CN102858826A - Production method for block copolymer and copolymer precursor - Google Patents

Production method for block copolymer and copolymer precursor Download PDF

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Publication number
CN102858826A
CN102858826A CN2011800178973A CN201180017897A CN102858826A CN 102858826 A CN102858826 A CN 102858826A CN 2011800178973 A CN2011800178973 A CN 2011800178973A CN 201180017897 A CN201180017897 A CN 201180017897A CN 102858826 A CN102858826 A CN 102858826A
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alkyl
repeating unit
alkylidene group
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CN102858826B (en
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新谷武士
立石祐一
冈户俊明
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Nippon Soda Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Abstract

Disclosed is a production method for a novel copolymer which is useful as a pigment dispersing agent or similar. The disclosed method is as follows: a polymer precursor is heated, said precursor containing: a block chain (A) formed from polymers containing at least one kind of repeating unit selected from the group consisting of a repeating unit having a tertiary amino group, and a repeating unit having a quaternary ammonium salt group; and a block chain (B) formed from copolymers containing repeating units having a polyoxyalkylene chain, and repeating units having a protected acidic group represented by formula (I). Thus, a block copolymer is produced which contains the block chain (A), and a block chain (B1) formed from copolymers containing repeating units having a polyoxyalkylene chain, and repeating units having an acidic group represented by formula (II).

Description

The manufacture method of segmented copolymer and copolymer precursor
Technical field
The present invention relates to manufacture method, and new copolymer precursor as the useful novel block copolymer of pigment dispersing agent.The application advocates right of priority 2010-092952 number to the Japan's patent application in application on April 14th, 2010, and its content is incorporated herein.
Background technology
Known following random copolymers: wherein comprise at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, contain the repeating unit of polyoxyalkylene chain and contain the repeating unit of acidic-group.
These polymkeric substance are owing to have based on the various characteristics of its specificity structure and studying in every field and developing.
In patent documentation 1, this random copolymers is applied to field of lithography.Particularly, having put down in writing by methacrylic acid, dimethylaminoethyl methacrylate, ethyl propenoate and molecular weight in the patent documentation 1 is multipolymer of obtaining of the ester cpds of 350 MPEG-550 and methacrylic acid etc.These are to adopt azobis isobutyronitrile (AIBN) as radical initiator, in the methylethyl ketone solvent, the mixing solutions of each monomer is carried out radical polymerization, thereby obtain as random copolymers.
In addition, in patent documentation 2, this random copolymers is used as the pigment dispersing agent in each field such as coating, printing ink, building materials.Particularly, put down in writing the random copolymers etc. of 10 parts of vinylbenzene, 15 parts of methyl methacrylates, 15 parts of β-dimethyl-aminoethylmethacrylates, 20 parts of methacrylic acids, 10 parts of methacrylic acid tridecyl esters, 20 parts of methacrylic acid PEG monomethyl ether (number-average molecular weight is 400), 10 parts of dimethylaminoethyl methacrylates in the patent documentation 2.These are to adopt 2, and 2 '-azo two (2,4-methyl pentane nitrile) is as radical initiator, in the alcohol mixture solvent of ethanol/methyl alcohol=95/5, the mixing solutions of each monomer is carried out radical polymerization, thereby obtain as random copolymers.
Patent documentation 1: Japanese kokai publication hei 6-128336
Patent documentation 2: TOHKEMY 2009-24165
Summary of the invention
The purposes of multipolymer becomes diversified in recent years, need to have the multipolymer of various characteristics.
For example, in the color liquid crystal display arrangement field, because the high-transmission rate of visible light and the demand of high-contrast are strengthened, therefore, pigment particles carries out micronize until below the visible at least light wavelength.Particulate like this, the specific surface area of pigment particles with usually compare increase, therefore, for the multipolymer that the existing pigment dispersing agent that uses is used always, the pigment-dispersing at initial stage and through the time dispersion stabilization insufficient.In addition, also require recently dispersing property high-performance in addition, existing multipolymer can't obtain sufficient performance.
In order to obtain to satisfy the multipolymer of above-mentioned performance, the manufacturing of the needs such as the present inventor is contained the segmented copolymer of block chain (A) and block chain (B1), described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, and described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains acidic-group that the repeating unit that contains polyoxyalkylene chain and formula (II) represent.
But the method for making the segmented copolymer that contains such structure is unknown.
The discoveries such as the present inventor, the copolymer precursor that contains block chain (A) and block chain (B) can be as the useful intermediate of segmented copolymer, described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, and described block chain (B) is formed by following multipolymer: this multipolymer contains the repeating unit of polyoxyalkylene chain and the repeating unit that formula (I) represents.
Find, by this copolymer precursor is heated, with the repeating unit that contains acidic-group of a repeating unit conversion accepted way of doing sth (II) expression of formula (I) expression, thus can the manufacturing objective segmented copolymer, so far finished the present invention.
That is, the present invention relates to following content,
(1) a kind of manufacture method of segmented copolymer; described segmented copolymer contains block chain (A) and block chain (B1); described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains acidic-group of the repeating unit that contains polyoxyalkylene chain and formula (II) expression; it is characterized in that; the copolymer precursor that contains block chain (A) and block chain (B) is heated; described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, and described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains the acidic-group of having protected that the repeating unit that contains polyoxyalkylene chain and formula (I) represent.
Figure BDA00002228158900031
(in the formula (I), R 1, R 2, R 3Represent independently of one another hydrogen atom or C1～C3 alkyl.X represents singly-bound or C1～C10 alkylidene group, is selected from-C(=O) OR 1a-,-C(=O) NHR 1a-,-OC(=O) R 1a-and-R 2a-OC(=O) R 1a-in group (R 1a, R 2aRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 4Expression hydrogen atom, C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl, R 5Expression C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl.）
Figure BDA00002228158900032
(in the formula (II), R 1, R 2, R 3, X the represents meaning identical with formula (I).）
(2) according to the manufacture method of (1) described segmented copolymer, it is characterized in that block chain (B) and (B1) further contain the repeating unit that formula (III) represents.
Figure BDA00002228158900041
(in the formula (III), R 6, R 7, R 8Represent independently of one another hydrogen atom or C1～C3 alkyl, R 9Expression C1～C10 alkyl or C6～C10 aryl C1～C6 alkyl.）
(3) according to the manufacture method of (1) or (2) described segmented copolymer, it is characterized in that the repeating unit that contains uncle's amino is the repeating unit that formula IV represents.
Figure BDA00002228158900042
(in the formula IV, R 10, R 11, R 12Represent independently of one another hydrogen atom or C1～C3 alkyl.Y represents C1～C10 alkylidene group, is selected from-C(=O) OR 1b-,-C(=O) NHR 1b-,-OC(=O) R 1b-and-R 2b-OC(=O) R 1b-in group (R 1b, R 2bRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 13, R 14Represent independently of one another C1～C6 alkyl or C6～C10 aryl C1～C6 alkyl.）
(4) according to the manufacture method of (1) or (2) described segmented copolymer, it is characterized in that the repeating unit that contains quaternary ammonium salt group is the repeating unit that formula V represents.
Figure BDA00002228158900043
(in the formula V, R 15, R 16, R 17Represent independently of one another hydrogen atom or C1～C3 alkyl.Y 1Expression C1～C10 alkylidene group, be selected from-C(=O) OR 1c-,-C(=O) NHR 1c-,-OC(=O) R 1c-and-R 2c-OC(=O) R 1c-in group (R 1c, R 2cRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 18, R 19, R 20The alkyl or the C6～C10 aryl C1～C6 alkyl that represent independently of one another C1～C6.Z -The expression counter ion.）
(5) according to the manufacture method of each described segmented copolymer in (1)～(4), it is characterized in that the repeating unit that contains polyoxyalkylene chain is represented by formula VI.
Figure BDA00002228158900051
(in the formula (VI), R 21, R 22, R 23Represent independently of one another hydrogen atom or C1～C3 alkyl.Z 1The expression be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1dExpression C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 24Expression C2～C4 alkylidene group, R 25Expression hydrogen atom or C1～C6 alkyl, m represents 2～150 arbitrarily integer, R 24O each other can be identical, also can be different.) and
(6) according to the manufacture method of each described segmented copolymer in (1)～(5), it is characterized in that, in the mixed solvent of the mixed solvent of glycol ether-ether series solvent and pure series solvent or glycol ether-ether series solvent and water, carry out.
In addition, the present invention relates to following content,
(7) a kind of copolymer precursor; it is characterized in that; contain block chain (A) and block chain (B); described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, and described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains the acidic-group of having protected that the repeating unit that contains polyoxyalkylene chain and formula (I) represent.
Figure BDA00002228158900061
(in the formula (I), R 1, R 2, R 3Represent independently of one another hydrogen atom or C1～C3 alkyl.X represents singly-bound or C1～C10 alkylidene group, is selected from-C(=O) OR 1a-,-C(=O) NHR 1a-,-OC(=O) R 1a-and-R 2a-OC(=O) R 1a-in group (R 1a, R 2aRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 4Expression hydrogen atom, C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl, R 5Expression C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl.）
According to (7) described copolymer precursor, it is characterized in that (8) block chain (B) further contains the repeating unit of formula (III) expression.
Figure BDA00002228158900062
(in the formula (III), R 6, R 7, R 8Represent independently of one another hydrogen atom or C1～C3 alkyl, R 9Expression C1～C10 alkyl or C6～C10 aryl C1～C6 alkyl.）
(9) according to (7) or (8) described copolymer precursor, it is characterized in that the repeating unit that contains uncle's amino is the repeating unit that formula IV represents.
Figure BDA00002228158900063
(in the formula IV, R 10, R 11, R 12Represent independently of one another hydrogen atom or C1～C3 alkyl.Y represents C1～C10 alkylidene group, is selected from-C(=O) OR 1b-,-C(=O) NHR 1b-,-OC(=O) R 1b-and-R 2b-OC(=O) R 1b-in group (R 1b, R 2bRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 13, R 14Represent independently of one another C1～C6 alkyl or C6～C10 aryl C1～C6 alkyl.）
(10) according to (7) or (8) described copolymer precursor, it is characterized in that the repeating unit that contains quaternary ammonium salt group is the repeating unit that formula V represents.
Figure BDA00002228158900071
(in the formula V, R 15, R 16, R 17Represent independently of one another hydrogen atom or C1～C3 alkyl.Y 1Expression C1～C10 alkylidene group, be selected from-C(=O) OR 1c-,-C(=O) NHR 1c-,-OC(=O) R 1c-and-R 2c-OC(=O) R 1c-in group (R 1c, R 2cRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 18, R 19, R 20The alkyl or the C6～C10 aryl C1～C6 alkyl that represent independently of one another C1～C6.Z -The expression counter ion.）
(11) according to each described copolymer precursor in (7)～(10), it is characterized in that the repeating unit that contains polyoxyalkylene chain is represented by formula (VI).
Figure BDA00002228158900072
(in the formula (VI), R 21, R 22, R 23Represent independently of one another hydrogen atom or C1～C3 alkyl.Z 1The expression be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1dExpression C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 24Expression C2～C4 alkylidene group, R 25Expression hydrogen atom or C1～C6 alkyl, m represents 2～150 arbitrarily integer, R 24O each other can be identical, also can be different).
Embodiment
(1) copolymer precursor
Copolymer precursor of the present invention contains respectively at least 1 following block chain (A) and block chain (B).
Block chain (A): the polymkeric substance that comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group
Block chain (B): comprise the repeating unit that contains polyoxyalkylene chain and the multipolymer that contains the repeating unit of the acidic-group of having protected
In addition, copolymer precursor of the present invention can also contain other block chain except containing above-mentioned block chain (A) and block chain (B).
1) block chain (A)
In block chain (A), what is called contains the repeating unit of uncle's amino and contains the repeating unit of quaternary ammonium salt group, as long as have above-mentioned cationic functional group at the side chain of repeating unit, then is not particularly limited.
Particularly, the polymkeric substance of block chain (A) comprising: only by the repeating unit that contains uncle's amino or contain a kind of homopolymer that forms in the repeating unit of quaternary ammonium salt group, by the repeating unit that contains uncle's amino or contain the multipolymer that forms more than 2 kinds in the repeating unit of quaternary ammonium salt group, by at least a kind of the repeating unit that contains uncle's amino with contain at least a kind of multipolymer that forms of the repeating unit of quaternary ammonium salt group, and the multipolymer from the repeating unit of the monomer that can carry out copolymerization of they and other.That multipolymer comprises is random, alternately, the multipolymer such as block.
(repeating unit that contains uncle's amino)
As the above-mentioned repeating unit that contains uncle's amino,, then be not particularly limited the repeating unit that for example can the following logical formula IV of illustration represents as long as contain uncle's amino.
Figure BDA00002228158900091
In the formula IV, R 10, R 11, R 12Represent independently of one another hydrogen atom or C1～C3 alkyl.Y represents C1～C10 alkylidene group, is selected from-C(=O) OR 1b-,-C(=O) NHR 1b-,-OC(=O) R 1b-and-R 2b-OC(=O) R 1b-in group (R 1b, R 2bRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group).R 13, R 14Represent independently of one another C1～C6 alkyl or C6～C10 aryl C1～C6 alkyl.
At this, as C1～C3 alkyl and C1～C6 alkyl, can the illustration methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc.
As C1～C10 alkylidene group, can the illustration methene chain, ethylidene chain, propylidene chain, methyl ethylidene chain, butylidene chain, 1,2-dimethyl ethylidene chain, pentylidene chain, 1-methyl butylidene chain, 2-methyl butylidene chain or hexylidene chain etc.
As C6～C10 aryl C1～C6 alkyl, can the illustration benzyl, styroyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalene-1-ylmethyl, naphthalene-2-base ethyl, 1-naphthalene-2-base-n-propyl, indenes-1-ylmethyl etc.
As the monomer of the raw material that becomes the repeating unit that formula IV represents, can illustration (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid dimethylamino butyl ester, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid diethylin propyl ester, (methyl) vinylformic acid diethylamino butyl ester etc.
(repeating unit that contains quaternary ammonium salt group)
As the above-mentioned repeating unit that contains quaternary ammonium salt group,, then be not particularly limited the repeating unit that for example can the following logical formula V of illustration represents as long as contain quaternary ammonium salt group.
In the formula (V), R 15, R 16, R 17Represent independently of one another hydrogen atom or C1～C3 alkyl.Y 1Expression C1～C10 alkylidene group, be selected from-C(=O) OR 1c-,-C(=O) NHR 1c-,-OC(=O) R 1c-and-R 2c-OC(=O) R 1c-in group (R 1c, R 2cRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group).R 18, R 19, R 20The alkyl or the C6～C10 aryl C1～C6 alkyl that represent independently of one another C1～C6.Z -The counter ion such as expression halide ions, haloalkyl ion, alkyl carboxylic acid salt ion, nitroxide ion, alkyl sulfate ion, sulfonate ion, phosphate anion or alkylphosphonic acid carboxylic acid radical ion.
At this, the alkyl of C1～C3 alkyl, C1～C6, C1～C10 alkylidene group and C6～C10 aryl C1～C6 alkyl can illustration the group identical with group in the formula IV of the above-mentioned repeating unit that contains uncle's amino.
As the monomer of the raw material that becomes the repeating unit that formula V represents, can illustration (methyl) acryloxy ethyl-trimethyl Neutral ammonium fluoride, (methyl) acryloxy ethyl-trimethyl salmiac, (methyl) acryloxy ethyl-trimethyl brometo de amonio, (methyl) acryloxy ethyl-trimethyl ammonium iodide, (methyl) acryloxy oxypropyl trimethyl Neutral ammonium fluoride, (methyl) acryloxy oxypropyl trimethyl ammonium chloride, (methyl) acryloxy oxypropyl trimethyl brometo de amonio, (methyl) acryloxy oxypropyl trimethyl ammonium iodide, (methyl) acryloxy butyl trimethylammonium Neutral ammonium fluoride, (methyl) acryloxy butyl trimethyl ammonium chloride, (methyl) acryloxy butyl trimethylammonium bromide, (methyl) acryloxy butyl trimethylammonium ammonium iodide etc.
(repeating unit that other can contain)
As other repeating unit that can contain in the block chain (A), can illustration from the repeating unit of (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc.
As (methyl) acrylic monomer, aromatic vinyl base system monomer, the conjugated diene monomer of the raw material that becomes above-mentioned repeating unit, can the following material of illustration.
As (methyl) acrylic monomer, can illustration (methyl) vinylformic acid; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) glycidyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 1-ethyl cyclohexyl, (methyl) acrylic compound such as (methyl) benzyl acrylate; (methyl) vinylformic acid 2-methoxyl group ethyl ester, methoxy poly (ethylene glycol) (unit number of ethylene glycol is 2～100) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
As aromatic vinyl base system monomer, can enumerate vinylbenzene, o-methyl styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene, to tert.-butoxy vinylbenzene, between tert.-butoxy vinylbenzene, to (1-ethoxy ethoxy) vinylbenzene, 2, the 4-dimethyl styrene, vinyl aniline, vinyl benzoic acid, vinyl naphthalene, vinyl anthracene, the 2-vinyl pyridine, 4-vinylpridine, the 2-vinylquinoline, the 4-vinylquinoline, 2-vinyl thiophene, the heteroaryl compounds such as 4-vinyl thiophene etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
As the conjugated diene monomer, can enumerate 1,3-butadiene, isoprene, 2-ethyl-1, the 3-divinyl, the 2-tertiary butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3-dimethyl-1, the 3-divinyl, 1,3-pentadiene, the 2-methyl isophthalic acid, the 3-pentadiene, the 3-methyl isophthalic acid, the 3-pentadiene, 1, the 3-hexadiene, the 2-methyl isophthalic acid, the 3-octadiene, 4,5-diethyl-1, the 3-octadiene, 3-butyl-1, the 3-octadiene, 1，3-cyclopentadiene, 1，3-cyclohexadiene, 1, the 3-cyclooctadiene, 1,3-three cyclodecadiene, myrcene, chloroprenes etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
2) block chain (B)
Block chain (B) is to comprise in the repeating unit that contains polyoxyalkylene chain at least a kind and contain at least a kind multipolymer in the repeating unit of the acidic-group of having protected.
That multipolymer comprises is random, alternately, the multipolymer such as block.
(repeating unit that contains polyoxyalkylene chain)
As containing the repeating unit of polyoxyalkylene chain in the block chain (B), as long as contain polyoxyalkylene chain, then be not particularly limited, for example can illustration formula (VI) repeating unit of expression.
Figure BDA00002228158900121
In the formula (VI), R 21, R 22, R 23Represent independently of one another hydrogen atom or C1～C3 alkyl.Z 1The expression be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1dExpression C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group).R 24Expression C2～C4 alkylidene group, R 25Expression hydrogen atom or C1～C6 alkyl.M represents 2～150 arbitrarily integer, R 24O each other can be identical, also can be different.
At this, as C1～C3 alkyl and C1～C6 alkyl, can the illustration methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc.
As C2～C4 alkylidene group and C1～C10 alkylidene group, can the illustration methene chain, ethylidene chain, propylidene chain, methyl ethylidene chain, butylidene chain, 1,2-dimethyl ethylidene chain, pentylidene chain, 1-methyl butylidene chain, 2-methyl butylidene chain or hexylidene chain etc.
In above-mentioned formula (VI), m is preferably 2～10.
As the monomer of the raw material of the repeating unit that becomes formula (VI) expression, can enumerate polyoxyethylene glycol (2～150: the value of the m in the expression (VI).Below identical) (methyl) acrylate, poly-(ethylene glycol (1～75) propylene glycol (1～75)) (methyl) acrylate, polypropylene glycol (2～150) (methyl) acrylate etc., these can be used alone, or two or more kinds in combination respectively.
(repeating unit that contains the acidic-group of having protected)
The repeating unit that contains the acidic-group of having protected in the block chain (B) is the repeating unit of formula (I) expression.
Figure BDA00002228158900131
In the formula (I), R 1, R 2, R 3Represent independently of one another hydrogen atom or C1～C3 alkyl.X represents singly-bound or C1～C10 alkylidene group, is selected from-C(=O) OR 1a-,-C(=O) NHR 1a-,-OC(=O) R 1a-and-R 2a-OC(=O) R 1a-in group (R 1a, R 2aRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group), R 4Expression hydrogen atom, C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl, R 5Expression C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl.
As the monomer of the raw material of the repeating unit that becomes formula (I) expression, can enumerate vinylformic acid methoxyl group methyl esters, vinylformic acid oxyethyl group methyl esters, vinylformic acid 1-oxyethyl group-ethyl ester, vinylformic acid 1-methoxyl group-ethyl ester, vinylformic acid 1-oxyethyl group-propyl ester, vinylformic acid 1-propoxy--ethyl ester, vinylformic acid 1-isopropoxy-ethyl ester, vinylformic acid 1-benzyl oxygen base-ethyl ester, 2-methyl-vinylformic acid 1-oxyethyl group-ethyl ester, 2-methyl-vinylformic acid 1-methoxyl group-ethyl ester, 2-methyl-vinylformic acid 1-oxyethyl group-propyl ester, 2-methyl-vinylformic acid 1-propoxy--ethyl ester, 2-methyl-vinylformic acid 1-isopropoxy ethyl ester, 2-methyl-vinylformic acid 1-benzyl oxygen base-ethyl ester etc.Among these, preferred vinylformic acid 1-oxyethyl group-ethyl ester, 2-methyl-vinylformic acid 1-oxyethyl group-ethyl ester.These can be used alone, or two or more kinds in combination respectively.
The repeating unit that contains the acidic-group of having protected adopts manufacture method of the present invention with the protecting group deprotection, can convert thus the repeating unit that contains acidic-group of following explanation to.
(repeating unit that other can contain)
As other repeating unit that can contain in the block chain (B), can illustration from the repeating unit of (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc.
Among these, the repeating unit of preferred formula (III) expression.
Figure BDA00002228158900141
In the formula (III), R 6, R 7, R 8Represent independently of one another hydrogen atom or C1～C3 alkyl.R 9Expression C1～C10 alkyl or C6～C10 aryl C1～C6 alkyl.
At this, as C1～C3 alkyl and C1～C6 alkyl, can the illustration methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc.
As C6～C10 aryl C1～C6 alkyl, can the illustration benzyl, styroyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalene-1-ylmethyl, naphthalene-2-base ethyl, 1-naphthalene-2-base-n-propyl, indenes-1-ylmethyl etc.
(methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer as the raw material that becomes above-mentioned repeating unit can the following materials of illustration.
As (methyl) acrylic monomer, can illustration (methyl) vinylformic acid; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) glycidyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 1-ethyl cyclohexyl, (methyl) acrylic compound such as (methyl) vinylformic acid benzyl; (methyl) vinylformic acid 2-methoxyl group ethyl ester, methoxy poly (ethylene glycol) (unit number of ethylene glycol is 2～100) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
As aromatic vinyl base system monomer, can enumerate vinylbenzene, o-methyl styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene, to tert.-butoxy vinylbenzene, between tert.-butoxy vinylbenzene, to (1-ethoxy ethoxy) vinylbenzene, 2, the 4-dimethyl styrene, vinyl aniline, vinyl benzoic acid, vinyl naphthalene, vinyl anthracene, the 2-vinyl pyridine, 4-vinylpridine, the 2-vinylquinoline, the 4-vinylquinoline, 2-vinyl thiophene, the heteroaryl compounds such as 4-vinyl thiophene etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
As the conjugated diene monomer, can enumerate 1,3-butadiene, isoprene, 2-ethyl-1, the 3-divinyl, the 2-tertiary butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3-dimethyl-1, the 3-divinyl, 1,3-pentadiene, the 2-methyl isophthalic acid, the 3-pentadiene, the 3-methyl isophthalic acid, the 3-pentadiene, 1, the 3-hexadiene, the 2-methyl isophthalic acid, the 3-octadiene, 4,5-diethyl-1, the 3-octadiene, 3-butyl-1, the 3-octadiene, 1，3-cyclopentadiene, 1，3-cyclohexadiene, 1, the 3-cyclooctadiene, 1,3-three cyclodecadiene, myrcene, chloroprenes etc., these can use separately a kind, perhaps mix more than 2 kinds and use.
(the block chain (A) in the multipolymer, the block chain that (B) can contain in addition)
Multipolymer of the present invention except have block chain (A) and (B), can also have the block chain that comprises other polymkeric substance.
As such polymkeric substance, can illustration contain homopolymer from repeating units such as (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomers, random copolymers, alternating copolymer, segmented copolymer etc.
For (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc., can illustration monomer same as described above.
(the block chain (A) in the multipolymer and the physical property such as the ratio of block chain (B) and molecular weight)
Block chain (A) in the multipolymer of the present invention is not particularly limited with the ratio of block chain (B), but counts 10～40 to 90～60 with the % by weight ratio, is preferably 15～35 to 85～65.
In addition, the weight-average molecular weight of utilizing GPC to measure is preferably 2000～500000, and more preferably 2000～20000.Especially as copolymer precursor, be preferably 4000～30000, more preferably 4000～15000.Utilizing weight-average molecular weight that GPC measures and the ratio of number-average molecular weight is 1.0～2.0, is preferably 1.0～1.5.
(2) manufacture method of copolymer precursor
The manufacture method of copolymer precursor of the present invention is not particularly limited, and can adopt known method to make, and for example, can make monomer polymerization form segmented copolymer by living polymerization.As living polymerization, can enumerate active free radical polymerization, active anionic polymerization, among these, further preferred active anionic polymerization.
Forming segmented copolymer can with behind block chain (A) or the monomer polymerization (B), make the monomer polymerization of other block carry out the block copolymerization materialization continuously; After also can making each autoreaction of each monomer of block chain (A) and block chain (B) be made into block, with each block combination.From preferred active anionic polymerization is considered in controlling composition, molecular weight aspect closely.
When making by active free radical polymerization, also can similarly react with active anionic polymerization, can also the monomer polymerization with a certain block after, before the next monomer of polymerization, refining polymkeric substance and after removing the remnants of monomer of previous reaction for the time being, the next monomer of polymerization.When the monomer of preferred each block does not mix mutually each other, preferably carry out the refining of polymkeric substance.
When making segmented copolymer by active anionic polymerization, for example, the monomer dropping of needs can be carried out polymerization in the solvent that is attached with additive and polymerization starter.At this moment, in order to form the block polymer of the arrangement that needs, the monomer of each block mode with the arrangement of needs is dripped in turn, make its reaction.
With the monomer polymerization of a certain block, during the monomer of next block of polymerization, begin to drip the monomer of next block after formerly the polyreaction of block finishes.The carrying out of polyreaction can be confirmed by the residual content that adopts vapor-phase chromatography, liquid phase chromatography to detect monomer.In addition, different and different according to the kind of monomer, solvent after the monomer dropping of previous block is finished, but after can stirring 1 minute～1 hour, begin to drip the monomer of next block.
When each block contains the monomer of a plurality of kinds, they can be dripped separately, also can drip simultaneously.
As the anionic polymerization initiator that is used for monomer polymerization, so long as nucleophilic reagent, and have the function of the polymerization that causes the anionoid polymerization monomer, then be not particularly limited, such as using basic metal, organic alkali metal compound etc.
As basic metal, can enumerate lithium, sodium, potassium, caesium etc.
As organic alkali metal compound, can enumerate above-mentioned alkali-metal alkylide, allylate, arylide etc., particularly preferably lithium alkylide.Concrete can use lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, sodium ethyl, xenyl lithium, naphthyl lithium, triphenyl lithium, sodium naphthalene, potassium naphthalide, alpha-methyl styrene sodium two negatively charged ion, 1,1-phenylbenzene hexyl lithium, 1,1-phenylbenzene-3-methyl amyl lithium, 1,4-two lithiums-2-butylene, 1,6-two lithium hexanes, polystyryl lithium, cumyl potassium, cumyl caesium etc.These anionic polymerization initiators can use separately a kind, perhaps are used in combination more than 2 kinds.
Whole with respect to the anionoid polymerization monomer that uses, the consumption of anionic polymerization initiator is generally 0.0001～0.2 equivalent, is preferably 0.0005～0.1 equivalent.By using the anionic polymerization initiator of this scope, manufacturing objective polymkeric substance with high yield.
With regard to polymerization temperature, so long as do not cause the side reactions such as shift reaction, termination reaction, consume monomer, the temperature range in that polymerization is finished then is not particularly limited, but preferably more than-100 ℃ and the temperature range below the solvent boiling point carry out.In addition, monomer is not particularly limited with respect to the concentration of polymer solvent, but is generally 1～40 % by weight, is preferably 2～15 % by weight.
The polymer solvent that uses in manufacture method of the present invention only otherwise participate in polyreaction and be the solvent that consistency is arranged with polymkeric substance then is not particularly limited, concrete can the illustration Anaesthetie Ether, tetrahydrofuran (THF) (THF), two
Figure BDA00002228158900171
Alkane, three Non-polar solvent or the low polar solvents such as the aliphatics such as tertiary amine isopolarity solvent, hexane, toluene, aromatic series or ester ring type hydrocarbon compound such as ether based compound, tetramethylethylened, the HMPA such as alkane.These solvents can use separately a kind, perhaps use as the mixed solvent more than 2 kinds.In manufacture method of the present invention, even with non-polar solvent or low polar solvent and polar solvent and time spent, also can control accurately polymerization, for example, whole with respect to solvent, non-polar solvent or low polar solvent can use more than the 5vol%, also can use more than the 20vol%, can also use more than the 50vol%.
In the present invention, also can as required, the finishing agent of the organo-metallic such as the dialkyl magnesiums such as dialkyl group zinc, dibutylmagnesium, triethyl aluminum such as zinc ethyl as polymerization-stable agent, monomer, solvent be used.
In the present invention, can as required, add the additives such as an alkali metal salt or alkali earth metal salt when polymerization begins or in the polymerization.As such additive, concrete can illustration sodium, inorganic acid salt, the halogenide such as the vitriol of potassium, barium, magnesium, nitrate, borate, can enumerate more specifically the muriate, bromide, iodide, lithium tetraborate, magnesium nitrate, sodium-chlor, Repone K of lithium, barium etc.Among these, the halogen thing of preferred lithium, for example lithium chloride, lithiumbromide, lithium iodide, lithium fluoride, particularly preferably lithium chloride.
The monomer polymerization that will contain quaternary ammonium salt group by active anionic polymerization is difficulty normally.
Therefore, when comprising the polymkeric substance of the repeating unit that contains quaternary ammonium salt group by the active anionic polymerization manufacturing, can behind the monomer polymerization of the raw material that will become the repeating unit that contains uncle's amino, adopt known method quaternized to this uncle's amino.As quaternizing agent, can enumerate the common alkylating agents such as alkyl sodium sulfate ester such as the haloalkyls such as benzyl chloride, bromotoluene, benzyl iodide etc., methyl chloride, monochloroethane, monobromethane, methyl iodide, methyl-sulfate, ethyl sulfate, sulfuric acid di-n-propyl ester.
(3) segmented copolymer
Segmented copolymer of the present invention contains respectively block chain (A) and the block chain (B1) below at least 1.
Block chain (A): the polymkeric substance that comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group
Block chain (B1): comprise the repeating unit that contains polyoxyalkylene chain and the multipolymer that contains the repeating unit of acidic-group
In addition, copolymer precursor of the present invention can also contain other block chain except containing above-mentioned block chain (A) and block chain (B1).
1) block chain (A)
Block chain (A) in the segmented copolymer is identical with block chain (A) in the above-mentioned copolymer precursor.
2) block chain (B1)
Block chain (B1) is to comprise in the repeating unit that contains polyoxyalkylene chain at least a kind and contain at least a kind multipolymer in the repeating unit of acidic-group.
That multipolymer comprises is random, alternately, the multipolymer such as block.
(repeating unit that contains polyoxyalkylene chain)
Repeating unit in the repeating unit that contains polyoxyalkylene chain in the block chain (B1) and the above-mentioned copolymer precursor, that contain polyoxyalkylene chain is identical.
(repeating unit that contains acidic-group)
The repeating unit that contains acidic-group in the block chain (B1) is the repeating unit of formula (II) expression.
In the formula (II), R 1, R 2, R 3, the expression of X and formula (I) the repeating unit that contains the acidic-group of having protected in the group same meaning.
The repeating unit of formula (II) expression can obtain by adopting manufacture method of the present invention that the protecting group of the acidic-group of having protected of formula (I) expression is carried out deprotection.
(repeating unit that other can contain)
As other repeating unit that can contain in the block chain (B1), with in the above-mentioned copolymer precursor, other repeating unit that can contain is identical in the block chain (B).
(the block chain (A) in the segmented copolymer, (B1) the block chain that can contain in addition)
Multipolymer of the present invention except have block chain (A) and (B1), can also have the block chain that comprises other polymkeric substance.
Such block chain is identical with the block chain that can contain in addition of block chain (A), (B) in copolymer precursor.
(the block chain (A) in the multipolymer and the physical property such as the ratio of block chain (B1) and molecular weight)
Block chain (A) in the multipolymer of the present invention is not particularly limited with the ratio of block chain (B1), but counts 10～40 to 90～60 with the % by weight ratio, is preferably 15～35 to 85～65.In addition, the repeating unit with acidic-group in the multipolymer contains proportional to be 0.5～20 % by weight, to be preferably 1～15 % by weight.
In addition, the weight-average molecular weight of utilizing GPC to measure is preferably 2000～50000, and more preferably 2000～20000.Especially as dispersion agent, be preferably 4000～30000, more preferably 4000～15000.Utilizing weight-average molecular weight that GPC measures and the ratio of number-average molecular weight is 1.0～2.0, especially as dispersion agent, is preferably 1.0～1.5.
(4) manufacture method of segmented copolymer
Segmented copolymer of the present invention can be by heating above-mentioned copolymer precursor to obtain.By the heating copolymer precursor, the protecting group of the protection acidic-group in the copolymer precursor is by deprotection.
Deprotection reaction can directly with the copolymer precursor heating, perhaps also can heat under the state that copolymer precursor is dissolved in the solvent.As such solvent, can enumerate water; The glycol ether-ether series solvents such as ethyl cellosolve acetate, methylcellosolve acetate, propylene glycol monomethyl ether (PGMEA) and propylene glycol list ethyl ether acetic ester; Glycol list or the diether series solvents such as ethyl cellosolve, methylcyclohexane, propylene glycol monomethyl ether, propylene glycol list ethyl ether and diethylene glycol dimethyl ether; The aromatic hydrocarbons series solvents such as toluene, monochloro benzene; The pure series solvents such as ethanol, Virahol, propyl carbinol, 1-methoxy-2-propanol (PGME); The ester series solvents such as ethyl lactate, butylacetate and Pyruvic Acid Ethyl ester; And by their mixed solvent that forms more than 2 kinds etc.Among these, the mixed solvent of the mixed solvent of preferred diol ether-ether series solvent, glycol ether-ether series solvent and pure series solvent, glycol ether-ether series solvent and water.Consider the mixed solvent of the mixed solvent of preferred diol ether-ether series solvent and pure series solvent, glycol ether-ether series solvent and water, the particularly preferably mixed solvent of glycol ether-ether series solvent and water from making temperature of reaction reduce this viewpoint.
Consider the mixed solvent of preferred diol ether-ether series solvent and water, the particularly preferably mixed solvent of PGMEA and water from removing easily this viewpoint of secondary resultant that is produced by deprotection reaction.
For the mixed solvent of glycol ether-ether series solvent and pure series solvent, as long as its blending ratio can be dissolved copolymer precursor, then be not particularly limited, but usually be preferably 95/5 % by weight～the 0.1/99.9 % by weight, more preferably 50/50～0.1/99.9 % by weight.
Mixed solvent for glycol ether-ether series solvent and water, as long as its blending ratio can be dissolved copolymer precursor, then be not particularly limited, but usually be preferably 95/5～50/50 % by weight, more preferably 90/10～60/40 % by weight is particularly preferably 90/10～75/25 % by weight.
The temperature of heating is different and different according to the structure, reaction solvent of the protecting group of protection acidic-group, but so long as the temperature that deprotection reaction carries out rapidly then be not particularly limited.
During glycol ether-ether series solvent, usually preferably under 80 ℃～200 ℃, carry out, more preferably under 100 ℃～160 ℃, carry out.During the mixed solvent of glycol ether-ether series solvent and pure series solvent, preferably under 100 ℃～140 ℃, carry out, more preferably under 110 ℃～140 ℃, carry out.During the mixed solvent of glycol ether-ether series solvent and water, preferably under 70 ℃～100 ℃, carry out, more preferably under 90 ℃～100 ℃, carry out.Consider from reducing painted this viewpoint of the polymers soln that is generated by deprotection reaction, preferably make the temperature of heating lower.
Embodiment
Below, utilize embodiment to describe in detail bright the present invention in detail, but technical scope of the present invention is not limited to these illustrations.
［ embodiment 1-1 ］
(polymerization process)
In the 1000mL flask, add tetrahydrofuran (THF) (below, sometimes economize slightly THF) 594.35g, lithium chloride (3.63 % by weight concentration THF solution) 10.98g, be cooled to-60 ℃.Then, add n-Butyl Lithium 7.89g(15.36 % by weight concentration hexane solution), slaking 10 minutes.
Then, with dripped in 30 minutes methacrylic acid 1-ethoxy ethyl ester (below, sometimes economize slightly EEMA) 4.04g, n-BMA (below, sometimes economize slightly nBMA) 61.33g, methoxy poly (ethylene glycol) monomethacrylates (PME-200 Japan Oil Co system) (below, sometimes economize slightly PEGMA) mixed solution of 26.19g, continue reaction 30 minutes after dripping.Then, the mensuration gas-chromatography (below, economize slightly GC) gel permeation chromatography (below, economize slightly GPC) (moving phase THF, DMF), confirm that monomer disappears.
Then, drip methacrylic acid 2-(dimethylamino) ethyl ester (below, sometimes economize slightly DMMA) 39.71g, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase DMF), after the affirmation monomer disappears, add methyl alcohol 3.21g and come termination reaction.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 5260, molecular weight distribution is 1.09, ratio of components is the multipolymer of DMMA-［ nBMA/PEGMA/EEMA ］=30-［ 47/20/3 ］ % by weight.
(deprotection operation)
The propylene glycol monomethyl ether of 50 % by weight concentration of the precursor polymer that obtains (below, sometimes economize slightly PGMEA) solution 200g is heated to 160 ℃ of reactions 3 hours.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 5140, molecular weight distribution is 1.08, ratio of components is the multipolymer (MA represents methacrylic acid) of DMMA-［ nBMA/PEGMA/MA ］=31-［ 47/20/2 ］ % by weight.
The polymers soln that obtains is filbert.
［ embodiment 1-2 ］
(deprotection operation)
PGMEA/ butanol solution (30/70 % by weight) 10.0g of 25 % by weight concentration of the precursor polymer that obtains in the polymerization process with embodiment 1-1 is heated to 115 ℃ of reactions 8 hours.Propyl carbinol is removed in distillation, is prepared into the PGMEA solution of 40 % by weight concentration.
The polymers soln that obtains is water white.
［ embodiment 1-3 ］
(deprotection operation)
The PGMEA/ aqueous solution (75/25 % by weight) of the PGMEA/ aqueous solution (62.5/37.5 % by weight) of 20 % by weight concentration of the precursor polymer that obtains in the polymerization process with embodiment 1-1, the PGMEA/ aqueous solution (65/35 % by weight) of 20 % by weight concentration, 20 % by weight concentration, the PGMEA/ aqueous solution (87.5/12.5 % by weight) of 20 % by weight concentration, the PGMEA/ aqueous solution (93.75/6.25 % by weight) of 20 % by weight concentration prepare respectively 12.80g.Solution is heated to respectively 100 ℃, reacted 8 hours.Dephlegmate is prepared into the PGMEA solution of 40 % by weight concentration.In PGMEA/ water (93.75/6.25 % by weight) solution, a precursor polymer residue part, but deprotection reaction is finished in other solution.Wherein, be deprotection reaction to be finished in 24 hours by making the reaction times in PGMEA/ water (93.75/6.25 % by weight) solution.
Each polymers soln that obtains is water white.
By the result of embodiment 1-1～embodiment 1-3 as can be known, grant heating condition by the PGMEA solution to precursor polymer, can be with the protecting group deprotection.In addition we know, by adopting the mixing solutions of PGMEA and alcohol, temperature of reaction is reduced, and then, by adopting the mixing solutions of PGMEA and water, temperature of reaction is further reduced.
［ embodiment 2 ］
(polymerization process)
In the 1000mL flask, add THF 695.92g, lithium chloride (3.63 % by weight concentration THF solution) 13.83g, be cooled to-60 ℃.Then, add n-Butyl Lithium (15.36 % by weight concentration hexane solution) 9.29g, slaking 10 minutes.
Then, with the mixed solution that dripped EEMA 8.47g, nBMA 71.15g, PEGMA 31.16g in 30 minutes, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA45.39g, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase DMF), after the affirmation monomer disappears, add methyl alcohol 3.21g and come termination reaction.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 5610, molecular weight distribution is 1.10, ratio of components is the multipolymer of DMMA-［ nBMA/PEGMA/EEMA ］=29-［ 46/20/5 ］ % by weight.
(deprotection operation)
The PGMEA solution 213g of 50 % by weight concentration of the multipolymer that obtains is heated to 160 ℃, slaking 3.5 hours.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 4800, molecular weight distribution is 1.12, ratio of components is the multipolymer of DMMA-［ nBMA/PEGMA/MA ］=30-［ 47/20/3 ］ % by weight.
［ embodiment 3 ］
(polymerization process)
In the 1000mL flask, add THF 578.66g, lithium chloride (3.63 % by weight concentration THF solution) 11.20g, be cooled to-60 ℃.Then, add n-Butyl Lithium (15.36 % by weight concentration hexane solution) 7.34g, slaking 10 minutes.
Then, the interpolation methyl methacrylate (below, sometimes economize slightly MMA) 4.30g, continue reaction 5 minutes.Then, measure to confirm that by GC monomer disappears after, sampling is carried out GPC and measured to a part, it is the 293(2.92 aggressiveness that the result has generated molecular weight) polymkeric substance.
Then, with dripped in 30 minutes EEMA 4.52g, methacrylic acid 2-(ethyl hexyl) ester (below, sometimes economize slightly EHMA) 19.80g, nBMA 19.50g, MMA 36.48g, methacrylic acid benzyl ester (below, sometimes economize slightly BzMA) mixed solution of 15.03g, PEGMA 11.99g, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA 36.98g, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase DMF) confirm that monomer disappears after, add methyl alcohol 3.21g and come termination reaction.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 6780, molecular weight distribution is 1.08, ratio of components is the multipolymer of DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/EEMA ］=25-［ 28/13/13/8/10/3 ］ % by weight.
(deprotection operation)
The PGMEA solution 200g of 50 % by weight concentration of the multipolymer that obtains is heated to 160 ℃ of reactions 3 hours.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 6120, molecular weight distribution is 1.10, ratio of components is the multipolymer of DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/MA ］=25-［ 28/13/14/8/10/2 ］ % by weight.
［ embodiment 4-1 ］
(polymerization process)
In the 1000mL flask, add THF 683.03g, lithium chloride (3.63 % by weight concentration THF solution) 11.92g, be cooled to-60 ℃.Then, add n-Butyl Lithium (15.36 % by weight concentration hexane solution) 8.32g, slaking 10 minutes.
Then, add MMA 5.06g, continue reaction 5 minutes.Then, measure to confirm that by GC monomer disappears after, sampling is carried out GPC and measured to a part, it is the 311(3.10 aggressiveness that the result generates molecular weight) polymkeric substance.
Then, with the mixed solution that dripped EEMA 9.68g, EHMA 22.0g, nBMA 22.09g, MMA 41.60g, BzMA 16.83g, PEGMA 13.75g in 30 minutes, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA 42.06g, continue reaction 30 minutes after dripping.Then, measure GCGPC(moving phase DMF), after the affirmation monomer disappears, add methyl alcohol 4.48g and come termination reaction.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, be confirmed to be molecular weight (Mw) and be 6980, molecular weight distribution is 1.10, ratio of components is the multipolymer of DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/EEMA ］=24-［ 27/13/13/8/10/5 ］ % by weight.
(deprotection operation)
The PGMEA solution 212.32g of 50 % by weight concentration of the precursor polymer that obtains is heated to 160 ℃, reacted 4 hours.
Utilize GPC(moving phase DMF) multipolymer that obtains is analyzed, confirm that molecular weight (Mw) is 5300, molecular weight distribution is 1.13, ratio of components is the multipolymer of DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/MA ］=25-［ 28/13/13/8/10/3 ］ % by weight.
The polymers soln that obtains is filbert.
［ embodiment 4-2 ］
(deprotection operation)
50 % by weight PGMEA solution 212.32g of the precursor polymer that obtains in the polymerization process with embodiment 4-1 are heated to 130 ℃ of reactions 17 hours.The polymers soln that obtains is yellow transparent.
［ embodiment 4-3 ］
(deprotection operation)
50 % by weight PGMEA/1-methoxy-2-propanol solution (20/80 % by weight) 4.64g of the precursor polymer that obtains in the polymerization process with embodiment 4-1 are heated to 130 ℃ of reactions 9 hours.PGME is removed in distillation, is prepared into the PGMEA solution of 40 % by weight concentration.The polymers soln that obtains is water white.
By the result of embodiment 4-1～embodiment 4-3 as can be known, grant heating condition by the PGMEA solution to precursor polymer, can be with the protecting group deprotection.And then as can be known, by adopting the mixing solutions of PGMEA and alcohol, can make temperature of reaction lower.As can be known by temperature of reaction being reduced, can reduce the painted of the polymers soln that obtains.
According to the present invention, can make the segmented copolymer that contains block chain (A) and block chain (B1), described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group, and described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains acidic-group that the repeating unit that contains polyoxyalkylene chain and formula (II) represent.These segmented copolymers are especially useful with pigment dispersing agent as color liquid crystal.

Claims (11)

1. the manufacture method of a segmented copolymer; described segmented copolymer contains block chain (A) and block chain (B1); described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains acidic-group of the repeating unit that contains polyoxyalkylene chain and formula (II) expression; it is characterized in that; the copolymer precursor that contains block chain (A) and block chain (B) is heated; described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group; described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains the acidic-group of having protected of the repeating unit that contains polyoxyalkylene chain and formula (I) expression
Figure FDA00002228158800011
In the formula (I), R 1, R 2, R 3Representing independently of one another hydrogen atom or C1～C3 alkyl, X represents singly-bound or C1～C10 alkylidene group, is selected from-C(=O) OR 1a-,-C(=O) NHR 1a-,-OC(=O) R 1a-and-R 2a-OC(=O) R 1a-in group, R 1a, R 2aRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 4Expression hydrogen atom, C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl, R 5Expression C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl,
Figure FDA00002228158800012
In the formula (II), R 1, R 2, R 3, X the represents meaning identical with formula (I).
2. the manufacture method of segmented copolymer according to claim 1 is characterized in that, block chain (B) and (B1) further contain the repeating unit of formula (III) expression,
Figure FDA00002228158800021
In the formula (III), R 6, R 7, R 8Represent independently of one another hydrogen atom or C1～C3 alkyl, R 9Expression C1～C10 alkyl or C6～C10 aryl C1～C6 alkyl.
3. the manufacture method of segmented copolymer according to claim 1 and 2 is characterized in that, the repeating unit that contains uncle's amino is the repeating unit that formula IV represents,
Figure FDA00002228158800022
In the formula IV, R 10, R 11, R 12Representing independently of one another hydrogen atom or C1～C3 alkyl, Y represents C1～C10 alkylidene group, is selected from-C(=O) OR 1b-,-C(=O) NHR 1b-,-OC(=O) R 1b-and-R 2b-OC(=O) R 1b-in group, R 1b, R 2bRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 13, R 14Represent independently of one another C1～C6 alkyl or C6～C10 aryl C1～C6 alkyl.
4. the manufacture method of segmented copolymer according to claim 1 and 2 is characterized in that, the repeating unit that contains quaternary ammonium salt group is the repeating unit of formula (V) expression,
Figure FDA00002228158800023
In the formula (V), R 15, R 16, R 17Represent independently of one another hydrogen atom or C1～C3 alkyl, Y 1Expression C1～C10 alkylidene group, be selected from-C(=O) OR 1c-,-C(=O) NHR 1c-,-OC(=O) R 1c-and-R 2c-OC(=O) R 1c-in group, R 1c, R 2cRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 18, R 19, R 20The alkyl or the C6～C10 aryl C1～C6 alkyl that represent independently of one another C1～C6, Z -The expression counter ion.
5. the manufacture method of each described segmented copolymer is characterized in that according to claim 1～4, contains the repeating unit of polyoxyalkylene chain by formula (VI) expression,
Figure FDA00002228158800031
In the formula (VI), R 21, R 22, R 23Represent independently of one another hydrogen atom or C1～C3 alkyl, Z 1The expression be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group, R 1dExpression C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 24Expression C2～C4 alkylidene group, R 25Expression hydrogen atom or C1～C6 alkyl, m represents 2～150 arbitrarily integer, R 24O each other can be identical, also can be different.
6. the manufacture method of each described segmented copolymer is characterized in that according to claim 1～5, carries out in the mixed solvent of the mixed solvent of glycol ether-ether series solvent and pure series solvent or glycol ether-ether series solvent and water.
7. copolymer precursor; it is characterized in that; contain block chain (A) and block chain (B); described block chain (A) is by following polymer formation: this polymkeric substance comprises at least a kind of repeating unit in the repeating unit that is selected from the repeating unit that contains uncle's amino and contains quaternary ammonium salt group; described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit that contains the acidic-group of having protected of the repeating unit that contains polyoxyalkylene chain and formula (I) expression
Figure FDA00002228158800032
In the formula (I), R 1, R 2, R 3Representing independently of one another hydrogen atom or C1～C3 alkyl, X represents singly-bound or C1～C10 alkylidene group, is selected from-C(=O) OR 1a-,-C(=O) NHR 1a-,-OC(=O) R 1a-and-R 2a-OC(=O) R 1a-in group, R 1a, R 2aRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 4Expression hydrogen atom, C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl, R 5Expression C1～C6 alkyl, C6～C10 aryl C1～C6 alkyl or C6～C10 aryl.
8. copolymer precursor according to claim 7 is characterized in that, block chain (B) further contains the repeating unit of formula (III) expression,
In the formula (III), R 6, R 7, R 8Represent independently of one another hydrogen atom or C1～C3 alkyl, R 9Expression C1～C10 alkyl or C6～C10 aryl C1～C6 alkyl.
9. according to claim 7 or 8 described copolymer precursor, it is characterized in that the repeating unit that contains uncle's amino is the repeating unit that formula IV represents,
Figure FDA00002228158800042
In the formula IV, R 10, R 11, R 12Representing independently of one another hydrogen atom or C1～C3 alkyl, Y represents C1～C10 alkylidene group, is selected from-C(=O) OR 1b-,-C(=O) NHR 1b-,-OC(=O) R 1b-and-R 2b-OC(=O) R 1b-in group, R 1b, R 2bRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 13, R 14Represent independently of one another C1～C6 alkyl or C6～C10 aryl C1～C6 alkyl.
10. according to claim 7 or 8 described copolymer precursor, it is characterized in that the repeating unit that contains quaternary ammonium salt group is the repeating unit that formula V represents,
Figure FDA00002228158800051
In the formula V, R 15, R 16, R 17Represent independently of one another hydrogen atom or C1～C3 alkyl, Y 1Expression C1～C10 alkylidene group, be selected from-C(=O) OR 1c-,-C(=O) NHR 1c-,-OC(=O) R 1c-and-R 2c-OC(=O) R 1c-in group, R 1c, R 2cRepresent independently of one another C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 18, R 19, R 20The alkyl or the C6～C10 aryl C1～C6 alkyl that represent independently of one another C1～C6, Z -The expression counter ion.
11. each described copolymer precursor is characterized in that according to claim 7～10, contains the repeating unit of polyoxyalkylene chain by formula (VI) expression,
Figure FDA00002228158800052
In the formula (VI), R 21, R 22, R 23Represent independently of one another hydrogen atom or C1～C3 alkyl, Z 1The expression be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group, R 1dExpression C1～C10 alkylidene group or C1～C10 alkylidene group-O-C1～C10 alkylidene group, R 24Expression C2～C4 alkylidene group, R 25Expression hydrogen atom or C1～C6 alkyl, m represents 2～150 arbitrarily integer, R 24O each other can be identical, also can be different.
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