such a (meth) acrylic block copolymer, an acrylic macromonomer is prepared in advance using a very small amount of a cobalt complex having an extremely high chain transfer constant, and the acrylic macromonomer and another acrylic monomer are copolymerized. A method for producing a (meth) acrylic block / graft copolymer is known (for example, see Patent Document 1).
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 2 and 3 are known. Patent Document 2 discloses 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 3, a nonmetal chain transfer agent is used to prevent crosslinking of the copolymer.

Special Table 2000-514845 International Publication No. 2014/098141 International Publication No. 2015/056668

However, the conventional method does not always have a sufficient macromonomer reaction rate. There is a concern that unreacted macromonomer may adversely affect the thermal decomposition resistance and physical properties.
An object of this invention is to provide the manufacturing method of the macromonomer copolymer by suspension polymerization with the high macromonomer reaction rate and few residual macromonomers.

The present invention has the following embodiments.
[1] A monomer-containing composition comprising a polymerizable component (X) comprising a macromonomer (a) represented by the following general formula (1) and a comonomer (b) copolymerizable with the macromonomer (a), A method for producing a macromonomer copolymer (Y) by polymerization reaction by bulk polymerization or suspension polymerization,
The manufacturing method of a macromonomer copolymer (Y) in which the said polymeric component (X) contains the said macromonomer (a) 3.0 mol% or more.

(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] The monomer-containing composition does not contain a sulfur-containing chain transfer agent, or contains less than 0.01 parts by mass of a sulfur-containing chain transfer agent with respect to 100 parts by mass of the polymerizable component (X). A method for producing the macromonomer copolymer (Y).
[3] The macromonomer copolymer of [1] or [2], wherein the syrup comprising the polymerizable component (X) used in the bulk polymerization or suspension polymerization has a viscosity at 25 ° C. of 7000 mPa · sec or less. The manufacturing method of (Y).
[4] The method for producing the macromonomer copolymer (Y) according to any one of [1] to [3], wherein the comonomer (b) contains 65% by mass or more of the acrylate (b1).

The production method of the present invention has a high macromonomer reaction rate.
The macromonomer copolymer (Y) produced by the production method of the present invention has little residual macromonomer.

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.
In the following, the monomer component before polymerization is referred to as “˜monomer”, and “monomer” may be omitted. In addition, the monomer unit constituting the polymer is referred to as “unit derived from” or “unit”. Moreover, (meth) acrylate shows a methacrylate or an acrylate.

  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 a polymerizable component (X) comprising 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. Examples of the hetero atom contained in the heterocyclic ring include an oxygen atom, a nitrogen atom, and a sulfur atom.

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 ″), a cyano group, Selected from the group consisting of 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. A group or an atom. R ′ and R ″ are each independently the same groups as R except for the heterocyclic ring.

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 at least half 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, compatibility and physical properties derived from the macromonomer (a) can be imparted to the macromonomer copolymer (Y). If the number average molecular weight Mn is not more than the upper limit, it becomes easy to set the mol% of the macromonomer (a) in the polymerizable component (X) to 3.0 mol% or more, and the macromonomer (a) and the comonomer ( The viscosity of the syrup obtained by mixing b) tends to be within the range where suspension polymerization is possible.

  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).

The macromonomer (a) may be a mixture of two or more kinds of macromonomers. In this case, the number average molecular weight Mn is calculated as a value for the entire macromonomer (a). When a plurality of types of macromonomers (a) having different number average molecular weights Mn are used in combination, the lower molecular weight macromonomer (a) plays a role in reducing the syrup viscosity and improving the mol% occupied by the macromonomer (a), and has a higher molecular weight. The macromonomer (b) having a large size plays a role of ensuring compatibility with the matrix resin when used as an additive.
Of the entire macromonomer (a), the macromonomer having a number average molecular weight Mn of 5,000 or less is preferably 20% by mass or more, and more preferably 30% by mass or more.

[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 (attacrylic acid ester) from the viewpoint of heat resistance of the macromonomer copolymer (Y) and a molded article containing the macromonomer copolymer (Y). Is preferred.
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. Among these, methyl acrylate is preferable in terms of availability.

The content of methacrylate in the total monomer for obtaining the macromonomer (a) is 80% by mass from the viewpoint of the heat resistance of the macromonomer copolymer (Y) as a product and the molded product 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.
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.

[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 step 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.

[Reaction mechanism of macromonomer (a) and comonomer (b)]
The 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) forms a branched structure in the copolymerization reaction with acrylate, and can be copolymerized. However, it is difficult to form a branched structure by the reaction of the terminal double bond group of the macromonomer (a) with methacrylate, and the terminal double bond group and the radical at the end of the methacrylate growth are mainly generated by re-cleavage. 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 industrial. Therefore, it is preferable that the comonomer (b) contains acrylate (b1) as a main component, and uses methacrylate (b2) or other monomers (b3) as necessary.

[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. Specific examples include the same monomers as those for obtaining the macromonomer (a), but it is preferable to mainly use the acrylate (b1) from the viewpoint of reactivity with the macromonomer (a). Moreover, a methacrylate (b2) and another monomer (b3) can be used as needed.

  Examples of the acrylate (b1) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, n-stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate and other acrylates; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Hydroxyl-containing acrylates such as 4-hydroxybutyl acrylate and glycerol acrylate; acrylic acid, 2 Acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-acryloyloxyethyl maleic acid, 2-acryloyloxypropyl maleic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, carboxy group-containing acrylate; glycidyl acrylate, glycidyl α-ethyl acrylate, epoxy group-containing acrylate such as 3,4-epoxybutyl acrylate; dimethylaminoethyl acrylate Amino group-containing acrylates such as diethylaminoethyl acrylate; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1, And polyfunctional acrylates such as 6-hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, and allyl acrylate. One or more of these can be appropriately selected and used.

  Among the above, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, n-stearyl acrylate Cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n -Lauryl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate are particularly preferred Arbitrariness.

In one aspect of the present invention, for the purpose of imparting flexibility, impact resistance, and tackiness, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl Acrylate, 4-hydroxybutyl acrylate can be used.
Moreover, as a high refractive index component for adjusting the refractive index, for example, phenyl acrylate, benzyl acrylate, or phenoxyethyl acrylate can be used. For other purposes, for example, methyl acrylate, ethyl acrylate or the like can be used for the purpose of ensuring compatibility with the macromonomer (a).

  Examples of the methacrylate (b2) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, methacrylates such as n-stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, phenoxyethyl methacrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerol methacrylate Hydroxyl group-containing methacrylates such as methacrylic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxypropylhexahydrophthalic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyloxy Carboxy group-containing methacrylates such as ethyl maleic acid, 2-methacryloyloxypropyl maleic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxypropyl succinic acid; epoxy such as glycidyl methacrylate and 3,4-epoxybutyl methacrylate Group-containing methacrylate; Amino group-containing methacrylate 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. Functional methacrylate; and the like. One or more of these can be appropriately selected and used.

  Among the above, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate Cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, phenoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n -Lauryl methacrylate, phenyl methacrylate, benzyl meta Relate, phenoxyethyl methacrylate is particularly preferred.

  Examples of the other monomer (b3) include carboxy group-containing vinyl monomers such as crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid; maleic anhydride, itaconic anhydride and the like. Acid anhydride group-containing vinyl monomers; (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) Vinyl monomers containing amide groups such as acrylamide, diacetone acrylamide, maleic acid amide, maleimide; styrene, α-methylstyrene, vinyl toluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate, etc. Vinyl monomer; divinylbenzene, N, N - methylenebis (meth) polyfunctional vinyl monomers such as acrylamide; and the like. One or more of these can be appropriately selected and used.

The comonomer (b) preferably contains 65% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more of the acrylate (b1) with respect to 100% by mass in total of the comonomer (b). preferable. It may be 100% by mass.
The composition ratio of the comonomer (b) is the weight ratio of the acrylate (b1) and the methacrylate (b2) from the viewpoint of reactivity with the macromonomer (a) described above (b1: b2) = 65: 35-100 : 0, preferably (b1: b2) = 70: 30 to 100: 0, more preferably (b1: b2) = 80: 20 to 100: 0. .
By keeping the ratio of acrylate (b1) and methacrylate (b2) within the above range, the reactivity between the macromonomer (a) and the comonomer (b) is ensured, and the block that the macromonomer copolymer (Y) contains The ratio of the polymer or graft polymer can be sufficiently increased. If the amount of acrylate (b1) is small, the macromonomer (a) may not react sufficiently and may remain unreacted, the molecular weight may not increase sufficiently, or the reaction time may become too long.
A smaller amount of the other monomer (b3) is preferred. For example, the proportion of the monomer (b3) is preferably 10% by mass or less and more preferably 5% by mass or less with respect to the total of 100% by mass of the comonomer (b). Zero is acceptable.

The molar ratio of the macromonomer (a) and the comonomer (b) is such that the macromonomer (a) is 3.0 mol% or more when the entire polymerizable component contained in the polymerizable component (X) is 100 mol%. Preferably, it is preferably 3.2 mol% or more, more preferably 3.4 mol% or more. If macromonomer (a) is 3.0 mol% or more, it can prevent that the polymer chain which consists of a comonomer (b) bridge | crosslinks at the time of superposition | polymerization.
When the comonomer (b) contains acrylate (b1) as a main component, branching may occur due to generation of a mid-chain radical from the polyacrylate chain, and as a result, the macromonomer copolymer (Y) may be crosslinked. . The present inventors give the macromonomer (a) a role as a chain transfer agent by setting the molar ratio of the macromonomer (a) within a predetermined range, and prevent crosslinking of the macromonomer copolymer (Y). I found out that I can.

[Radical polymerization initiator]
When the polymerization reaction 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 polymerizable component (X).
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.

[Viscosity of syrup]
The polymerizable component (X) composed of the macromonomer (a) and the comonomer (b) can be obtained as syrup by dissolving the macromonomer (a) in the comonomer (b). When the obtained syrup is used for suspension polymerization, it is necessary to disperse it as fine droplets in an aqueous solution. In suspension polymerization, the dispersion of the polymerizable component relies on mechanical shearing force, so that the viscosity of the syrup needs to be kept below a certain level. The viscosity at 25 ° C. of the syrup comprising the polymerizable component (X) is preferably 7000 mPa · sec or less, more preferably 5000 mPa · sec or less, and further preferably 3000 mPa · sec or less. If the viscosity of syrup at 25 ° C. is 7000 mPa · sec or less, the droplets can be uniformly dispersed in the aqueous solution.
The viscosity of syrup can be adjusted by the molecular weight of the macromonomer (a), the composition ratio of the macromonomer (a) and the comonomer (b), and the type of the comonomer (b).

[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). In addition, there is a possibility that the polymer (Y2) consisting only of the comonomer (b) unit and the unreacted macromonomer (a) are included. It is preferable that the contents of the polymer (Y2) and the unreacted macromonomer (a) are small.

  Since the polymer (Y2) composed only of the comonomer (b) unit may interfere with the control of the microphase separation structure when the macromonomer copolymer (Y) is used as an additive for various resins, Less is preferable. Specifically, the polymer (Y2) is preferably 5% by mass or less, more preferably 2% by mass or less, and substantially 0% by mass with respect to 100% by mass of the macromonomer copolymer (Y). Further preferred.

  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 the 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). .

  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. When the mass average molecular weight Mw is 30,000 or more, the mechanical strength and heat decomposability of the resin molded article are good, and when it is 10,000,000 or less, moldability and solubility in the matrix resin are good.

[Production of Macromonomer Copolymer (Y)]
The macromonomer copolymer (Y) of the present invention is produced by suspension polymerization or bulk polymerization. In bulk polymerization, the polymerization field is the same as that of suspension polymerization, and a target molded product can be obtained by injecting a monomer-containing composition containing a polymerizable component (X) into a mold and polymerizing and curing. In suspension polymerization, the macromonomer copolymer (Y) can be obtained as fine beads (particles), so it can be used directly as a molding material for melt molding, mixed with other resins and used as an additive, Or as a component of an adhesive.

[Production of Macromonomer Copolymer (Y) by Suspension Polymerization]
For example, when the macromonomer copolymer (Y) is produced by suspension polymerization using the macromonomer (a) produced by suspension polymerization, the following steps i) to v) are preferably included.

i) Syrup preparation step The beads of the macromonomer (a) are dissolved in the comonomer (b) to prepare syrup. During the preparation of syrup, it is preferable to increase the temperature of the mixture comprising the macromonomer (a) and the comonomer (b) within a range below the boiling point of the comonomer, thereby assisting the dissolution of the macromonomer. The syrup preparation temperature is preferably in the range of 20 ° C to 100 ° C, more preferably in the range of 40 ° C to 80 ° C. When the syrup can be prepared within the range where the radical polymerization initiator does not react, the initiator-containing syrup can be prepared by simultaneously mixing the radical polymerization initiator.

ii) Radical polymerization initiator dissolution step When the radical polymerization initiator reacts at the syrup preparation temperature, the syrup is once cooled after the syrup preparation, and then the radical polymerization initiator is added and dissolved to obtain a uniform initiator-containing syrup. . The temperature at which the radical polymerization initiator is added is preferably not more than a temperature obtained by subtracting 15 ° C. from the 10-hour half-life temperature of the radical polymerization initiator.

iii) Preparation Step of Aqueous Solution The aqueous solution can contain a dispersant, an electrolyte, and other auxiliaries. The dispersibility of syrup droplets in an aqueous solution is controlled by a combination of a dispersant and an electrolyte.
The water used in the aqueous solution is preferably deionized water from the viewpoint of dispersibility control.
Examples of the dispersant include poly (meth) acrylic acid alkali metal salts, (meth) acrylic acid alkali metal salts and (meth) acrylic acid ester copolymers, and (meth) acrylic acid sulfoalkyl alkali metal salts. And (meth) acrylic acid ester copolymer, polystyrenesulfonic acid alkali metal salt, styrenesulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, or a combination of these monomers Combined: Polyvinyl alcohol having a saponification degree of 70 to 100%, methyl cellulose, starch and hydroxyapatite can be mentioned. These can be used alone or in combination of two or more. Among these, a copolymer of an alkali metal salt of (alkyl) sulfoalkyl (meth) acrylate and (meth) acrylic acid ester and a (meth) acrylic acid alkali metal salt (meta) having good dispersion stability during suspension polymerization. ) A copolymer of acrylic ester is preferred. As an addition amount of a dispersing agent, it is used in 0.0005-0.5 mass part with respect to 100 mass parts of polymeric components (X), for example.
Examples of the electrolyte include sodium carbonate, sodium sulfate, manganese sulfate and the like. As addition amount of electrolyte, it is used in 0.01-1.0 mass part with respect to 100 mass parts of polymeric components (X), for example.

iv) Polymerization Reaction Step A suspension (monomer-containing composition) in which a mixture of a syrup containing a radical polymerization initiator and an aqueous solution is stirred to disperse syrup droplets is prepared. Next, the temperature of the suspension is increased while stirring to initiate the polymerization reaction. It is preferable to carry out vacuum degassing and nitrogen substitution for the purpose of removing dissolved oxygen contained in the syrup and the aqueous solution in any step before the polymerization is started by raising the temperature.
The polymerization temperature is an important polymerization condition for obtaining a macromonomer copolymer (Y) comprising a block / graft copolymer efficiently. The polymerization temperature here refers to the temperature of the suspension. The polymerization temperature is preferably 50 ° C to 90 ° C, more preferably 60 ° C to 80 ° C, and further preferably 65 ° C to 75 ° C. If the polymerization temperature is too low, there is a concern that the reaction proceeds slowly and the polymerization time becomes long. On the other hand, when the polymerization temperature is too high, the cleavage of the reaction intermediate is prioritized and the block / graft polymer is hardly formed.
At the end of the polymerization reaction, the suspension can be heated for the purpose of increasing the reaction rate of the polymerizable component (X) and eliminating the unreacted radical polymerization initiator. The temperature to be raised is preferably 80 ° C. or higher, and more preferably 85 ° C. or higher. The temperature raising time may be determined by calculating the time until the radical polymerization initiator disappears, but is preferably about 60 minutes to 2 hours.

v) Recovery step The produced macromonomer copolymer (Y) beads are recovered after cooling the suspension. If necessary, beads made of the macromonomer copolymer (Y) are obtained through a washing process for removing impurities such as a dispersant and an electrolyte, a removal process of beads mixed with bubbles, a drying process, and the like.

[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.

According to the production method of the present invention, when suspension polymerization is performed using a monomer-containing composition containing a polymerizable component (X), the macromonomer (a) contained in the polymerizable component (X) is 3.0%. By setting it as mol% or more, the macromonomer (a) is given a role as a chain transfer agent. When the comonomer (b) contains acrylate (b1) as a main component, the polymer chain containing the comonomer (b) unit is likely to be crosslinked during the production of the macromonomer copolymer (Y), but the macromonomer (a) is chained. Cross-linking can be prevented by acting as a transfer agent.
Further, the macromonomer (a) serves as a chain transfer agent in the process of copolymerization with the comonomer (b), and is finally taken into the macromonomer copolymer (Y). Therefore, in the production method of the present invention, the reaction rate of the macromonomer (a) is high, and the thermal decomposition resistance of the resulting macromonomer copolymer (Y) is improved. Therefore, it is suitable as an additive for various polymers, and can impart impact resistance and flexibility.

For example, in the Example of the said patent document 3, the crosslinking | crosslinking of a copolymer is prevented using 0.05-0.2 mass part of sulfur containing chain transfer agents with respect to 100 mass parts of polymeric component (X). However, as shown in Comparative Examples described later, when a sulfur-containing chain transfer agent is used, a large amount of macromonomer tends to remain.
According to the production method of the present invention, even if the amount of the sulfur-containing chain transfer agent used relative to 100 parts by mass of the polymerizable component (X) is less than 0.01 parts by mass, it is possible to prevent crosslinking from occurring during the polymerization reaction. Can do. When the monomer-containing composition does not contain a sulfur-containing chain transfer agent or contains a sulfur-containing chain transfer agent, it is preferably less than 0.01 parts by mass with respect to 100 parts by mass of the polymerizable component (X).
Examples of the sulfur-containing chain transfer agent include alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan.

In the following, “part” which is a unit of blending amount means “part by mass”.
<Measurement method / Evaluation method>
[Analysis Method of Macromonomer Copolymer (Y)]
[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

[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

[HPLC measurement]
The reaction rate of the macromonomer (a) was measured using HPLC (high performance liquid chromatography). The measurement conditions are shown below.
Apparatus: Alliance e2695 (Waters)
Column: TSKgel ODS100V (5 μm, 4.6 × 150 mm, manufactured by Tosoh Corporation)
Eluent: acetonitrile (liquid A), tetrahydrofuran (liquid B)
Gradient condition: linear gradient 0 minutes (A liquid / B liquid = 100/0) -10 minutes (A liquid / B liquid = 0/100) -15 minutes (A liquid / B liquid = 0/100)
Measurement temperature: 40 ° C
Flow rate: 1.0 mL / min Detector: Charged particle detector Corona ultra RS (manufactured by Thermo Fisher Scientific)
Each sampled polymerization reaction solution was dissolved in tetrahydrofuran to obtain a sample solution. Further, the macromonomer (a) was dissolved in tetrahydrofuran to obtain a standard solution. A calibration curve was created from the area and height of the peak corresponding to the macromonomer (a) in the chromatogram of the standard solution. Using this calibration curve, the reaction rate of the macromonomer (a) was determined from the area and height of the peak corresponding to the macromonomer (a) in the chromatogram of the sample.

[Evaluation of thermal decomposition resistance (measurement of 5% weight loss temperature)]
The thermal decomposition resistance was evaluated by following the weight loss of the polymer to be measured using a thermogravimetry / differential thermal analyzer. The measurement conditions are shown below.
Equipment: TG / DTA6300 manufactured by SII Nano Technology
Measurement conditions: Nitrogen stream 200 mL / min, 40 ° C. to 550 ° C., heating rate 10 ° C./min

[Measurement of viscosity of syrup]
Viscosity measurement was evaluated using an E-type viscometer. The measurement conditions are shown below.
Equipment: TV-25 manufactured by Toki Sangyo Co., Ltd.
Measurement conditions: 25 ° C

[Judgment of cross-linking]
The presence or absence of cross-linking was determined by whether or not it was soluble in tetrahydrofuran. After 5 mL of tetrahydrofuran was added to 10 mg of the target polymer and dissolved, the solution was passed through a Cosmonis filter S (Merck, pore size 0.45 μm).

<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, 0.0016 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) 0.13 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 through 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 32,500, and Mn was 16,500. The introduction rate of the terminal double bond of the macromonomer (a-1) was almost 100%.

<Production Examples 4 to 5: Synthesis of macromonomers (a-2) and (a-3)>
Macromonomers (a-2) and (a-3) were obtained in the same manner as in Production Example 3, except that the amounts used of the chain transfer agent (1) and the polymerization initiator were changed as shown in Table 1. . The evaluation results are also shown in Table 1.

<Example 1: Synthesis of macromonomer copolymer (Y-1)>
In a separable flask equipped with a stirrer, a condenser, and a thermometer, 50 parts of macromonomer (a-3) and 50 parts of n-butyl acrylate were added and stirring was started. Next, the separable flask was heated with warm water at 50 ° C., and the macromonomer (a-3) was dissolved in n-butyl acrylate to obtain uniform syrup. The viscosity of syrup was measured and found to be 770 mPa · sec (25 ° C.).
The polymerizable component (X) comprises a macromonomer (a-3) and n-butyl acrylate, and the macromonomer (a) in the polymerizable component (X) is 4.5 mol%.

Next, after once cooling the syrup to room temperature, 0.3 part of 2,2′-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-59) as a radical polymerization initiator Was added, stirred and dissolved to obtain an initiator-containing syrup.
Next, a mixed solution of 150 parts of deionized water, 0.66 part of the dispersant (1), and 0.3 part of sodium sulfate was prepared as an aqueous solution and added to the initiator-containing syrup. Next, the inside of the separable flask was stirred while purging with nitrogen by nitrogen bubbling to obtain a syrup dispersion.
The syrup dispersion was heated to 69 ° C. and held for 5 hours to carry out the polymerization reaction.
The suspension was cooled to 40 ° C. or lower, filtered through a filter cloth, and the filtrate was washed with deionized water. Thereafter, the filtrate was dried under reduced pressure at 40 ° C. for 12 hours to obtain a bead-like macromonomer copolymer (Y).
The items described in Table 2 were measured by the above method. The results are shown in Table 2.

<Examples 2-3 and Comparative Examples 1-3>
The macromonomer copolymer (Y) was produced by changing the polymerization recipe to the contents shown in Table 2. The contents not described in Table 2 were performed in the same manner as in Example 1.
Comparative Example 3 is an example using n-octyl mercaptan which is a sulfur-containing chain transfer agent.

As shown in Table 2, in Examples 1 to 3 in which the polymerizable component (X) contains 3.0 mol% or more of the macromonomer (a), the macromonomer copolymer (Y) was obtained without crosslinking. The reaction rate of the macromonomer (a) and the reaction rate of the comonomer (b) were both high, and the thermal decomposition resistance was good.
In the HPLC measurement results, no peak was detected at any position corresponding to the retention time of the polymer consisting only of the comonomer (b) unit in the samples of Examples 1 to 3. That is, in Examples 1-3, the macromonomer copolymer (Y) which does not contain the polymer (Y2) which consists only of a comonomer (b) unit was obtained.

On the other hand, in Comparative Examples 1 and 2 in which the macromonomer (a) in the polymerizable component (X) is less than 3.0 mol%, the macromonomer copolymer (Y) has been crosslinked. Therefore, no measurement was performed on items other than the presence or absence of crosslinking.
In Comparative Example 3, the macromonomer (a) in the polymerizable component (X) was less than 3.0 mol%, but since n-octyl mercaptan was used as a chain transfer agent, crosslinking was prevented. The reaction rate of (a) was low. The content of the unreacted macromonomer (a) in the macromonomer copolymer (Y) was 25% by mass.
In addition, although the macromonomer copolymer (Y) of Comparative Example 3 contains a large amount of unreacted macromonomer (a), the reason why the 5% weight loss temperature is high is that the unreacted macromonomer (a) This is thought to be because the terminal double bond disappeared in a part of. In this phenomenon, after the radical is added to the macromonomer (a) during the copolymerization reaction, the radical generated at the terminal of the macromonomer (a) reacts with n-octyl mercaptan, and the terminal double bond disappears. This is probably because of this. That is, a part of the remaining macromonomer (a) has no terminal double bond, so depolymerization does not occur and the thermal decomposition resistance is high, but the copolymerizability with the comonomer (b) is lost, and n-octyl is lost. It is thought that the formation of the macromonomer copolymer was inhibited by the mercaptan.

Claims (4)

A monomer-containing composition comprising a macromonomer (a) represented by the following general formula (1) and a polymerizable component (X) comprising a comonomer (b) copolymerizable with the macromonomer (a) A method for producing a macromonomer copolymer (Y) by a polymerization reaction by suspension polymerization,
The manufacturing method of a macromonomer copolymer (Y) in which the said polymeric component (X) contains the said macromonomer (a) 3.0 mol% or more.

(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 said monomer containing composition does not contain a sulfur-containing chain transfer agent, or contains less than 0.01 mass part of sulfur-containing chain transfer agents with respect to 100 mass parts of said polymeric components (X). A method for producing the macromonomer copolymer (Y).   The macromonomer copolymer (Y) according to claim 1 or 2, wherein the syrup comprising the polymerizable component (X) used in the bulk polymerization or suspension polymerization has a viscosity at 25 ° C of 7000 mPa · sec or less. Manufacturing method.   The manufacturing method of the macromonomer copolymer (Y) as described in any one of Claims 1-3 in which the said comonomer (b) contains 65 mass% or more of acrylates (b1).