JP7035327B2 - Method for producing macromonomer copolymer - Google Patents

Description

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

Many of the monomers having a reactive unsaturated bond can be reacted under appropriate conditions using a catalyst that causes chain transfer to form a polymer. When polymers are used industrially, homopolymers using a kind of monomer cannot meet the various demands of materials, so a method of mixing different kinds of polymers is used. However, simply mixing dissimilar polymers causes phase separation (called macrophase separation) with relatively large size domains without the polymers incompatible with each other, and a mixture of dissimilar polymers is produced by each polymer. It is often difficult to express both of these properties.

As a method for solving the above problems, a method using a block copolymer in which two or more kinds of polymer segments are chemically bonded is known. As mentioned above, in a mixture of dissimilar polymers, phase separation occurs because the compatibility between the polymers is low, but in the block polymer, the polymer segments are chemically bonded to each other, so that the phase separation structure is nanometer-sized. (Called microphase separation). Therefore, the characteristics of each polymer segment can be expressed together.

For example, an acrylic resin molded product has excellent transparency, but has a problem of being hard and brittle.
In the case of a (meth) acrylic block copolymer in which two or more of the above-mentioned polymer segments are chemically bonded, the phase separation structure is a microphase separation structure. Therefore, by demonstrating the characteristics of each polymer segment, the transparency is excellent. Moreover, it can be expected that an acrylic resin molded body having excellent impact resistance and flexibility can be obtained.

As a method for producing such a (meth) acrylic block copolymer, an acrylic macromonomer is previously produced using a very small amount of a cobalt complex having an extremely high chain transfer constant, and the acrylic macromonomer is copolymerized with another acrylic monomer. A method for producing a (meth) acrylic block / graft copolymer is known (see, for example, Patent Document 1).
The macromonomer is a polymer having a functional group capable of a polymerization reaction, and is also called a macromer.

Further, as a method for obtaining a (meth) acrylic block / graft copolymer which is a copolymer of an acrylic macromonomer and an acrylic monomer, the method by suspension polymerization described in Patent Documents 2 and 3 is known. Patent Document 2 describes a method in which two or more types having different solubility parameters are used in combination as a comonomer to be combined with an acrylic macromonomer. In Patent Document 3, a non-metal chain transfer agent is used to prevent cross-linking of the copolymer.

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

However, it cannot be said that the reaction rate of the macromonomer is always sufficient by the conventional method. The unreacted macromonomer may adversely affect the heat-decomposability and physical properties.
An object of the present invention is to provide a method for producing a macromonomer copolymer by suspension polymerization, which has a high reaction rate of macromonomers and a small amount of residual macromonomers.

The present invention has the following embodiments.
[1] A monomer-containing composition containing a polymerizable component (X) composed of 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 polymerizing it by massive polymerization or suspension polymerization.
A method for producing a macromonomer copolymer (Y), wherein the polymerizable component (X) contains 3.0 mol% or more of the macromonomer (a).

(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 independent hydrogen atoms or methyls, respectively. Group. Z is a terminal group. N is a natural number from 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) [1]. A method for producing a macromonomer copolymer (Y).
[3] The macromonomer copolymer of [1] or [2] used in the bulk polymerization or suspension polymerization, in which the viscosity of the syrup composed of the polymerizable component (X) at 25 ° C. is 7,000 mPa · sec or less. (Y) manufacturing method.
[4] The method for producing a 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 reaction rate of macromonomers.
The macromonomer copolymer (Y) produced by the production method of the present invention has a small amount of residual macromonomer.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the following description and is within the scope of the gist thereof. It can be modified in various ways.
In the following, the monomer component before polymerization is referred to as "-monomer", and "monomer" may be omitted. Further, the monomer unit constituting the polymer is referred to as "-derived unit" or "-unit". Further, the (meth) acrylate indicates methacrylate or 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) composed of a 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 from 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.

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

Examples of the alkyl groups of R and R ¹ to R ⁿ include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group and an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a 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, due to the availability, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, and octyl group are used. Preferably, 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.

Examples of the cycloalkyl groups of R and R ¹ to R ⁿ include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, an adamantyl group and the like. Cyclopropyl group, cyclobutyl group, and adamantyl group are preferable because of their availability.

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

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

The substituents of R or R ¹ to R ⁿ are independently an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, and the like. It is 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. Examples include groups or atoms. In addition, R'or R'independently includes the same group as R except for the heterocycle.

Examples of the alkoxycarbonyl group as a substituent of R or R ¹ to R ⁿ include a methoxycarbonyl group.
Examples of the carbamoyl group as a substituent of 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 of R or R ¹ to R ⁿ include a dimethylamide group.
Examples of the halogen atom as a substituent of R or R ¹ to R ⁿ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group as the substituent of R or R ¹ to R ⁿ include 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 an alkali salt of a carboxy group, an alkali salt of a sulfoxyl group, a polyethylene oxide group, a poly (alkylene oxide) such as a polypropylene oxide group. ) Groups and cationic substituents such as quaternary ammonium bases.

As R and R ¹ to R ⁿ , at least one selected from an alkyl group and a cycloalkyl group is preferable, and an alkyl group is more preferable.
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 easy availability.

[X ₁ to X _n ]
In the general formula (1), X ₁ to X _n are hydrogen atoms or methyl groups, respectively, and a methyl group is preferable. Further, from the viewpoint of easiness of synthesizing the macromonomer (a), it is preferable that more than 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 of the number average molecular weight Mn of the macromonomer (a) is more preferably 1,000 or more, further preferably 1,500 or more. Further, the upper limit of the number average molecular weight Mn of the macromonomer (a) is more preferably 50,000 or less, further preferably 20,000 or less. When the number average molecular weight Mn is at least the lower limit value, the macromonomer copolymer (Y) can be imparted with compatibility and physical properties derived from the macromonomer (a). When 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 the calibration curve of polymethylmethacrylate using gel permeation chromatography (GPC).

The macromonomer (a) may be a mixture of two or more kinds of macromonomers. In that case, the number average molecular weight Mn is calculated as the value of 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), resulting in a higher molecular weight. The macromonomer (b) having a large molecular weight plays a role of ensuring compatibility with the matrix resin when used as an additive.
Of the whole macromonomer (a), it is preferable that the macromonomer having a number average molecular weight Mn of 5,000 or less is contained in an amount of 20% by mass or more, and more preferably 30% by mass or more.

[Raw material monomer of macromonomer (a)]
Examples of the monomer (raw material monomer) for obtaining the macromonomer (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl. (Meta) 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 and other (meth) acrylates; Hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; (meth) acrylic acid, 2- ( Meta) Acryloyloxyethyl Hexahydrophthalic Acid, 2- (Meta) Acryloyloxypropyl Hexahydrophthalic Acid, 2- (Meta) Acryloyloxyethylphthalic Acid, 2- (Meta) Acryloyloxypropylphthalic Acid, 2- (Meta) Acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid , Monomethyl maleate, monomethyl itaconate and other carboxy group-containing vinyl monomers; Maleic anhydride, itaconic acid anhydride and other acid anhydride group-containing vinyl monomers; , 3,4-Epoxy group-containing vinyl-based monomer such as epoxybutyl (meth) acrylate; Amino group-containing (meth) acrylate-based vinyl-based single such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. Quantities; (meth) acrylamide, N-t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid Acrylate, Murray Vinyl-based monomers containing amide groups such as mid; vinyl-based monomers such as styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate; divinylbenzene, ethylene Glycoldi (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 Examples thereof include polyfunctional vinyl-based monomers such as propylene glycol di (meth) acrylate, trimethyl propanetri (meth) acrylate, allyl (meth) acrylate, and N, N'-methylenebis (meth) acrylamide. One or more of these can be appropriately selected and used.
Among these, methacrylate (methacrylic acid ester) is preferable in terms 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, and methyl methacrylate and n-butyl methacrylate are preferable. And 2-ethylhexyl methacrylate are more preferred.

Further, 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 the molded product containing the macromonomer copolymer (Y). 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. Of 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) which is a product and the molded product containing the same. More than 100% by mass is preferable. The content of methacrylate is more preferably 82% by mass or more and 99% by mass or less, and further 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.

[Manufacturing method of macromonomer (a)]
The macromonomer (a) can be produced by a known method. Examples of the method for producing a macromonomer include a method for producing a macromonomer using a cobalt chain transfer agent (US Pat. No. 4,680,352) and a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (US Pat. No. 4,680,352). International Publication No. 88/04304), a method for 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). ) Etc. can be mentioned.
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 the cobalt chain transfer agent include a bulk polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method such as 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, the cobalt chain transfer agent represented by the formula (2) can be used, and for example, Japanese Patent No. 3587530, US Pat. No. 4,526,945, and No. 4694054 can be used. , No. 4886861, No. 5324879, International Publication No. 95/17435, Japanese Patent Application Laid-Open No. 9-510499, Japanese Patent Application Laid-Open No. 2012-158696, etc. Can be done.

[In the formula, R ₁ to R ₄ are independently alkyl groups, cycloalkyl groups and aryl groups; X are independently F atoms, Cl atoms, Br atoms, OH groups, alkoxy groups and aryls, respectively. It is 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 (borondifluorodiphenylglioxymate). Cobalt (II), Cobalt (II) complex of bicinaluiminohydroxyimino compound, Cobalt (II) complex of tetraazatetraalkylcyclotetradecatetraene, N, N'-bis (salicylidene) ethylenediaminocobalt (II) complex , Cobalt (II) complex of dialkyldiazadioxodialkyldodecadien, cobalt (II) porphyrin complex and the like. Of these, bis (borondifluorodiphenylgrioxymate) cobalt (II) ( _R1 to _R4 : 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 the monomers for obtaining the macromonomer (a). If the amount of the cobalt chain transfer agent used is less than 20 ppm, the decrease in molecular weight tends to be insufficient, and if it exceeds 350 ppm, the obtained 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 the report by Yamada et al. (Prog. Polym. Sci. 31 (2006) p835-877) and the like. Specifically, the terminal double bond group of the macromonomer (a) can form a branched structure in the copolymerization reaction with the acrylate and can be copolymerized. 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 branch structure is mainly reopened to generate the terminal double bond group and the radical of the methacrylate growth end. When styrene is used as the comonomer (b), a branched structure can be formed, but the reaction progresses extremely slowly and is not industrial. Therefore, it is preferable that the comonomer (b) contains acrylate (b1) as a main component, and methacrylate (b2) or another monomer (b3) is used as needed.

[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 needed. Specifically, the same as the monomer for obtaining the macromonomer (a) can be mentioned, but it is preferable to mainly use the acrylate (b1) in terms of the reactivity with the macromonomer (a) described above. Moreover, methacrylate (b2) and other monomers (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, and n-lauryl acrylate. Acrylate such as n-stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Hydroxyl-containing acrylates such as 4-hydroxybutyl acrylate and glycerol acrylate; acrylic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxypropyl Phthalic acid, 2-acryloyloxyethyl maleic acid, 2-acryloyloxypropylmaleic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxypropylsuccinic acid, carboxy group-containing acrylate; , 3,4-Epoxy group-containing acrylates such as butyl acrylate; Amino group-containing acrylates such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate; Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol Examples thereof include polyfunctional acrylates such as diacrylates, triethylene glycol diacrylates, tetraethylene glycol diacrylates, tripropylene glycol diacrylates, trimethylolpropane triacrylates and allyl acrylates. 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, preferably methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n -Lauryl acrylate, phenyl acrylate, benzyl acrylate and phenoxyethyl acrylate are particularly preferable.

In one aspect of the present invention, for the purpose of imparting flexibility, impact resistance and adhesiveness, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl. Acrylate and 4-hydroxybutyl acrylate can be used.
Further, 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 the purpose of ensuring compatibility with the macromonomer (a), for example, methyl acrylate, ethyl acrylate and the like can be used.

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, and 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, Hydroxyl-containing methacrylates such as 4-hydroxybutyl methacrylate and glycerol methacrylate; methacrylic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxypropyl hexahydrophthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloxypropyl Propyl-containing methacrylates such as phthalic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxypropylmaleic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloxypropyl succinic acid; -Epyl group-containing methacrylate such as epoxy butyl methacrylate; amino group-containing methacrylate such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, tri Polyfunctional methacrylates such as ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, allyl methacrylate; and the like can be mentioned. 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, preferably methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n. -Lauryl methacrylate, phenyl methacrylate, benzyl methacrylate and phenoxyethyl methacrylate are particularly preferable.

Examples of the other monomer (b3) include carboxy group-containing vinyl monomers such as crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate; Acid anhydride group-containing vinyl-based monomer; (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) Vinyl-based monomers containing amide groups such as acrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc .; styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate, etc. Vinyl-based monomers; polyfunctional vinyl-based monomers such as divinylbenzene and N, N'-methylenebis (meth) 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 of the acrylate (b1), more preferably 70% by mass or more, and further preferably 80% by mass or more, based on 100% by mass of the 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 the reactivity with the macromonomer (a) described above (b1: b2) = 65: 35 to 100. It is preferably in the range of: 0, more preferably in the range of (b1: b2) = 70:30 to 100: 0, and even more preferably in the range of (b1: b2) = 80:20 to 100: 0. ..
By keeping the ratio of the acrylate (b1) and the methacrylate (b2) within the above range, the reactivity between the macromonomer (a) and the commonomer (b) is ensured, and the block contained in the macromonomer copolymer (Y) is contained. The proportion of 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 be sufficiently increased, or the reaction time may become too long.
It is preferable that the amount of the other monomer (b3) used is small. For example, the ratio of the monomer (b3) to 100% by mass of the total of the comonomer (b) is preferably 10% by mass or less, more preferably 5% by mass or less. It may be zero.

As for the molar ratio of the macromonomer (a) and the comonomer (b), the macromonomer (a) is 3.0 mol% or more when the total polymerizable component contained in the polymerizable component (X) is 100 mol%. It is preferably present, more preferably 3.2 mol% or more, still more preferably 3.4 mol% or more. When the macromonomer (a) is 3.0 mol% or more, it is possible to prevent the polymer chain composed of the comonomer (b) from cross-linking during polymerization.
When the comonomer (b) contains the acrylate (b1) as a main component, branching may occur due to the generation of mid-chain radicals 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 cross-linking of the macromonomer copolymer (Y). I found that I could do it.

[Radical polymerization initiator]
When the polymerization reaction is carried out 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 organic peroxides include, for example, 2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, and the like. Octanoyl peroxide, t-butyl peroxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroper Examples thereof include oxides and di-t-butyl peroxide.
Specific examples of the azo compound include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 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 in the 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).
The polymerization temperature is not particularly limited, and is, for example, −100 to 250 ° C., preferably 0 to 200 ° C.

[Viscosity of syrup]
The polymerizable component (X) composed of the macromonomer (a) and the comonomer (b) can be obtained as a 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. Since suspension polymerization relies on mechanical shear to disperse the polymerizable component, it is necessary to keep the viscosity of the syrup below a certain level. The viscosity of the syrup composed of the polymerizable component (X) at 25 ° C. is preferably 7,000 mPa · sec or less, more preferably 5000 mPa · sec or less, and even more preferably 3000 mPa · sec or less. If the viscosity of the syrup at 25 ° C. is 7,000 mPa · sec or less, the droplets can be uniformly dispersed in the aqueous solution.
The viscosity of the 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) contains a block / graft copolymer (Y1) containing both a unit derived from the macromonomer (a) and a unit derived from the comonomer (b). In addition, a polymer (Y2) consisting of only a comonomer (b) unit and an unreacted macromonomer (a) may be contained. It is preferable that the content of the polymer (Y2) and the unreacted macromonomer (a) is small.

Since the polymer (Y2) consisting 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). More preferred.

The unreacted macromonomer (a) may interfere with the control of the microphase-separated structure when the macromonomer copolymer (Y) is used as an additive for various resins. Further, 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, still more preferably 10% by mass or less, based on 100% by mass of the macromonomer copolymer (Y). ..

The mass average molecular weight Mw of the macromonomer copolymer (Y) is preferably 30,000 or more and 10,000,000 or less, more preferably 50,000 or more and 8,000,000 or less, and 100,000 or more and 6,000, More preferably, it is 000 or less. When the mass average molecular weight Mw is 30,000 or more, the mechanical strength and heat-resistant decomposition property of the resin molded body are good, and when it is 10,000,000 or less, the moldability and the solubility in the matrix resin are good.

[Manufacturing 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 equivalent to suspension polymerization, and a desired molded product can be obtained by injecting a monomer-containing composition containing a polymerizable component (X) into a mold, polymerizing and curing the mixture. Since the macromonomer copolymer (Y) can be obtained as fine beads (particles) by suspension polymerization, it can be used as it is for melt molding as a molding material, or it can be mixed with other resins and used as an additive, or as a paint. It can also be used as a component of adhesives and adhesives.

[Production of macromonomer copolymer (Y) by suspension polymerization]
For example, when the macromonomer copolymer (Y) produced by suspension polymerization is used and the macromonomer copolymer (Y) is produced by suspension polymerization, it is preferable to include the steps i) to v) below.

i) Syrup preparation step The beads of the macromonomer (a) are dissolved in the comonomer (b) to prepare the syrup. At the time of preparing the syrup, it is preferable to raise the temperature of the mixture composed of the macromonomer (a) and the comonomer (b) within the range below the boiling point of the comonomer to help 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 in which the radical polymerization initiator does not react, the radical polymerization initiator can be mixed at the same time to prepare the initiator-containing syrup.

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 higher than the temperature obtained by subtracting 15 ° C. from the 10-hour half-life temperature of the radical polymerization initiator.

iii) Step of preparing an aqueous solution The aqueous solution can contain a dispersant, an electrolyte, and other auxiliaries. The dispersity of the syrup droplets in the aqueous solution is controlled by the combination of the dispersant and the electrolyte.
As the water used for the aqueous solution, it is preferable to use deionized water from the viewpoint of controlling the dispersibility.
Examples of the dispersant include an alkali metal salt of poly (meth) acrylic acid, a polymer of an alkali metal salt of (meth) acrylic acid and a (meth) acrylic acid ester, and an alkali metal salt of sulfoalkyl (meth) acrylic acid. And (meth) acrylic acid ester copolymer, polystyrene sulfonic acid alkali metal salt, styrene sulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, or a combination of these monomers. Combined; Examples thereof include polyvinyl alcohol, methyl cellulose, starch and hydroxyapatite having a saponification degree of 70 to 100%. These can be used alone or in combination of two or more. Among these, a copolymer of an alkali metal salt of (meth) acrylic acid sulfoalkyl and a (meth) acrylic acid ester, which has good dispersion stability during suspension polymerization, and a (meth) acrylic acid alkali metal salt and (meth). ) A copolymer of acrylic acid ester is preferable. The amount of the dispersant added is, for example, in the range of 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of the polymerizable component (X).
Examples of the electrolyte include sodium carbonate, sodium sulfate, manganese sulfate and the like. The amount of the electrolyte added is, for example, in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the polymerizable component (X).

iv) Polymerization reaction step A mixture of syrup containing a radical polymerization initiator and an aqueous solution is stirred to prepare a suspension (monomer-containing composition) in which syrup droplets are dispersed. Then, the temperature of the suspension is raised while stirring, and the polymerization reaction is started. It is preferable to perform degassing under reduced pressure or nitrogen substitution for the purpose of removing dissolved oxygen contained in the syrup and the aqueous solution in any of the steps before the temperature is raised and the polymerization is started.
The polymerization temperature is an important polymerization condition for efficiently obtaining a macromonomer copolymer (Y) made of a block / graft copolymer. 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 even more preferably 65 ° C. to 75 ° C. If the polymerization temperature is too low, there is a concern that the reaction will proceed slowly and the polymerization time will be long. Further, if the polymerization temperature is too high, cleavage of the reaction intermediate is prioritized and it becomes difficult to form a block / graft polymer.
At the end of the polymerization reaction, the temperature of the suspension can be raised for the purpose of increasing the reaction rate of the polymerizable component (X) and eliminating the unreacted radical polymerization initiator. The temperature for raising the temperature is preferably 80 ° C. or higher, more preferably 85 ° C. or higher. The temperature rise time may be determined by calculating the time until the radical polymerization initiator disappears, but it is preferably about 60 minutes to 2 hours.

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

[Use]
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 a melt-moldable molding material for various molded bodies such as sheets, films, various housings and covers, and light guides. In addition, it can be used as a paint or an adhesive by applying it after dissolving it in a solvent.
When the macromonomer copolymer (Y) is used as an additive for other resins, the main component resin is, for example, an acrylic resin such as polymethyl methacrylate, a polyolefin, a polyamide, an unsaturated polyester, or a polyethylene terephthalate. , Saturated polyester such as polybutylene terephthalate, polycarbonate, polystyrene, ABS resin, AS resin, polyvinyl chloride, polylactic acid, polyvinylidene fluoride and the like.
The functions that the macromonomer copolymer (Y) imparts to other resins include flexibility, toughness, impact resistance, weather resistance, processability, mold releasability, scratch resistance, surface hardness, compatibility, and crystal size. Control, ductility, etc. can be mentioned.
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 carried out using a monomer-containing composition containing a polymerizable component (X), the macromonomer (a) contained in the polymerizable component (X) is 3.0. When the content is mol% or more, the macromonomer (a) is given a role as a chain transfer agent. When the comonomer (b) contains the acrylate (b1) as a main component, cross-linking is likely to occur in the polymer chain containing the comonomer (b) unit during the production of the macromonomer copolymer (Y), but the macromonomer (a) is chained. By acting as a transfer agent, cross-linking can be prevented.
Further, the macromonomer (a) plays a role as a chain transfer agent in the process of the copolymerization reaction with the comonomer (b), and then is finally incorporated 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 thermostable decomposition property of the obtained 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 embodiment of Patent Document 3, the sulfur-containing chain transfer agent is used in an amount of 0.05 to 0.2 parts by mass with respect to 100 parts by mass of the polymerizable component (X) to prevent cross-linking of the copolymer. However, as shown in the comparative example 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 for 100 parts by mass of the polymerizable component (X) is less than 0.01 parts by mass, it is possible to prevent cross-linking from occurring during the polymerization reaction. Can be done. The monomer-containing composition does not contain a sulfur-containing chain transfer agent, or when it contains a sulfur-containing chain transfer agent, it is preferably less than 0.01 part by mass with respect to 100 parts by mass of the polymerizable component (X).
Examples of sulfur-containing chain transfer agents include alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan.

In the following, "parts", which is a unit of the blending amount, means "parts by mass".
<Measurement method / evaluation method>
[Analysis method for macromonomer copolymer (Y)]
[GPC measurement]
Mw and Mn were determined using gel permeation chromatography (GPC). The measurement conditions are shown below.
Equipment: HLC-8220 (manufactured by Tosoh)
Column: TSK GUARD COLUMN SUPER H-H (4.6 x 35 mm, manufactured by Tosoh) and two TSK-GEL SUPER HM-H (6.0 x 150 mm, manufactured by Tosoh) connected in series Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow velocity: 0.6 mL / min Mw (mass average molecular weight) and (Mn) number average molecular weight are polymethylmethacrylate (Mp (peak molecular weight) = 141,500, 55,600, 11,100 and 1, manufactured by Polymer Laboratories. It was calculated using a calibration curve prepared using 4 types of 590).

[NMR measurement]
The reaction rate of the comonomer (b) is determined by ^{1 1} H-NMR measurement. ^{1 1} H-NMR measurement was carried out using a nuclear magnetic resonance apparatus. The measurement conditions are shown below.
Equipment: UNITY INOVA500 (manufactured by Varian)
Deuterated 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 of 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.
Equipment: Alliance e2695 (manufactured by Waters)
Column: TSKgel ODS100V (5 μm, 4.6 x 150 mm, manufactured by Tosoh Corporation)
Eluent: acetonitrile (solution A), tetrahydrofuran (solution B)
Gradient condition: Linear gradient 0 minutes (Liquid A / Liquid B = 100/0) -10 minutes (Liquid A / Liquid B = 0/100) -15 minutes (Liquid A / Liquid B = 0/100)
Measurement temperature: 40 ° C
Flow velocity: 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 prepare a sample solution. Further, the macromonomer (a) was dissolved in tetrahydrofuran to prepare a standard solution. A calibration curve was prepared 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 heat-resistant decomposition (measurement of 5% weight loss temperature)]
Thermal decomposition was assessed by tracking the weight loss of the polymer under measurement using a thermogravimetric / differential thermal analyzer. The measurement conditions are shown below.
Equipment: TG / DTA6300 manufactured by SII Nanotechnology Inc.
Measurement conditions: Nitrogen air flow 200 mL / min, 40 ° C to 550 ° C, heating rate 10 ° C / min

[Measurement of syrup viscosity]
Viscosity measurements were 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 the presence or absence of cross-linking]
The presence or absence of cross-linking was determined by whether it could be dissolved in tetrahydrofuran. After 5 mL of tetrahydrofuran was added to 10 mg of the target polymer to dissolve it, the solution was passed through a Cosmonice filter S (manufactured by Merck, pore size 0.45 μm), and if filtration was not possible, it was determined that there was cross-linking.

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

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

<Production Example 2: Synthesis of Chain Transfer Agent (1)>
Cobalt (II) acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) 2.00 g (8.03 mmol) and diphenylglycime (Tokyo Kasei) in a synthesizer equipped with a stirrer under a nitrogen atmosphere. 3.86 g (16.1 mmol) of EP grade manufactured by the same company and 100 ml of diethyl ether previously deoxidized by nitrogen bubbling were added, and the mixture was stirred at room temperature for 2 hours.

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

<Production Example 3: Synthesis of macromonomer (a-1)>
In a polymerization apparatus equipped with a stirrer, a condenser and a thermometer, 135 parts of deionized water, 0.1 part of sodium sulfate (Na ₂ SO ₄ ) and the dispersant (1) (solid content 10) produced in Production Example 1 (% by 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 parts of the chain transfer agent (1) produced in Production Example 2, and Perocta O (1,1,3,3 manufactured by Nichiyu Co., Ltd.) as a polymerization initiator. -Tetramethylbutylperoxy2-ethylhexanoate, trade name) 0.13 part was added to prepare an aqueous dispersion.

Next, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, the temperature of the aqueous dispersion was raised to 80 ° C., and then the temperature was raised to 90 ° C. for 3 hours, and then the temperature was raised to 90 ° C. and held for 2 hours. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension of macromonomer. The aqueous suspension was filtered through a filter cloth, the filtrate was washed with deionized water and dried at 40 ° C. for 16 hours to give the 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 of the chain transfer agent (1) and the polymerization initiator used were changed as shown in Table 1. .. The evaluation results are also shown in Table 1.

<Example 1: Synthesis of macromonomer copolymer (Y-1)>
50 parts of macromonomer (a-3) and 50 parts of n-butyl acrylate were added to a separable flask equipped with a stirrer, a cooling tube, and a thermometer, 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 a uniform syrup. The viscosity of the syrup was measured and found to be 770 mPa · sec (25 ° C.).
The polymerizable component (X) is composed of a macromonomer (a-3) and n-butyl acrylate, and the macromonomer (a) in the polymerizable component (X) is 4.5 mol%.

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

<Examples 2 to 3, Comparative Examples 1 to 3>
The polymerization formulation was changed to the contents shown in Table 2 to produce a macromonomer copolymer (Y). The contents not shown in Table 2 were carried out 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) contained 3.0 mol% or more of the macromonomer (a), the macromonomer copolymer (Y) was obtained without cross-linking. Both the reaction rate of the macromonomer (a) and the reaction rate of the comonomer (b) were high, and the heat-resistant decomposition property was also good.
Further, in the measurement results of HPLC, no peak was detected at the position corresponding to the retention time of the polymer consisting only of the comonomer (b) unit in any of the samples of Examples 1 to 3. That is, in Examples 1 to 3, a macromonomer copolymer (Y) containing only a comonomer (b) unit and not containing a polymer (Y2) was obtained.

On the other hand, in Comparative Examples 1 and 2 in which the macromonomer (a) in the polymerizable component (X) was less than 3.0 mol%, the macromonomer copolymer (Y) was crosslinked. Therefore, no measurements were made for items other than the presence or absence of cross-linking.
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 the chain transfer agent, cross-linking was prevented, but the macromonomer. The reaction rate of (a) was low. The content of the unreacted macromonomer (a) in the macromonomer copolymer (Y) was 25% by mass.
The reason why the 5% weight loss temperature is high even though the macromonomer copolymer (Y) of Comparative Example 3 contains a large amount of the unreacted macromonomer (a) is the unreacted macromonomer (a). It is considered that this is because the terminal double bond has disappeared in a part of. In this phenomenon, after a radical is added to the macromonomer (a) during the copolymerization reaction, the radical generated at the end of the macromonomer (a) reacts with n-octyl mercaptan, and the terminal double bond disappears. It is thought that this is the reason. That is, since a part of the remaining macromonomer (a) does not have a terminal double bond, depolymerization does not occur and the heat-decomposability is high, but the copolymerizability with the comonomer (b) is lost, and n-octyl is lost. It is considered that mercaptan inhibited the formation of macromonomer copolymer.

Claims (3)

A monomer-containing composition containing a polymerizable component (X) composed of a macromonomer (a) represented by the following general formula (1) and a comonomer (b) copolymerizable with the macromonomer (a) is polymerized in bulk or A method for producing a macromonomer copolymer (Y) by subjecting it to a polymerization reaction by suspension polymerization.
The comonomer (b) contains 80% by mass or more of the acrylate (b1), and the comonomer (b) contains 80% by mass or more.
A method for producing a macromonomer copolymer (Y), wherein the polymerizable component (X) contains the macromonomer (a) in an amount of 3.2 mol% or more and 4.5 mol% or less.

(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 independent hydrogen atoms or methyls, respectively. Group. Z is a terminal group. N is a natural number from 2 to 10,000.) The first aspect of claim 1, wherein 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 a macromonomer copolymer (Y). The macromonomer copolymer (Y) according to claim 1 or 2, wherein the syrup composed of the polymerizable component (X) used in the bulk polymerization or suspension polymerization has a viscosity of 7,000 mPa · sec or less at 25 ° C. Manufacturing method.