Method for producing macromonomers

Abstract

To provide a production method that can produce a macromonomer containing a carboxy group, while suppressing the inactivation of a cobalt catalyst in a reaction step.SOLUTION: According to a production method, a methacrylate including an acetal group is polymerized in a reaction vessel including water, enabling the production of a macromonomer including a carboxy group generated from the hydrolysis of the acetal group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a macromonomer. [Background technology]

[0002] Conventionally, polymers obtained by radical polymerization have been used in paints, resists, films, dispersants, These polymers are widely used in the fields of surface conditioners, molding materials, etc. The physical and chemical properties required vary depending on the material. This can be done by combining various ethylenically unsaturated monomers (monomers) that are used as raw materials. However, in recent years, further improvements in the performance of polymer materials have been made in each application. These demands cannot be met by simply adjusting the combination of the above ingredients. It is becoming like this.

[0003] Therefore, in order to further improve the performance of polymers, polymers with different properties are linked in a linear chain. Polymers that are combined with the backbone polymer (block copolymers), polymers with different properties or the same properties Polymers with branched bonds (graft copolymers) are being investigated. Catalytic Chain Transfer Polymerization Using a Ruthenium Catalyst obtained by CCTP (Chemical Polymerization: CCTP method) The macromonomer is polymerized with other copolymerizable monomers to produce block / group polymers. Methods for obtaining RAFT copolymers are being investigated.

[0004] In addition, as a method for changing the properties of block / graft copolymers, polar groups (acidic groups, In this method, polar groups are introduced into the block / graft copolymer. By containing the group, hydrophilicity is improved and it can be used as a useful pigment dispersant. do.

[0005] As a method for introducing polar groups into block / graft copolymers, macromonomers containing polar groups have been However, in the CCTP method, the covalent bond is broken down under acidic or basic conditions. However, the catalyst is deactivated, making it difficult to efficiently introduce polar groups.

[0006] In Patent Document 1, a solution polymerization method is used, and a cobalt catalyst is added to compensate for the deactivated cobalt catalyst. A technique for synthesizing a polar group-containing macromonomer by adding a solvent has been disclosed. However, this method requires a large amount of solvent and a large amount of cobalt catalyst, which increases production costs. There are issues with this. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 3096645 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, the present invention provides a method for producing a macromonomer containing a carboxy group. The present invention also aims to provide a method for producing cobalt-based catalysts while suppressing deactivation of the cobalt catalyst in the reaction step. The object of the present invention is to provide a method for producing a macromonomer containing a carboxy group. [Means for solving the problem]

[0009] As a result of extensive research to solve the above problems, the present inventors have found that a compound containing an acetal group (methacrylamide) p) The acrylate is polymerized in a reaction vessel containing water, and the acrylate is hydrolyzed to form a carboxylic acid. The inventors have found that it is possible to produce macromonomers containing carboxyl groups, which led to the completion of the present invention. I arrived.

[0010] The present invention has the following aspects. [1] A polymerizable component containing an acetal group-containing (meth)acrylate and water are placed in a reaction vessel. and carrying out a polymerization reaction. [2] The macromonomer containing a carboxy group is represented by the following general formula (MM-1): [1] A method for producing a macromonomer having the structure:

[0011] [ka]

[0012] (Wherein R′ and Y 1 ~Y n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, Y is an alkyl group, an aryl group, a heterocyclic group, or a 1-alkyloxy group; 1 ~Y n At least One is a hydrogen atom, and the other is an X 1 ~X n are each independently a hydrogen atom or a methyl group, Z is a terminal group, and n is a natural number from 2 to 10,000. [3] The acetal group-containing monomer is represented by the following formula (1), (2), or (3): The macromonomer according to [1] or [2] is a (meth)acrylate containing a structure -Manufacturing method.

[0013] [ka]

[0014] (Wherein, X is —O -of Indication 、 R 1 and R 2 each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 and R 5 each represents an alkyl group, a cycloalkyl group, or an aryl group having 1 to 20 carbon atoms; R 4 teeth Represents an alkylene group having 1 to 10 carbon atoms. and R 6 represents an alkylene group having 2 to 10 carbon atoms .) [4] The method for producing a macromonomer according to any one of [1] to [3], wherein the polymerization reaction is aqueous polymerization, and the aqueous polymerization is one selected from the group consisting of suspension polymerization, miniemulsion polymerization, and emulsion polymerization. [5] A method for producing the macromonomer according to any one of [1] to [4], wherein the polymerization is carried out in the presence of a chain transfer agent represented by the following formula (7):

[0015] [ka]

[0016] (In the formula, R1 to R4 each independently represent an alkyl group or a cycloalkyl group.) or An aryl group; X's each independently represent a F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, or an alkyl group. or is an aryl group. [6] The method for producing a macromonomer according to any one of [1] to [5], wherein the (meth)acrylate having an acetal group is contained in an amount of 1 mass% or more relative to 100 mass% in total of polymerizable components including the (meth)acrylate having an acetal group. [7] The method for producing a macromonomer according to any one of [1] to [6], wherein the methacrylate is contained in an amount of 80% by mass or more relative to 100% by mass of the total of polymerizable components including the (meth)acrylate having an acetal group. [8] The method for producing a macromonomer according to any one of [1] to [7], wherein the macromonomer has a number average molecular weight of 500 to 100,000. [Effects of the Invention]

[0017] The present invention provides a method for efficiently producing a macromonomer containing a carboxy group. Furthermore, the present invention can prevent the deactivation of the cobalt catalyst in the reaction step. The present invention provides a production method for efficiently producing a macromonomer containing a carboxy group while suppressing the It can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present embodiment will be described in detail below. Note that the following description is an embodiment of the present invention. The present invention is not limited to the following configurations. In the present invention, "(meth)acrylic" refers to the total of "acrylic" and "methacrylic". "(Meth)acrylate" is a general term for "acrylate" and "methacrylate." Methacrylates are methacrylic acid and methacrylic acid derivatives. Acid derivatives include methacrylates and methacrylic acid esters. Acrylic acid and acrylic acid derivatives. Acrylic acid derivatives include acrylates, acrylic acid derivatives, and "(Meth)acryloyl group" includes "acryloyl group" and "methacryloyl group". is a general term for the "acryloyl group" and is CH2=C(R)-C(=O)- (R is a hydrogen atom or a methyl The monomer component before polymerization is called a "monomer" and the "monomer The structural units that make up a polymer are sometimes abbreviated as "monomer units." This is what happens.

[0019] <(Meth)acrylate (X) containing an acetal group> The (meth)acrylate (X) containing an acetal group is hydrolyzable. The term "hydrolyzable" means that the (meth)acrylate (X) containing an acetal group reacts with water. The reaction produces decomposition products derived from (meth)acrylate (X) containing an acetal group. This means that the (meth)acrylate (X) unit containing an acetal group is hydrolyzed. Whether or not the product has been hydrolyzed can be confirmed by identifying the functional groups (carboxyl groups, etc.) produced by hydrolysis. do. By polymerizing (meth)acrylate (X) in a reaction vessel containing water, the polymerization reaction and hydration The decomposition reaction can be allowed to proceed to synthesize a macromonomer (A) containing a carboxy group.

[0020] The (meth)acrylate (X) containing an acetal group is represented by any one of the formulas (1) to (3): It is preferred that the structure include a structure that is

[0021] [ka]

[0022] (Wherein, X is —O -of Indication 、 R 1 and R 2 each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 and R 5 each represents an alkyl group, a cycloalkyl group, or an aryl group having 1 to 20 carbon atoms; R 4 represents an alkylene group having 1 to 10 carbon atoms, and R 6 represents an alkylene group having 2 to 10 carbon atoms.

[0024] R 1 and R 2 Examples of the alkyl group having 1 to 10 carbon atoms in group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, Examples include a 2-ethylhexyl group. R 1 and R 2 The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. More preferably, 1 or 2.

[0025] R 1 and R 2 Preferred combinations include a combination of a hydrogen atom and a methyl group, a combination of a methyl group and a hydrogen atom; and an alkyl group having 2 to 10 carbon atoms (hereinafter referred to as "long chain"). a combination of a methyl group and a long-chain alkyl group; Combinations of hydrogen atoms, combinations of long-chain alkyl groups, etc. Among these, in terms of hydrolysis, a combination of a hydrogen atom and a methyl group is preferred. is preferred.

[0026] R 3 Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, and a propyl group. propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, 2-ethyl group Examples of the alkyl group include an alkylhexyl group, a decyl group, a dodecyl group, and a tetradecyl group. The cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, for example, Examples include a cyclohexyl group and a cyclopentyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a naphthalene group, or the like. Examples thereof include a butyl group. R 3 As the alkyl group, an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms is preferred.

[0027] R 3 The alkyl group, cycloalkyl group, and aryl group in When the compound has a substituent, the number of the substituents may be one or two or more. Examples of the aryl group include a cycloalkyl group, an aryl group, an alkoxy group, and an alkanoyloxy group. groups, aralkyl groups, acetoxy groups, etc. Among the substituents, the cycloalkyl group and the aryl group are R 3 Cycloalkanes in The alkoxy group includes the same as the alkoxy group, eth ... Examples of the alkanoyloxy group include an alkoxy group, a propoxy group, and a butoxy group. Examples of the aralkyl group include a benzyl group.

[0028] X in formula (2) is the same as X in formula (1), and the preferred embodiments are also the same. R 4 Examples of the alkylene group having 1 to 10 carbon atoms in the formula (I) include a methylene group and an ethylene group. The number of carbon atoms in the alkylene group is, for example, 2 to 7 is preferred, and 3 to 4 is more preferred. The alkylene group may have a substituent. When the alkylene group has a substituent, the number of the substituent is one. The alkylene group may have one or more substituents, and may have two or more substituents. 3 Inoke The substituents are the same as those used for the aryl group.

[0029] X in formula (3) is the same as X in formula (1), and the preferred embodiments are also the same. R 5 is R in Eq. (1). 3 The same applies to the preferred embodiments. R 6 Examples of the alkylene group having 2 to 10 carbon atoms in the formula (I) include an ethylene group, a propylene group, and the like. The alkylene group preferably has 2 to 7 carbon atoms. It is preferable that the number is 3 to 4.

[0030] The (meth)acrylate (X) containing an acetal group includes those represented by the structure (1), the structure (2), It is preferable that the compound contains at least one structure selected from the group consisting of structures (3).

[0031] Examples of the (meth)acrylate (X) containing an acetal group include those represented by the following formula (M1-1 ), (M1-2) or (M1-3).

[0032] [ka]

[0033] (Wherein, X and R 1 ~R 6 is as defined above, and Q is CH2=CH-COO-, CH2 =C(CH3)-COO-, CHR X =CH-COO-, CH2=C(CH2R X )-C OO- or CH2=CR X -CH2COO-, R X is the structure (1), the structure (2), the structure (3) or an alkyl ester group.

[0034] In Q, CH2=CH-COO- is an acryloyloxy group, CH2=C(CH3) -COO- is a methacryloyloxy group. CH(CH3)=CH-COO- is a crotonoyloxy group (an ethylenically unsaturated bond) trans-form) or isocrotonoyloxy group (ethylenically unsaturated bond is cis-form). CHR X =CH-COO- means that the carboxyl group is structure (1), structure (2), structure (3) or is a maleinoyloxy group (an ethylenically unsaturated bond is substituted with an alkyl ester group) The ethylenically unsaturated bond is either trans or fumaroyloxy. R X The alkyl ester group in X1 It is expressed as R X1 is an alkyl group Indicates R X1 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. is particularly preferred. Q is CHR X =CH-COO-, CH2=C(CH2R X )-COO- or CH2=C R X -CHCOO-, when R in Q X has the same structure as the group to which Q is attached For example, the compound represented by formula (M1-1) is In the case of a compound, R in Q X is the structure (1)(-CR 1 R 2 -XR 3 ) or alkyl esters Preferably, it is a ter group. CH2=C(CH2R X )-COO- or CH2=CR X -CH2COO- is a carbon The hydroxy group is represented by the structure (1), the structure (2), the structure (3), or an alkyl ester group. R is a hydroxyl group. X is the same as above. Q is preferably CH2=CH-COO- or CH(CH3)=CH-COO- .

[0035] Specific examples of the monomer represented by formula (M1-1), (M1-2) or (M1-3) include: The following are some examples:

[0036] [ka]

[0037] <Macromonomer (A)> The macromonomer (A) of the present invention is a polymer having a radical polymerizable group. The macromonomer (A) of the invention has a carboxy group. When the macromonomer (A) has a radical polymerizable group, There is no particular limitation on the number of radically polymerizable groups, but it is preferable that the number is one.

[0038] The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an unsaturated bond include CH2=C(COOR)-CH2-, (meta) Examples include an acryloyl group, a 2-(hydroxymethyl)acryloyl group, and a vinyl group. Here, R is a hydrogen atom, an alkyl group which may have a substituent, or a an alicyclic group which may have a substituent, an aryl group which may have a substituent, a heteroaromatic group which may have a substituent, an aryl group, an optionally substituted non-aromatic heterocyclic group, an optionally substituted an aralkyl group, an alkaryl group which may have a substituent, an ... an organosilyl group, or a (poly)organosiloxane group which may have a substituent, represents an alkyloxy group.

[0039] Examples of the alkyl group include branched or linear alkyl groups having 1 to 22 carbon atoms. Specific examples of the branched or linear alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, and -propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, pentyl Amyl group, i-pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, Octyl group, i-octyl group, nonyl group, i-nonyl group, decyl group, i-decyl group, undecyl group Cyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group, pentadecyl group, Hexadecyl group, heptadecyl group, octadecyl group (stearyl group), i-octadecyl group, nonadecyl group, icosyl group, and docosyl group.

[0040] The alicyclic group may be a monocyclic group or a polycyclic group, and may be, for example, a group having 3 to 20 carbon atoms. As the alicyclic group, a saturated alicyclic group is preferable, and specific examples thereof include: , cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group butyl, bicyclo[2.2.1]heptyl, cyclooctyl, and adamantyl groups etc.

[0041] Examples of the aryl group include aryl groups having 6 to 18 carbon atoms. Specific examples of the aryl group of 8 include a phenyl group and a naphthyl group. Examples of the heteroaryl group include a pyridyl group and a carbazolyl group. Examples of the non-aromatic heterocyclic group include a pyrrolidinyl group, a pyrrolidone group, and a lactam group. Examples include: Examples of the aralkyl group include a benzyl group and a phenylethyl group.

[0042] Examples of organosilyl groups include -SiR 21 R 22 R 23 Examples of the group include a group represented by In addition, R 21 ~R 23 each independently represents an alkyl group which may have a substituent, It represents an alicyclic group which may have a substituent, or an aryl group which may have a substituent. R 21 ~R 23an alkyl group which may have a substituent, The alicyclic group and the aryl group which may have a substituent are the same as those described above for R. The alkyl group which may have a substituent, the alicyclic group which may have a substituent, and the substituted group An aryl group which may have a substituent is exemplified. 21 ~R 23 are the same group or may be different groups.

[0043] Examples of the (poly)organosiloxane group include -SiR 24 R 25 -OR 26 , or -(SiR 27 R 28 -O-)mR 29 Examples of such groups include groups represented by R 24 ~R 29 teeth each independently an alkyl group which may have a substituent, an alicyclic group which may have a substituent, represents a cyclic group or an aryl group which may have a substituent, and m represents an integer of 1 to 100. . R 24 ~R 29 The alkyl group, alicyclic group, and aryl group in 21 ~R 23 Examples of the groups include the same groups as those listed in the above.

[0044] The substituents that these groups may have are not particularly limited, and examples thereof include alkyl, group, aryl group, -COOR 30 , cyano group, -OR 31 , -NR 32 R 33 , -CON R 34 R 35 , halogen atoms, allyl groups, epoxy groups, siloxy groups, and hydrophilic or ionic groups. In this case, at least one selected from the group consisting of groups exhibiting carboxylic acid functionality is preferred. 30 ~ R 35 are each a hydrogen atom, an alkyl group which may have a substituent, or a R represents an optionally substituted alicyclic group or an optionally substituted aryl group. 30 ~R 35 to The alkyl group, alicyclic group, and aryl group in 21 ~R 23 The same groups as those listed in The following groups are mentioned: In addition, -COOR 30 R 30 is preferably a hydrogen atom or an unsubstituted alkyl group. The unsubstituted alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, for example: For example, a methyl group can be mentioned. -OR 31 R 31 is preferably a hydrogen atom or an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, for example, An example is a methyl group. -NR 32 R 33 R 32 and R 33 are each independently a hydrogen atom or an unsubstituted The unsubstituted alkyl group is preferably a C1 to C12 alkyl group. Examples include alkyl groups, such as a methyl group. -CONR 34 R 35 R 34 and R 35 are each independently a hydrogen atom or An unsubstituted alkyl group is preferred. The unsubstituted alkyl group preferably has 1 to 1 carbon atoms. 2 includes alkyl groups, such as methyl groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. can be done. Examples of the poly(alkylene oxide) group include polyethylene oxide and polypropylene. Examples include poly(alkylene oxide) groups such as pyrene oxide groups. Examples of the 1-alkyloxy group include groups represented by the following formula (4), (5) or (6): can be done.

[0045] [ka]

[0046] (In the formula, R 1 ~R 6 has the same meaning as above.)

[0047] Among the above, R is an alkyl group which may have a substituent, or a substituted An alicyclic group which may be substituted is preferred, and an unsubstituted alkyl group, an unsubstituted alicyclic group, or An alicyclic group having an alkyl group is more preferred, and a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, Octyl, cyclopropyl, cyclobutyl, isobornyl and adamantyl groups Preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t- More preferred are butyl, cyclopropyl, cyclobutyl, isobornyl and adamantyl groups. More preferable.

[0048] The macromonomer (A) is a polymer having a degree of polymerization of 2 or more and having a radical at the end thereof. A macromonomer having a polymerizable group introduced therein is preferred, and the macromonomer is represented by the following formula (MM-1): Monomers are more preferred.

[0049] [ka]

[0050] (Wherein R′ and Y 1 ~Y n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, Y is an alkyl group, an aryl group, a heterocyclic group, or a 1-alkyloxy group. 1 ~Y n At least One is a hydrogen atom. X 1 ~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.

[0051] (Meth)acrylate (X) containing an acetal group can be hydrolyzed to release a carboxyl group. The polymerization reaction of macromonomer (A) generates decomposition products containing acetal groups (methacrylonitrile). p) The hydrolysis of acrylate (X) proceeds at the same time, and decomposition products containing carboxyl groups are formed. In this case, a macromonomer (A) containing the formula (MM-1) as a part of the structural unit can be synthesized. The macromonomer represented by the formula Y 1 ~Y n becomes a hydrogen atom.

[0052] R' and Y 1 ~Y n The alkyl group, cycloalkyl group, aryl group, and heterocyclic group include The same groups as those in the chromonomer (A) can be used.

[0053] In addition, R' and Y 1 ~Y n R' and Y may have a substituent. 1 ~Y n is a substituent and each independently represents an alkyl group, an aryl group, a carboxy group, an alkoxy group, Carbonyl group (-COOR''), carbamoyl group (-CONR''R'''), cyano groups, hydroxy groups, amino groups, amide groups (-NR''R'''), halogen atoms, allyl groups, epoxy groups, alkoxy groups (-OR''), and groups that exhibit hydrophilic or ionic properties. Examples of the group include a group or atom selected from the group consisting of:

[0054] Representative examples of the respective substituents include an alkoxycarbonyl group and a methoxycarbonyl group. The carbamoyl group includes an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group. The amide group includes a dimethylamide group, and the halogen atom includes a fluorine atom. The alkoxy group includes a methoxy group. The hydrophilic or ionic group may be an alkali salt of a carboxyl group or a sulfoxyl group. Alkali salts of the group, poly(alkoxy) groups such as polyethylene oxide groups and polypropylene oxide groups Cationic substituents such as ethylene oxide groups and quaternary ammonium salt groups are also included.

[0055] X 1 ~X n are each a hydrogen atom or a methyl group, and a methyl group is preferred. From the viewpoint of ease of synthesis of macromonomer (A), X 1 ~X n More than half of the groups are methyl groups It is preferable.

[0056] Z is a terminal group of the macromonomer (A). The terminal group of the macromonomer (A) is For example, the terminal groups of the polymer obtained by known radical polymerization may contain hydrogen atoms and radicals. Examples of the groups include groups derived from a methyl polymerization initiator.

[0057] 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. The number average molecular weight Mn of the macromonomer (A) is preferably 1,500 or more. The upper limit of the number is more preferably 70,000 or less, and even more preferably 50,000 or less. If the average molecular weight Mn is within the above range, the macromonomer copolymer contains the macromonomer (A). It is possible to impart compatibility and physical properties derived from the polymer.

[0058] The number average molecular weight Mn of the macromonomer (A) was determined by gel permeation chromatography (GPC). It is a relative value calculated from a calibration curve using polymethyl methacrylate as the standard substance. means.

[0059] <Polymerizable component (Y)> The polymerizable component (Y) contains an acetal group-containing (meth)acrylate (X), and the acetal It is a monomer that can be copolymerized with (meth)acrylate (X) containing a methyl group. The component (Y) may be, for example, a compound having a radical polymerizable group. The radical polymerizable group contained in the alkylene group is preferably a group having an ethylenically unsaturated bond. As the polymerizable component (Y) other than the (meth)acrylate (X) containing an acetal group, various For example, Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate 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 acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzo Dimethyl (meth)acrylate, Isobornyl (meth)acrylate, 2-Methoxyethyl ( meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate (meth)acrylates such as methacrylate; 2-hydroxyethyl (meth)acrylate 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate acrylate, glycerol (meth)acrylate, and other hydroxyl group-containing (meth)acrylates; Meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2- (Meth)acryloyloxypropylhexahydrophthalate, 2-(meth)acryloyl Oxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxypropyl phthalate ) Acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl maleate Acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl succinic acid Xylopyrsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomaleic acid carboxyl group-containing vinyl monomers such as methyl ester, monomethyl itaconate, etc.; maleic anhydride, Acid anhydride group-containing vinyl monomers such as itaconic anhydride; glycidyl (meth)acrylate; Glydicyl α-ethyl acrylate, 3,4-epoxybutyl (meth)acrylate, etc. Epoxy group-containing vinyl monomer; dimethylaminoethyl (meth)acrylate, diethyl Vinyl-based (meth)acrylates containing amino groups, such as aminoethyl (meth)acrylate Monomers: (meth)acrylamide, Nt-butyl (meth)acrylamide, N-methyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl Dimethyl (meth)acrylamide, diacetone acrylamide, maleic acid amide, vinyl monomers containing amide groups such as vinylimides; styrene, α-methylstyrene, vinyl Toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol Lithium di(meth)acrylate, tripropylene glycol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, N, Polyfunctional vinyl monomers such as N'-methylenebis(meth)acrylamide; One or more of these can be appropriately selected and used. Among these, methacrylate (methacrylic acid ester) is the most popular due to the ease of obtaining the monomer. (ru) is preferred. Methacrylates include methyl methacrylate, n-butyl methacrylate, and lauryl methacrylate. Dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate Xyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate methyl methacrylate, n-butyl methacrylate, and 4-hydroxybutyl methacrylate are preferred. 2-ethylhexyl methacrylate and 2-ethylhexyl methacrylate are more preferred; The monomers may be used alone or in combination of two or more. At least a part of the polymerizable component (Y) is preferably a (meth)acrylic monomer. .

[0060] <Composition of polymerizable component (Y)> (Meth)acrylate containing an acetal group relative to 100% by mass of the total polymerizable component (Y) The proportion of (X) is preferably 1% by mass or more and 70% by mass or less, and more preferably 2% by mass or more and 60% by mass or less. More preferably, the content is 5% by mass or more and 50% by mass or less, and even more preferably, the content is 5% by mass or more and 50% by mass or less. If the proportion of meth)acrylate (X) units is equal to or greater than the above lower limit, the copolymer (X) containing an acetal group The hydrolysis property of methacrylate (X) is improved, and a macromonomer having a high content of carboxyl groups is obtained. The mer (A) can be synthesized.

[0061] The proportion of methacrylate to the total mass of the polymerizable component (Y) is preferably 80 mass % or more. It is preferable that the content is 90% by mass or more, and more preferable that the content is 100% by mass or less. If this is the case, macromonomers can be easily synthesized.

[0062] [Method for producing macromonomer (A)] The macromonomer (A) can be produced by a known method. For example, a method for producing the copolymer using a cobalt chain transfer agent (U.S. Pat. No. 4,680,352) is known. (Details) and the use of α-substituted unsaturated compounds such as α-bromomethylstyrene as chain transfer agents. method (International Publication No. 88 / 04304), and a method of chemically bonding a polymerizable group (Japanese Patent Application Laid-Open No. 608544). No. 5,147,952) and a method using thermal decomposition (Patent Patent Publication No. 11-240854). Among these, the method for producing macromonomer (A) is one that has a small number of production steps and is suitable for chain synthesis. The production method using a cobalt chain transfer agent is preferred in that it uses a catalyst with a high transfer constant. stomach.

[0063] Examples of the method for producing the macromonomer (A) using a cobalt chain transfer agent include: Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, mini-emulsion polymerization, and other aqueous polymerization methods Among these, the synthesis of macromonomer (A) is carried out in a reaction vessel. By including water in the polymer, the (meth)acrylate (X)-derived structural unit containing an acetal group can be Aqueous dispersion polymerization is preferred because it is easily hydrolyzed. In this case, adding water to the reaction vessel is also effective for synthesizing the macromonomer (A). be.

[0064] The cobalt chain transfer agent used in the present invention is a cobalt chain transfer agent represented by formula (7): Chain transfer agents can be used, for example, as described in Japanese Patent No. 3587530 and U.S. Pat. No. 452694 Specification No. 5, Specification No. 4694054, Specification No. 4886861, Specification No. 5324 879, International Publication No. 95 / 17435, Japanese Patent Publication No. 9-510499, Those described in Publication No. 2012-158696 and the like can be used.

[0065] [ka]

[0066] In formula (7), R1 to R4 each independently represent an alkyl group or a cycloalkyl group. or An aryl group; X's each independently represent a F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, or an alkyl group. or It is an aryl group.

[0067] Specific examples of cobalt chain transfer agents include bis(borondifluorodimethyldioxy) Iminocyclohexane)cobalt(II), bis(borondifluorodimethylglyoxy) mate) cobalt(II), bis(boron difluorodiphenylglyoximate) cobalt Cobalt(II), vicinaliminohydroxyimino complexes of cobalt(II), tetra Cobalt(II) complexes of azatetraalkylcyclotetradecatetraenes, N,N'-bi Bis(salicylidene)ethylenediaminocobalt(II) complexes, dialkyldiazadioxo Cobalt(II) complexes of dialkyldodecadienes, cobalt(II) porphyrin complexes, etc. Among them, bis(boron) diols, which exist stably in aqueous media and have a high chain transfer effect, are Difluorodiphenylglyoximate)cobalt(II) (R1 to R4: phenyl group, X: F atom) is preferred. One or more of these may be appropriately selected and used.

[0068] The amount of the cobalt chain transfer agent used was 20 ppm relative to 100 parts of the total amount of the polymerizable component (Y). The amount of cobalt chain transfer agent used is preferably from 20 ppm to 350 ppm. If the amount of the macromonomer (A ) is easy to color.

[0069] Usable radical polymerization initiators include organic peroxides and azo compounds. , organic peroxides, azo compounds, etc., depending on the solvent and raw materials used in the polymerization reaction. Specific examples of organic peroxides include 2,4-dichloro Benzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide -oxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxy Side, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl per oxide, lauroyl peroxide, diisopropylbenzene hydroperoxide t-butyl hydroperoxide, di-t-butyl peroxide, etc. Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2, 2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-di Among these, the most readily available At this point, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2, 2'-Azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) These radical polymerization initiators may be used alone or in combination of two or more. It can be used as such.

[0070] The amount of radical polymerization initiator used is 0. Preferably 0.05 parts by mass or more, more preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more When the amount of the radical polymerization initiator used is 0.005 or more, the radical polymerization In addition, the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. The amount of the radical polymerization initiator used is more preferably 1 part by mass or less, and even more preferably 1 part by mass or less. If the temperature is lower than this, the radical polymerization proceeds without runaway, which is preferable.

[0071] The macromonomer (A) preferably contains a methacrylate as a constituent unit. The ratio of the methacrylate units to the total amount of all the constituent units constituting the monomer (A) is Although there are no particular limitations, it is preferably 80% by mass or more, and more preferably 90% by mass or more. is particularly preferred, while the content is 100 mass % or less. The agent functions efficiently.

[0072] [Macromonomer copolymer] By copolymerizing the macromonomer (A) and the comonomer (d), a macromonomer copolymer is obtained. The comonomer (d) can be copolymerized with the macromonomer (A) to synthesize a polymer. The comonomer (d) is a monomer having the same properties as the polymerizable component (Y). - are some examples.

[0073] As the comonomer (d), acrylate is used in view of its applicability for copolymerization with the macromonomer (A). The acrylate preferably contains, relative to 100 mol % of the comonomer (d), It is preferably 50 mol % or more, more preferably 60 mol % or more, and even more preferably 70 mol % or more. Preferably, it may be 100 mol %. The content of comonomer (d) units in the macromonomer copolymer (unit: mass%) ) is 30% by mass or more and 95% by mass or less relative to 100% by mass of the total mass of the macromonomer copolymer. When the lower limit of the content of the comonomer (d) is 30% by mass or more, This allows the macromonomer copolymer to have the characteristics of the comonomer (d). The lower limit of the content of the monomer (d) is preferably 30% by mass or more, more preferably 35% by mass or more. On the other hand, the upper limit of the content of the comonomer (d) is preferably 40 mass % or more, and more preferably 40 mass % or more. If the content of the macromonomer (A) is 95% by mass or less, the macromonomer copolymer has the characteristics of the macromonomer (A). The upper limit of the content of the comonomer (d) is preferably 95% by mass or less. It is preferably 90% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0074] When the macromonomer copolymer contains the macromonomer (A) of the present invention, The macromonomer (A) can be added to the copolymer. Since the macromonomer (A) has a carboxy group, the macromonomer does not have a carboxy group. The glass transition temperature (Tg) can be increased compared to when no such polymer is used.

[0075] Macromonomer copolymers can be synthesized using radical polymerization initiators. The radical polymerization initiators used in the synthesis of mer (A) are the same as those used in the polymerization reaction. It can be appropriately selected depending on the solvent and raw materials used. [Example]

[0076] The present invention will be described in more detail below based on examples, but the present invention will not go beyond the gist thereof. Unless otherwise specified, the present invention is not limited to the following examples. Unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass".

[0077] [Measurement and evaluation method] <Molecular weight measurement> The number average molecular weight and weight average molecular weight are calculated based on the standard polymethyl methacrylate under the following conditions: The calculation was made as follows. Gel filtration chromatography (GPC) device: Tosoh Corporation, HLC-8320 column M Column (TSK-guardcolumn SuperH-H (4.6 x 35 mm, East (manufactured by Thor Corporation) and two TSKgel Super HM-H (6.0 x 150 mm, Tosoh Corporation) connected in series Sample solution: tetrahydrofuran (THF) solution of macromonomer (sample concentration 0.02 g / 10mL) 10μL Flow rate: 0.6mL / min Eluent: THF (stabilizer: butylhydroxytoluene (BHT)) Column temperature: 40℃

[0078] <1H NMR Measurement> A nuclear magnetic resonance spectrometer (JNM-ECZ400, manufactured by JEOL Ltd.) was used. Chloroform (measurement sample 100 mg / d2 chloroform 1 g) or deuterated dimethyl sulfoxide dimethyl sulfoxide (measurement sample 100 mg / deuterated dimethyl sulfoxide 1 g) at 23°C. Measured.

[0079] <Acid value measurement> Weigh out 1.0 g of macromonomer, 25 mL of toluene, and 25 mL of ethanol as indicators. Then, 0.05 g of an ethanol solution containing 1% by volume of phenolphthalein was added. Titrate with 0.1 mol / L KOH ethanol solution while stirring until the solution changes from colorless to pink. The point at which the color changed was taken as the end point, and the acid value was calculated using the following formula. Acid value (mgKOH / g)=A×5.611 (In the formula, A is the amount (mL) of 0.1 mol / L KOH ethanol solution added dropwise until the end point.) show)

[0080] <Production of (meth)acrylate (X) containing acetal groups (IBEMA)> Isobutyl vinyl ether 90.1 parts (0.9 mol), hydroquinone 0.14 parts, 0.28 parts of ethenothiazin was added and mixed at room temperature until uniform. Air (10 ml / m While blowing in 51.7 parts (0.6 mol) of methacrylic acid, the reaction mixture was heated to a temperature of 6 The temperature was kept below 0°C during the dropwise addition. After the dropwise addition, the temperature of the reaction mixture was raised to 80°C and the mixture was stirred for 6 hours. To the reaction mixture was added 158.7 parts (1.8 mol) of t-butyl methyl ether. The mixture was mixed, and the organic phase was washed once with 200 parts of a 20% by mass aqueous solution of potassium carbonate. Benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl 0.03 parts The resulting residue was distilled under reduced pressure to give a solution with a boiling point of 6 97.5 parts of 1-isobutoxyethyl methacrylate (IBEMA) at 0°C / 3 torr ( 0.52 mol) was obtained.

[0081] [Dispersant] <Production of Dispersant 1> In a polymerization apparatus equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube, 900 ml of deionized water was added. parts, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and Add 12 parts of methyl methacrylate (MMA) and stir. While replacing the inside of the polymerization apparatus with nitrogen, The temperature was raised to 50°C. 2,2'-azobis(2-methylpropane) 0.08 parts of pyonamidine dihydrochloride was added, and the temperature was further increased to 60°C. Using a pump, MMA was continuously added dropwise at a rate of 0.24 part / min for 75 minutes. After keeping the mixture at 60°C for 6 hours, it was cooled to room temperature and a transparent aqueous solution with a solid content of 10% by mass was obtained. Dispersant 1 was obtained.

[0082] <Production of Chain Transfer Agent 1> In a synthesis apparatus equipped with a stirrer, add cobalt(II) acetate tetrahydrate under a nitrogen atmosphere. 00g and diphenylglyoxime 1.93g, deoxygenated in advance by bubbling with nitrogen 80 mL of diethyl ether was added and stirred at room temperature for 30 minutes. 10 mL of methylcellulose diethyl ether complex was added and stirred for an additional 6 hours. The product was washed with diethyl ether and dried in vacuum for 15 hours to obtain chain transfer agent 1, which was a reddish-brown solid. 2.12g was obtained.

[0083] Example 1 In a polymerization apparatus equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube, 145 ml of deionized water was added. Add 0.1 part of sodium sulfate and 0.25 parts of dispersant 1 (solid content 10% by mass) and stir. Next, 35 parts of MMA, 55 parts of BMA, 10 parts of IBEMA, and MA were added to obtain a homogeneous aqueous solution. 5 parts of chain transfer agent 1, 0.004 parts of Perocta O (registered trademark) as a polymerization initiator The mixture was added to form an aqueous suspension. Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 75°C, and the reaction was carried out for 3.5 hours. To increase the temperature, the reaction mixture was heated to 90°C and maintained at that temperature for 1 hour. An aqueous suspension containing chromium monomer was obtained. This aqueous suspension was filtered through a filter. The residue remaining on the surface was washed with deionized water, dehydrated, and dried at 40°C for 16 hours to obtain macromonomers. The number average molecular weight and weight average molecular weight of this macromonomer are shown in Table 1.

[0084] <Examples 2 and 3> In Example 1, the amounts of the monomer, chain transfer agent, and polymerization initiator were as shown in Table 1. Examples 2 and 3 were carried out in the same manner as in Example 1, except that the macromonomers were The number average molecular weight and weight average molecular weight are shown in Table 1. The units of the blending amounts in Table 1 are all All are parts by weight.

[0085] <Comparative Example 1> In Table 1, the amounts of monomer, chain transfer agent, and polymerization initiator charged are as shown in Table 1. The polymer was obtained in the same manner as in Example 1, except that the units of the blending amounts in Table 1 are all All are parts by weight.

[0086] [Table 1]

[0087] The abbreviations in Table 1 are as follows: MMA: Methyl methacrylate BMA: Butyl methacrylate IBEMA: 1-Isobutoxyethyl methacrylate TBMA: t-butyl methacrylate MA: methyl acrylate Perocta O: 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate Route

[0088] [Table 2]

[0089] The acid value of the macromonomers produced in Examples 1 to 3 was titrated to determine the IBEMA-derived The value was almost the same as the theoretical value when the structural unit of Macromonomers containing hydroxy groups were synthesized.

[0090] The macromonomer produced in Comparative Example 1 was titrated for acid value, and the value was 0. That is, the TBMA-derived structural unit is not hydrolyzed and is a macromonomer that does not contain a carboxyl group. The nomer was synthesized.

[0091] For the polymer prepared in Example 1, 1 H NMR measurement revealed that the terminal double bonds In the case of the comparative example, a hydrogen peak was confirmed, and the macromonomer was synthesized. For the polymer produced in 2, 1 H NMR measurement revealed that the terminal double bond No hydrogen peak was observed, and no macromonomer was synthesized.

Claims

1. A method for producing a macromonomer having a carboxy group, comprising charging a polymerizable component containing an acetal group-containing (meth)acrylate and water into a reaction vessel and carrying out a polymerization reaction.

2. 2. The method for producing a macromonomer according to claim 1, wherein the macromonomer containing a carboxy group has a structure represented by the following general formula (MM-1): 【Chemistry 1】 (Wherein R′ and Y １ ~Y ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a 1-alkyloxy group, and Y １ ~Y ｎ at least one of X is a hydrogen atom; １ ~X ｎ are each independently a hydrogen atom or a methyl group, Z is a terminal group, and n is a natural number from 2 to 10,000.

3. 3. The method for producing a macromonomer according to claim 1, wherein the (meth)acrylate containing an acetal group is a (meth)acrylate containing a structure represented by the following formula (1), (2), or (3): 【Chemistry 2】 (In the formula, X represents —O—; R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 3 and R 5 each represent an alkyl group, cycloalkyl group, or aryl group having 1 to 20 carbon atoms; R 4 represents an alkylene group having 1 to 10 carbon atoms; and R 6 represents an alkylene group having 2 to 10 carbon atoms.)

4. 4. The method for producing a macromonomer according to claim 1, wherein the polymerization reaction is aqueous polymerization, and the aqueous polymerization is one type selected from the group consisting of suspension polymerization, miniemulsion polymerization, and emulsion polymerization.

5. The method for producing the macromonomer according to claim 1 , wherein the polymerization is carried out in the presence of a chain transfer agent represented by the following formula (7): 【Transformation 3】 (In the formula, R １ ~R ４ are each independently an alkyl group, a cycloalkyl group, or an aryl group; and X are each independently an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.

6. 6. The method for producing a macromonomer according to claim 1, wherein the (meth)acrylate having an acetal group is contained in an amount of 1% by mass or more relative to 100% by mass of a total of polymerizable components including the (meth)acrylate having an acetal group.

7. The method for producing a macromonomer according to claim 1 , wherein the polymerizable component contains 80% by mass or more of methacrylate relative to a total of 100% by mass of polymerizable components including the (meth)acrylate having an acetal group.

8. The method for producing a macromonomer according to any one of claims 1 to 7, wherein the macromonomer has a number average molecular weight of 500 to 100,000.

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