CN102858826B - 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
CN102858826B
CN102858826B CN201180017897.3A CN201180017897A CN102858826B CN 102858826 B CN102858826 B CN 102858826B CN 201180017897 A CN201180017897 A CN 201180017897A CN 102858826 B CN102858826 B CN 102858826B
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repeating unit
alkylidene group
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CN102858826A (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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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 the manufacture method as the useful novel block copolymer of pigment dispersing agent and new copolymer precursor.Its content, to the Japan patent application 2010-092952 CLAIM OF PRIORITY applied on April 14th, 2010, is incorporated herein by the application.
Background technology
Known following random copolymers: wherein comprise at least a kind of repeating unit in the repeating unit be selected from containing tertiary amino and the repeating unit containing quaternary ammonium salt group, the repeating unit containing polyoxyalkylene chain and the repeating unit containing acidic-group.
These polymkeric substance are being studied due to the various characteristic had based on its specificity structure and are being developed in every field.
In patent documentation 1, this random copolymers is applied to field of lithography.Specifically, describing by methacrylic acid, dimethylaminoethyl methacrylate, ethyl propenoate and molecular weight in patent documentation 1 is the multipolymer etc. that the MPEG-550 of 350 and the ester cpds of methacrylic acid obtain.These adopt azobis isobutyronitrile (AIBN) as radical initiator, in methyl acetate, the mixing solutions of each monomer carried out radical polymerization, thus obtains as random copolymers.
In addition, in patent documentation 2, this random copolymers is as the pigment dispersing agent application in each fields such as coating, ink, building materials.Specifically, the random copolymers etc. of vinylbenzene 10 parts, methyl methacrylate 15 parts, β-dimethyl-aminoethylmethacrylate 15 parts, methacrylic acid 20 parts, Tridecyl methacrylate base ester 10 parts, methacrylic acid PEG monomethyl ether (number-average molecular weight is 400) 20 parts, dimethylaminoethyl methacrylate 10 parts is described in patent documentation 2.These are employings 2, and the mixing solutions of each monomer, as radical initiator, in the alcohol mixture solvent of ethanol/methyl alcohol=95/5, is carried out radical polymerization, thus obtains as random copolymers by 2 '-azo two (2,4-methyl pentane nitrile).
Patent documentation 1: Japanese Unexamined Patent Publication 6-128336
Patent documentation 2: Japanese Unexamined Patent Publication 2009-24165
Summary of the invention
The purposes of multipolymer becomes variation in recent years, needs the multipolymer with various characteristic.
Such as, in color liquid crystal display arrangement field, owing to strengthening the demand of the high-transmission rate of visible ray and high-contrast, therefore, pigment particles carry out micronize until at least visible ray wavelength below.Particulate like this, specific surface area increase compared with usually of pigment particles, therefore, for the multipolymer of the existing pigment dispersing agent used always, the pigment-dispersing at initial stage and through time dispersion stabilization insufficient.In addition, also require the high-performance beyond dispersing property recently, existing multipolymer cannot obtain sufficient performance.
In order to obtain the multipolymer meeting above-mentioned performance, the present inventor etc. need the segmented copolymer manufactured containing block chain (A) and block chain (B1), described block chain (A) is by following polymer formation: this polymkeric substance comprises the repeating unit that is selected from containing tertiary amino and containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group, described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit containing acidic-group that repeating unit containing polyoxyalkylene chain and formula (II) represent.
But the method manufacturing the segmented copolymer containing such structure is unknown.
The discoveries such as the present inventor, copolymer precursor containing block chain (A) and block chain (B) can as the useful intermediate of segmented copolymer, described block chain (A) is by following polymer formation: this polymkeric substance comprises the repeating unit that is selected from containing tertiary amino and containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group, described block chain (B) is formed by following multipolymer: this multipolymer contains the repeating unit that the repeating unit of polyoxyalkylene chain and formula I represent.
Find, by heating this copolymer precursor, the repeating unit represented by formula I converts the repeating unit containing acidic-group that formula II represents to, thus can manufacturing objective segmented copolymer, so far completes 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 containing acidic-group that repeating unit containing polyoxyalkylene chain and formula II represent, it is characterized in that, copolymer precursor containing 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 be selected from containing tertiary amino and the repeating unit containing quaternary ammonium salt group, described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit containing the acidic-group protected that repeating unit containing polyoxyalkylene chain and formula I represent.
(in formula I, R 1, R 2, R 3represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 4represent hydrogen atom, C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl, R 5represent C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl.）
(in formula II, R 1, R 2, R 3, X represents the meaning identical with formula I.）
(2) manufacture method of the segmented copolymer Gen Ju (1), is characterized in that, block chain (B) and (B1) are further containing the repeating unit that formula III represents.
(in formula III, R 6, R 7, R 8represent hydrogen atom or C1 ~ C3 alkyl independently of one another, R 9represent C1 ~ C10 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl.）
(3) manufacture method of basis (1) or the segmented copolymer described in (2), it is characterized in that, the repeating unit containing tertiary amino is the repeating unit that formula IV represents.
(in formula IV, R 10, R 11, R 12represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 13, R 14represent C1 ~ C6 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl independently of one another.）
(4) manufacture method of basis (1) or the segmented copolymer described in (2), it is characterized in that, the repeating unit containing quaternary ammonium salt group is the repeating unit that formula (V) represents.
(in formula (V), R 15, R 16, R 17represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Y 1represent 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 18, R 19, R 20represent alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl of C1 ~ C6 independently of one another.Z-represents counter ion.）
(5) according to the manufacture method of the segmented copolymer according to any one of (1) ~ (4), it is characterized in that, the repeating unit containing polyoxyalkylene chain is represented by formula VI.
(in formula VI, R 21, R 22, R 23represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Z 1represent and be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1drepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group), R 24represent C2 ~ C4 alkylidene group, R 25represent hydrogen atom or C1 ~ C6 alkyl, m represents the arbitrary integer of 2 ~ 150, R 24o each other can be identical, also can be different.) and
(6) according to the manufacture method of the segmented copolymer according to any one of (1) ~ (5), it is characterized in that, carry out in diol alcohol esters solvent and the mixed solvent of alcoholic solvent or the mixed solvent of diol alcohol esters solvent and water.
In addition, the present invention relates to following content,
(7) a kind of copolymer precursor; it is characterized in that; containing block chain (A) and block chain (B); described block chain (A) is by following polymer formation: this polymkeric substance comprises the repeating unit that is selected from containing tertiary amino and containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group, described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit containing the acidic-group protected that repeating unit containing polyoxyalkylene chain and formula I represent.
(in formula I, R 1, R 2, R 3represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 4represent hydrogen atom, C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl, R 5represent C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl.）
(8) copolymer precursor Gen Ju (7), is characterized in that, block chain (B) is further containing the repeating unit that formula III represents.
(in formula III, R 6, R 7, R 8represent hydrogen atom or C1 ~ C3 alkyl independently of one another, R 9represent C1 ~ C10 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl.）
(9) according to (7) or the copolymer precursor described in (8), it is characterized in that, the repeating unit containing tertiary amino is the repeating unit that formula IV represents.
(in formula IV, R 10, R 11, R 12represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 13, R 14represent C1 ~ C6 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl independently of one another.）
(10) according to (7) or the copolymer precursor described in (8), it is characterized in that, the repeating unit containing quaternary ammonium salt group is the repeating unit that formula (V) represents.
(in formula (V), R 15, R 16, R 17represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Y 1represent 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 18, R 19, R 20represent alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl of C1 ~ C6 independently of one another.Z-represents counter ion.）
(11) according to the copolymer precursor according to any one of (7) ~ (10), it is characterized in that, the repeating unit containing polyoxyalkylene chain is represented by formula VI.
(in formula VI, R 21, R 22, R 23represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Z 1represent and be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1drepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group), R 24represent C2 ~ C4 alkylidene group, R 25represent hydrogen atom or C1 ~ C6 alkyl, m represents the arbitrary integer of 2 ~ 150, R 24o each other can be identical, also can be different).
Embodiment
(1) copolymer precursor
Copolymer precursor of the present invention is respectively containing less than at least 1 block chain (A) and block chain (B).
Block chain (A): the polymkeric substance comprising at least a kind of repeating unit in the repeating unit be selected from containing tertiary amino and the repeating unit containing quaternary ammonium salt group
Block chain (B): the multipolymer comprising the repeating unit containing polyoxyalkylene chain and the repeating unit containing the acidic-group protected
In addition, copolymer precursor of the present invention, except containing except above-mentioned block chain (A) and block chain (B), can also contain other block chain.
1) block chain (A)
In block chain (A), the so-called repeating unit containing tertiary amino and the repeating unit containing quaternary ammonium salt group, as long as have above-mentioned cationic functional group on the side chain of repeating unit, be then not particularly limited.
Specifically, the polymkeric substance of block chain (A) comprising: only by the repeating unit containing tertiary amino or containing a kind of homopolymer formed in the repeating unit of quaternary ammonium salt group, by the repeating unit containing tertiary amino or containing two or more multipolymer formed in the repeating unit of quaternary ammonium salt group, by at least a kind of multipolymer formed of at least a kind of the repeating unit containing tertiary amino and repeating unit containing quaternary ammonium salt group, and they and other from the multipolymer that can carry out the repeating unit of the monomer of copolymerization.Multipolymer comprise random, alternately, the multipolymer such as block.
(repeating unit containing tertiary amino)
As the above-mentioned repeating unit containing tertiary amino, as long as amino containing uncle, be then not particularly limited, such as, can illustrate the repeating unit that following logical formula IV represents.
In formula IV, R 10, R 11, R 12represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another).R 13, R 14represent C1 ~ C6 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl independently of one another.
At this, as C1 ~ C3 alkyl and C1 ~ C6 alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc. can be illustrated.
As C1 ~ C10 alkylidene group, methene chain, ethylidene chain, propylidene chain, methyl ethylidene chain, butylidene chain, 1,2-dimethylethylene chain, pentylidene chain, 1-methylbutylene chain, 2-methylbutylene chain or hexylidene chain etc. can be illustrated.
As C6 ~ C10 aryl C1 ~ C6 alkyl, 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. can be illustrated.
As the monomer of raw material becoming the repeating unit that formula IV represents, (methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) acrylate butyl ester, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid diethylin propyl ester, (methyl) vinylformic acid diethylamino butyl ester etc. can be illustrated.
(repeating unit containing quaternary ammonium salt group)
As the above-mentioned repeating unit containing quaternary ammonium salt group, such as, as long as containing quaternary ammonium salt group, be then not particularly limited, the repeating unit that following logical formula V represents can be illustrated.
In formula (V), R 15, R 16, R 17represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Y 1represent 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another).R 18, R 19, R 20represent alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl of C1 ~ C6 independently of one another.Z-represents the counter ion such as 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 illustrate the group identical with the group in the formula IV of the above-mentioned repeating unit containing tertiary amino.
As the monomer of raw material becoming the repeating unit that formula V represents, (methyl) acryloyloxyethyl trimethyl Neutral ammonium fluoride can be illustrated, (methyl) acryloyloxyethyl trimethyl ammonium chloride, (methyl) acryloyloxyethyl trimethyl brometo de amonio, (methyl) acryloyloxyethyl trimethyl ammonium iodide, (methyl) acryloxypropyl trimethylammonium Neutral ammonium fluoride, (methyl) acryloxypropyl trimethyl ammonium chloride, (methyl) acryloxypropyl trimethylammonium bromide, (methyl) acryloxypropyl trimethylammonium 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.
(other repeating unit that can contain)
As other repeating unit that can contain in block chain (A), the repeating unit from (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc. can be illustrated.
As (methyl) acrylic monomer, aromatic vinyl base system monomer, the conjugated diene monomer of raw material becoming above-mentioned repeating unit, following material can be illustrated.
As (methyl) acrylic monomer, (methyl) vinylformic acid can be illustrated, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) 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-cyclohexyl ester, (methyl) acrylic compound such as (methyl) benzyl acrylate, (methyl) vinylformic acid 2-methoxy acrylate, 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 be used alone a kind, or two or more is used in combination.
As aromatic vinyl base system monomer, vinylbenzene can be enumerated, o-methyl styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene, to t-butoxystyrene, between t-butoxystyrene, to (1-ethoxy ethoxy) vinylbenzene, 2, 4-dimethyl styrene, vinyl aniline, vinyl benzoic acid, vinyl naphthalene, vinyl anthracene, 2-vinyl pyridine, 4-vinylpridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinyl thiophene, the heteroaryl compounds etc. such as 4-vinyl thiophene, these can be used alone a kind, or two or more is used in combination.
As conjugated diene monomer, can 1 be enumerated, 3-divinyl, isoprene, 2-ethyl-1, 3-divinyl, the 2-tertiary butyl-1, 3-divinyl, 2-phenyl-1, 3-divinyl, 2, 3-dimethyl-1, 3-divinyl, 1, 3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 1, 3-hexadiene, 2-methyl isophthalic acid, 3-octadiene, 4, 5-diethyl-1, 3-octadiene, 3-butyl-1, 3-octadiene, 1, 3-cyclopentadiene, 1, 3-cyclohexadiene, 1, 3-cyclooctadiene, 1, 3-tri-cyclodecadiene, myrcene, chloroprene etc., these can be used alone a kind, or two or more is used in combination.
2) block chain (B)
Block chain (B) comprises the multipolymer of at least a kind containing at least a kind in the repeating unit of polyoxyalkylene chain and the repeating unit containing the acidic-group protected.
Multipolymer comprise random, alternately, the multipolymer such as block.
(repeating unit containing polyoxyalkylene chain)
As the repeating unit containing polyoxyalkylene chain in block chain (B), such as, as long as containing polyoxyalkylene chain, be then not particularly limited, the repeating unit that formula VI represents can be illustrated.
In formula VI, R 21, R 22, R 23represent hydrogen atom or C1 ~ C3 alkyl independently of one another.Z 1represent and be selected from-C(=O) O-,-C(=O) NH-,-OC(=O)-and-R 1d-OC(=O)-in group (R 1drepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group).R 24represent C2 ~ C4 alkylidene group, R 25represent hydrogen atom or C1 ~ C6 alkyl.M represents the arbitrary integer of 2 ~ 150, R 24o each other can be identical, also can be different.
At this, as C1 ~ C3 alkyl and C1 ~ C6 alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc. can be illustrated.
As C2 ~ C4 alkylidene group and C1 ~ C10 alkylidene group, methene chain, ethylidene chain, propylidene chain, methyl ethylidene chain, butylidene chain, 1,2-dimethylethylene chain, pentylidene chain, 1-methylbutylene chain, 2-methylbutylene chain or hexylidene chain etc. can be illustrated.
In above-mentioned formula VI, m is preferably 2 ~ 10.
As the monomer of raw material becoming the repeating unit that formula VI represents, polyoxyethylene glycol (2 ~ 150: the value representing the m in formula VI can be enumerated.Identical below) (methyl) acrylate, poly-(ethylene glycol (1 ~ 75) propylene glycol (1 ~ 75)) (methyl) acrylate, polypropylene glycol (2 ~ 150) (methyl) acrylate etc., these can individually use, or two or more is used in combination.
(repeating unit containing the acidic-group protected)
The repeating unit containing the acidic-group protected in block chain (B) is the repeating unit that formula I represents.
In formula I, R 1, R 2, R 3represent hydrogen atom or C1 ~ C3 alkyl independently of one another.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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another), R 4represent hydrogen atom, C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl, R 5represent C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl.
As the monomer of raw material becoming the repeating unit that formula I represents, methoxyethyl methyl esters can be enumerated, ethioxy methyl esters, vinylformic acid 1-oxyethyl group-ethyl ester, vinylformic acid 1-methoxy-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-acrylic acid 1-oxyethyl group-ethyl ester, 2-methyl-acrylic acid 1-methoxy-ethyl ester, 2-methyl-acrylic acid 1-oxyethyl group-propyl ester, 2-methyl-acrylic acid 1-propoxy--ethyl ester, 2-methyl-acrylic acid 1-isopropoxyethyl cyanoacrylate, 2-methyl-acrylic acid 1-benzyl oxygen base-ethyl ester etc.Among these, preferred vinylformic acid 1-oxyethyl group-ethyl ester, 2-methyl-acrylic acid 1-oxyethyl group-ethyl ester.These can individually use, or two or more is used in combination.
Repeating unit containing the acidic-group protected adopts manufacture method of the present invention by protecting group deprotection, can convert the repeating unit containing acidic-group of following explanation thus to.
(other repeating unit that can contain)
As other repeating unit that can contain in block chain (B), the repeating unit from (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc. can be illustrated.
Among these, the repeating unit that preferred formula III represents.
In formula III, R 6, R 7, R 8represent hydrogen atom or C1 ~ C3 alkyl independently of one another.R 9represent C1 ~ C10 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl.
At this, as C1 ~ C3 alkyl and C1 ~ C6 alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc. can be illustrated.
As C6 ~ C10 aryl C1 ~ C6 alkyl, 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. can be illustrated.
As becoming (methyl) acrylic monomer of raw material of above-mentioned repeating unit, aromatic vinyl base system monomer, conjugated diene monomer can illustrate following material.
As (methyl) acrylic monomer, (methyl) vinylformic acid can be illustrated, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) 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-cyclohexyl ester, (methyl) acrylic compound such as (methyl) benzyl acrylate, (methyl) vinylformic acid 2-methoxy acrylate, 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 be used alone a kind, or two or more is used in combination.
As aromatic vinyl base system monomer, vinylbenzene can be enumerated, o-methyl styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene, to t-butoxystyrene, between t-butoxystyrene, to (1-ethoxy ethoxy) vinylbenzene, 2, 4-dimethyl styrene, vinyl aniline, vinyl benzoic acid, vinyl naphthalene, vinyl anthracene, 2-vinyl pyridine, 4-vinylpridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinyl thiophene, the heteroaryl compounds etc. such as 4-vinyl thiophene, these can be used alone a kind, or two or more is used in combination.
As conjugated diene monomer, can 1 be enumerated, 3-divinyl, isoprene, 2-ethyl-1, 3-divinyl, the 2-tertiary butyl-1, 3-divinyl, 2-phenyl-1, 3-divinyl, 2, 3-dimethyl-1, 3-divinyl, 1, 3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 1, 3-hexadiene, 2-methyl isophthalic acid, 3-octadiene, 4, 5-diethyl-1, 3-octadiene, 3-butyl-1, 3-octadiene, 1, 3-cyclopentadiene, 1, 3-cyclohexadiene, 1, 3-cyclooctadiene, 1, 3-tri-cyclodecadiene, myrcene, chloroprene etc., these can be used alone a kind, or two or more is used in combination.
(the block chain that can contain except block chain (A), block chain (B) in multipolymer)
Multipolymer of the present invention, except having block chain (A) and (B), can also have the block chain be made up of other polymkeric substance.
As such polymkeric substance, can illustrate containing the homopolymer, random copolymers, alternating copolymer, segmented copolymer etc. from repeating units such as (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomers.
For (methyl) acrylic monomer, aromatic vinyl base system monomer, conjugated diene monomer etc., monomer same as described above can be illustrated.
(physical property such as the ratio of the block chain (A) in multipolymer and block chain (B) and molecular weight)
Block chain (A) in multipolymer of the present invention is not particularly limited with the ratio of block chain (B), but with % by weight than counting 10 ~ 40 to 90 ~ 60, is preferably 15 ~ 35 to 85 ~ 65.
In addition, the weight-average molecular weight utilizing GPC to measure is preferably 2000 ~ 50000, is more preferably 2000 ~ 20000.Especially as copolymer precursor, be preferably 4000 ~ 30000, be more preferably 4000 ~ 15000.The weight-average molecular weight utilizing GPC to measure is 1.0 ~ 2.0 with the ratio of number-average molecular weight, 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 known method can be adopted to manufacture, and such as, monomer polymerization can be made to form segmented copolymer by living polymerization.As living polymerization, active free radical polymerization, active anionic polymerization can be enumerated, among these, preferred active anionic polymerization further.
Forming segmented copolymer can, by after the monomer polymerization of block chain (A) or (B), make the monomer polymerization of other block to carry out block copolymerization materialization continuously; Also, after block chain (A) and each autoreaction of each monomer of block chain (B) can be made to be made into block, each block is combined.From the viewpoint of controlling composition, molecular weight closely, preferred active anionic polymerization.
When being manufactured by active free radical polymerization, also can react in the same manner as active anionic polymerization, can also by after the monomer polymerization of a certain block, before being polymerized next monomer, finished polymer and after removing the remnants of the monomer of previously reaction, be polymerized next monomer for the time being.When the monomer of preferred each block does not mix mutually each other, preferably carry out the refining of polymkeric substance.
When manufacturing segmented copolymer by active anionic polymerization, such as, the monomer dropping of needs can be polymerized in the solvent being attached with additive and polymerization starter.Now, in order to form the block polymer of the arrangement of needs, the monomer of each block being dripped in turn in the mode of the arrangement needed, makes it react.
By the monomer polymerization of a certain block, when being polymerized the monomer of next block, after the polyreaction of previous block terminates, start the monomer dripping next block.The carrying out of polyreaction can be confirmed by the residual content adopting vapor-phase chromatography, liquid phase chromatography to detect monomer.In addition, after the monomer dropping of previous block completes, different and different according to the kind of monomer, solvent, but after 1 minute ~ 1 hour can be stirred, start the monomer dripping next block.
When each block contains the monomer of multiple kind, they can be dripped separately, also can drip simultaneously.
As the anionic polymerization initiator for monomer polymerization, as long as nucleophilic reagent, and there is the function of the polymerization causing anionoid polymerization monomer, be then not particularly limited, such as, can use basic metal, organic alkali metal compound etc.
As basic metal, lithium, sodium, potassium, caesium etc. can be enumerated.
As organic alkali metal compound, above-mentioned alkali-metal alkylide, allylate, arylide etc. can be enumerated, 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-bis-lithiums-2-butylene, 1,6-bis-lithium hexane, polystyryl lithium, cumyl potassium, cumyl caesium etc.These anionic polymerization initiators can be used alone a kind, or two or more combinationally uses.
Overall relative to the anionoid polymerization monomer used, 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, can manufacturing objective polymkeric substance with high yield.
With regard to polymerization temperature, as long as do not cause the side reaction such as shift reaction, termination reaction, consume monomer, the temperature range of being polymerized, be then not particularly limited, but the temperature range preferably more than-100 DEG C and below solvent boiling point is carried out.In addition, monomer is not particularly limited relative to the concentration of polymer solvent, but is generally 1 ~ 40 % by weight, is preferably 2 ~ 15 % by weight.
Only otherwise participate in polyreaction and be the solvent having consistency with polymkeric substance, be then not particularly limited, concrete can illustrate Anaesthetie Ether, tetrahydrofuran (THF) (THF), two to the polymer solvent used in manufacture method of the present invention alkane, three non-polar solvent or the low polar solvents such as the aliphatics such as tertiary amine polar solvent, hexane, toluene such as the ether compounds such as alkane, tetramethylethylened, HMPA, aromatic series or ester ring type hydrocarbon compound.These solvents can be used alone a kind, or use as mixed solvent of more than two kinds.In manufacture method of the present invention, even if by non-polar solvent or low polar solvent and polar solvent and the used time, also polymerization can be controlled accurately, such as, overall relative to solvent, non-polar solvent or low polar solvent can use more than 5vol%, also can use more than 20vol%, can also use more than 50vol%.
In the present invention, also can as required, the finishing agent of the organo-metallic such as dialkyl magnesium, triethyl aluminum such as dialkyl group zinc, dibutylmagnesium such as zinc ethyl as polymerization-stable agent, monomer, solvent be used.
In the present invention, as required, the additive such as an alkali metal salt or alkali earth metal salt can be added when being polymerized beginning or in polymerization.As such additive, concrete inorganic acid salt, the halogenide such as vitriol, nitrate, borate that can illustrate sodium, potassium, barium, magnesium, can enumerate the muriate, bromide, iodide, lithium tetraborate, magnesium nitrate, sodium-chlor, Repone K etc. of lithium, barium more specifically.Among these, the halogen thing of preferred lithium, such as lithium chloride, lithiumbromide, lithium iodide, lithium fluoride, particularly preferably lithium chloride.
By active anionic polymerization by the monomer polymerization containing quaternary ammonium salt group normally difficulty.Therefore, when comprising the polymkeric substance of the repeating unit containing quaternary ammonium salt group by active anionic polymerization manufacture, can, after the monomer polymerization of the raw material of the repeating unit that will become containing tertiary amino, adopt known method quaternized to this tertiary amino.As quaternizing agent, the common alkylating agents such as alkyl sodium sulfate ester such as the haloalkyl such as benzyl chloride, bromotoluene, benzyl iodide etc., methyl chloride, monochloroethane, monobromethane, methyl iodide, methyl-sulfate, ethyl sulfate, sulfuric acid di-n-propyl ester can be enumerated.
(3) segmented copolymer
Segmented copolymer of the present invention is respectively containing block chain (A) and the block chain (B1) of less than at least 1.
Block chain (A): the polymkeric substance comprising at least a kind of repeating unit in the repeating unit be selected from containing tertiary amino and the repeating unit containing quaternary ammonium salt group
Block chain (B1): the multipolymer comprising the repeating unit containing polyoxyalkylene chain and the repeating unit containing acidic-group
In addition, copolymer precursor of the present invention, except containing except above-mentioned block chain (A) and block chain (B1), can also contain other block chain.
1) block chain (A)
Block chain (A) in segmented copolymer is identical with the block chain (A) in above-mentioned copolymer precursor.
2) block chain (B1)
Block chain (B1) comprises containing at least a kind in the repeating unit of polyoxyalkylene chain with containing the multipolymer of at least a kind in the repeating unit of acidic-group.
Multipolymer comprise random, alternately, the multipolymer such as block.
(repeating unit containing polyoxyalkylene chain)
The repeating unit containing polyoxyalkylene chain in block chain (B1) is identical with the repeating unit containing polyoxyalkylene chain in above-mentioned copolymer precursor.
(repeating unit containing acidic-group)
The repeating unit containing acidic-group in block chain (B1) is the repeating unit that formula II represents.
In formula II, R 1, R 2, R 3, group same meaning in the repeating unit containing the acidic-group protected that represents of X and formula I.
The repeating unit that formula II represents can carry out deprotection to obtain by the protecting group of the acidic-group protected adopting manufacture method of the present invention to be represented by formula I.
(other repeating unit that can contain)
As other repeating unit that can contain in block chain (B1), identical with other repeating unit that can contain in the block chain (B) in above-mentioned copolymer precursor.
(the block chain that can contain except block chain (A), (B1) in segmented copolymer)
Multipolymer of the present invention, except having block chain (A) and (B1), can also have the block chain be made up of other polymkeric substance.
Such block chain is identical with the block chain that can contain in copolymer precursor except block chain (A), (B).
(physical property such as the ratio of the block chain (A) in multipolymer and block chain (B1) and molecular weight)
Block chain (A) in multipolymer of the present invention is not particularly limited with the ratio of block chain (B1), but with % by weight than counting 10 ~ 40 to 90 ~ 60, is preferably 15 ~ 35 to 85 ~ 65.In addition, in multipolymer have the repeating unit of acidic-group containing proportional be 0.5 ~ 20 % by weight, be preferably 1 ~ 15 % by weight.
In addition, the weight-average molecular weight utilizing GPC to measure is preferably 2000 ~ 50000, is more preferably 2000 ~ 20000.Especially as dispersion agent, be preferably 4000 ~ 30000, be more preferably 4000 ~ 15000.The weight-average molecular weight utilizing GPC to measure is 1.0 ~ 2.0 with the ratio of number-average molecular weight, especially as dispersion agent, is preferably 1.0 ~ 1.5.
(4) manufacture method of segmented copolymer
Segmented copolymer of the present invention can by obtaining above-mentioned copolymer precursor heating.By heating copolymer precursor, the protecting group of the protection acidic-group in copolymer precursor is by deprotection.
Copolymer precursor can directly heat by deprotection reaction, or also can heat under copolymer precursor is dissolved state in a solvent.As such solvent, water can be enumerated; The diol alcohol esters solvents such as ethyl cellosolve acetate, methylcellosolve acetate, propylene glycol monomethyl ether (PGMEA) and propylene glycol monoethyl acetic ester; Glycol list or two ether solvents such as ethyl cellosolve, methylcyclohexane, propylene glycol monomethyl ether, propylene glycol monoethyl and diethylene glycol dimethyl ether; The aromatic hydrocarbons series solvents such as toluene, monochloro benzene; The alcoholic solvents such as ethanol, Virahol, propyl carbinol, 1-methoxy-2-propanol (PGME); The esters solvents such as ethyl lactate, butylacetate and Pyruvic Acid Ethyl ester; And by their two or more mixed solvent etc. formed.Among these, the mixed solvent of the mixed solvent of preferred diol solvent of ether ester type, diol alcohol esters solvent and alcoholic solvent, diol alcohol esters solvent and water.Reduce this viewpoint from temperature of reaction can be made to consider, the mixed solvent of the mixed solvent of preferred diol solvent of ether ester type and alcoholic solvent, diol alcohol esters solvent and water, the particularly preferably mixed solvent of diol alcohol esters solvent and water.
Consider from easily removing this viewpoint of secondary resultant produced by deprotection reaction, the mixed solvent of preferred diol solvent of ether ester type and water, the particularly preferably mixed solvent of PGMEA and water.
For the mixed solvent of diol alcohol esters solvent and alcoholic solvent, as long as its blending ratio can dissolve copolymer precursor, be then not particularly limited, but be usually preferably 9,5/5 % by weight ~ 0.1/99.9 % by weight, be more preferably 50/50 ~ 0.1/99.9 % by weight.
For the mixed solvent of diol alcohol esters solvent and water, as long as its blending ratio can dissolve copolymer precursor, be then not particularly limited, but be usually preferably 95/5 ~ 50,/50 % by weight, be more preferably 90/10 ~ 60,/40 % by weight, be particularly preferably 90/10 ~ 75,/25 % by weight.
The temperature of heating is different and different according to the structure of protecting group of protection acidic-group, reaction solvent, as long as but the deprotection reaction temperature of carrying out rapidly, be then not particularly limited.
During diol alcohol esters solvent, usually preferably to carry out at 80 DEG C ~ 200 DEG C, more preferably carry out at 100 DEG C ~ 160 DEG C.During the mixed solvent of diol alcohol esters solvent and alcoholic solvent, preferably carry out at 100 DEG C ~ 140 DEG C, more preferably carry out at 110 DEG C ~ 140 DEG C.During the mixed solvent of diol alcohol esters solvent and water, preferably carry out at 70 DEG C ~ 100 DEG C, more preferably carry out at 90 DEG C ~ 100 DEG C.Considering from reducing the polymers soln generated by deprotection reaction this viewpoint painted, preferably making the temperature of heating lower.
Embodiment
, utilize embodiment to describe the present invention in detail below, but technical scope of the present invention is not limited to these illustrations.
［ embodiment 1-1 ］
(polymerization process)
In 1000mL flask, add tetrahydrofuran (THF) (following, sometimes to economize slightly THF) 594.35g, lithium chloride (3.63 % by weight concentration THF solution) 10.98g, be cooled to-60 DEG C.Then, add n-Butyl Lithium 7.89g(15.36 % by weight concentration hexane solution), slaking 10 minutes.
Then, methacrylic acid 1-ethoxy ethyl ester is dripped (following with 30 minutes, sometimes slightly EEMA is economized) 4.04g, n-BMA be (following, sometimes slightly nBMA is economized) 61.33g, methoxy poly (ethylene glycol) monomethacrylates (PME-200 Japan Oil Co system) be (following, sometimes slightly PEGMA is economized) mixed solution of 26.19g, continues reaction 30 minutes after dripping.Then, measure gas-chromatography (following, to economize slightly GC) gel permeation chromatography (following, to economize slightly GPC) (moving phase THF, DMF), confirm that monomer disappears.
Then, methacrylic acid 2-(dimethylamino is dripped) ethyl ester (following, sometimes to economize slightly DMMA) 39.71g, continues reaction 30 minutes after dripping.Then, measure GCGPC(moving phase DMF), after confirming that monomer disappears, add methyl alcohol 3.21g and carry out termination reaction.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 5260, molecular weight distribution is 1.09, ratio of components is DMMA-［ nBMA/PEGMA/EEMA ］=30-［ 47/20/3 ］ % by weight.
(deprotection operation)
Propylene glycol monomethyl ether (following, sometimes to economize slightly PGMEA) the solution 200g of 50 % by weight concentration of the precursor polymer obtained is heated to 160 DEG C of reactions 3 hours.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer (MA represents methacrylic acid) that molecular weight (Mw) is 5140, molecular weight distribution is 1.08, ratio of components is DMMA-［ nBMA/PEGMA/MA ］=31-［ 47/20/2 ］ % by weight.
The polymers soln obtained 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 obtained in the polymerization process of embodiment 1-1 is heated to 115 DEG C of reactions 8 hours.Distillation removing propyl carbinol, is prepared into the PGMEA solution of 40 % by weight concentration.
The polymers soln obtained is water white.
［ embodiment 1-3 ］
(deprotection operation)
The PGMEA/ aqueous solution (87.5/12.5 % by weight) of the PGMEA/ aqueous solution (75,/25 % by weight) of the PGMEA/ aqueous solution (65,/35 % by weight) of the PGMEA/ aqueous solution (62.5/37.5 % by weight) of 20 % by weight concentration of the precursor polymer obtained in the polymerization process of embodiment 1-1,20 % by weight concentration, 20 % by weight concentration, 20 % by weight concentration, the PGMEA/ aqueous solution (93.75/6.25 % by weight) of 20 % by weight concentration are prepared 12.80g respectively.Solution is heated to 100 DEG C respectively, reacts 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 in other solution, deprotection reaction completes.Wherein, in PGMEA/ water (93.75/6.25 % by weight) solution by making the reaction times be make deprotection reaction complete in 24 hours.
Each polymers soln obtained is water white.
From the result of embodiment 1-1 ~ embodiment 1-3, by granting heating condition to the PGMEA solution of precursor polymer, can by protecting group deprotection.In addition we know, by adopting the mixing solutions of PGMEA and alcohol, temperature of reaction can be made to reduce, and then, by adopting the mixing solutions of PGMEA and water, temperature of reaction can be made to reduce further.
［ embodiment 2 ］
(polymerization process)
In 1000mL flask, add THF695.92g, lithium chloride (3.63 % by weight concentration THF solution) 13.83g, be cooled to-60 DEG C.Then, n-Butyl Lithium (15.36 % by weight concentration hexane solution) 9.29g is added, slaking 10 minutes.
Then, drip the mixed solution of EEMA8.47g, nBMA71.15g, PEGMA31.16g with 30 minutes, after dripping, continue reaction 30 minutes.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA45.39g, after dripping, continue reaction 30 minutes.Then, measure GCGPC(moving phase DMF), after confirming that monomer disappears, add methyl alcohol 3.21g and carry out termination reaction.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 5610, molecular weight distribution is 1.10, ratio of components is DMMA-［ nBMA/PEGMA/EEMA ］=29-［ 46/20/5 ］ % by weight.
(deprotection operation)
The PGMEA solution 213g of 50 % by weight concentration of the multipolymer obtained is heated to 160 DEG C, slaking 3.5 hours.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 4800, molecular weight distribution is 1.12, ratio of components is DMMA-［ nBMA/PEGMA/MA ］=30-［ 47/20/3 ］ % by weight.
［ embodiment 3 ］
(polymerization process)
In 1000mL flask, add THF578.66g, lithium chloride (3.63 % by weight concentration THF solution) 11.20g, be cooled to-60 DEG C.Then, n-Butyl Lithium (15.36 % by weight concentration hexane solution) 7.34g is added, slaking 10 minutes.
Then, add methyl methacrylate (following, sometimes to economize slightly MMA) 4.30g, continue reaction 5 minutes.Then, by GC measure confirm monomer disappear after, to a part sampling carry out GPC mensuration, it is 293(2.92 aggressiveness that result generates molecular weight) polymkeric substance.
Then, EEMA4.52g, methacrylic acid 2-(ethyl hexyl) ester is dripped (below with 30 minutes, sometimes slightly EHMA is economized) 19.80g, nBMA19.50g, MMA36.48g, benzyl methacrylate be (following, sometimes slightly BzMA is economized) mixed solution of 15.03g, PEGMA11.99g, continues reaction 30 minutes after dripping.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA36.98g, after dripping, continue reaction 30 minutes.Then, measure GCGPC(moving phase DMF) confirm that monomer disappears after, add methyl alcohol 3.21g and carry out termination reaction.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 6780, molecular weight distribution is 1.08, ratio of components is 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 obtained is heated to 160 DEG C of reactions 3 hours.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 6120, molecular weight distribution is 1.10, ratio of components is DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/MA ］=25-［ 28/13/14/8/10/2 ］ % by weight.
［ embodiment 4-1 ］
(polymerization process)
In 1000mL flask, add THF683.03g, lithium chloride (3.63 % by weight concentration THF solution) 11.92g, be cooled to-60 DEG C.Then, n-Butyl Lithium (15.36 % by weight concentration hexane solution) 8.32g is added, slaking 10 minutes.
Then, add MMA5.06g, continue reaction 5 minutes.Then, by GC measure confirm monomer disappear after, to a part sampling carry out GPC mensuration, result generate molecular weight be 311(3.10 aggressiveness) polymkeric substance.
Then, drip the mixed solution of EEMA9.68g, EHMA22.0g, nBMA22.09g, MMA41.60g, BzMA16.83g, PEGMA13.75g with 30 minutes, after dripping, continue reaction 30 minutes.Then, measure GCGPC(moving phase THF, DMF), confirm that monomer disappears.
Then, drip DMMA42.06g, after dripping, continue reaction 30 minutes.Then, measure GCGPC(moving phase DMF), after confirming that monomer disappears, add methyl alcohol 4.48g and carry out termination reaction.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, be confirmed to be the multipolymer that molecular weight (Mw) is 6980, molecular weight distribution is 1.10, ratio of components is 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 obtained is heated to 160 DEG C, reacts 4 hours.
Utilize GPC(moving phase DMF) multipolymer obtained is analyzed, confirm the multipolymer that molecular weight (Mw) is 5300, molecular weight distribution is 1.13, ratio of components is DMMA-［ MMA/nBMA/EHMA/PEGMA/BzMA/MA ］=25-［ 28/13/13/8/10/3 ］ % by weight.
The polymers soln obtained is filbert.
［ embodiment 4-2 ］
(deprotection operation)
50 % by weight PGMEA solution 212.32g of the precursor polymer obtained in the polymerization process of embodiment 4-1 are heated to 130 DEG C of reactions 17 hours.The polymers soln obtained 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 obtained in the polymerization process of embodiment 4-1 are heated to 130 DEG C of reactions 9 hours.Distillation removing PGME, is prepared into the PGMEA solution of 40 % by weight concentration.The polymers soln obtained is water white.
From the result of embodiment 4-1 ~ embodiment 4-3, by granting heating condition to the PGMEA solution of precursor polymer, can by protecting group deprotection.And then known, by adopting the mixing solutions of PGMEA and alcohol, temperature of reaction can be made lower.Known by making temperature of reaction reduce, the painted of the polymers soln obtained can be reduced.
According to the present invention, the segmented copolymer containing block chain (A) and block chain (B1) can be manufactured, described block chain (A) is by following polymer formation: this polymkeric substance comprises the repeating unit that is selected from containing tertiary amino and containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group, described block chain (B1) is formed by following multipolymer: this multipolymer comprises the repeating unit containing acidic-group that repeating unit containing polyoxyalkylene chain and formula (II) represent.These segmented copolymers are especially useful as color liquid crystal pigment dispersing agent.

Claims (5)

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 containing acidic-group that repeating unit containing polyoxyalkylene chain and formula II represent, it is characterized in that, copolymer precursor containing block chain (A) and block chain (B) is heated, described block chain (A) is by following polymer formation: this polymkeric substance is formed by the repeating unit be selected from containing tertiary amino with containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group, described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit containing the acidic-group protected that repeating unit containing polyoxyalkylene chain and formula I represent,
In formula I, R 1, R 2, R 3represent hydrogen atom or C1 ~ C3 alkyl independently of one another, 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 4represent hydrogen atom, C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl, R 5represent C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl,
In formula II, R 1, R 2, R 3, X represents the meaning identical with formula I,
Wherein, the repeating unit containing tertiary amino is represented by formula IV,
In formula IV, R 10, R 11, R 12represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Y represent C1 ~ C10 alkylidene group, the (=O) OR that is selected from-C 1b-,-C (=O) NHR 1b-,-OC (=O) R 1b-and-R 2b-OC (=O) R 1b-in group, R 1b, R 2brepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 13, R 14represent C1 ~ C6 alkyl independently of one another;
Repeating unit containing quaternary ammonium salt group is represented by formula (V),
In formula (V), R 15, R 16, R 17represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Y 1represent 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 18, R 19, R 20represent the alkyl of C1 ~ C6 independently of one another, Z -represent counter ion;
Repeating unit containing polyoxyalkylene chain is represented by formula VI,
In formula VI, R 21, R 22, R 23represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Z 1represent and be selected from-C (=O) O-,-C (=O) NH-,-OC (=O)-and-R 1d-OC (=O)-in group, R 1drepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group, R 24represent C2 ~ C4 alkylidene group, R 25represent hydrogen atom or C1 ~ C6 alkyl, m represents the arbitrary integer of 2 ~ 150, R 24o each other can be identical, also can be different.
2. the manufacture method of segmented copolymer according to claim 1, is characterized in that, block chain (B) and (B1) contain the repeating unit that formula III represents further,
In formula III, R 6, R 7, R 8represent hydrogen atom or C1 ~ C3 alkyl independently of one another, R 9represent 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, carries out in diol alcohol esters solvent and the mixed solvent of alcoholic solvent or the mixed solvent of diol alcohol esters solvent and water.
4. a copolymer precursor; it is characterized in that; containing block chain (A) and block chain (B); described block chain (A) is by following polymer formation: this polymkeric substance is formed by the repeating unit be selected from containing tertiary amino with containing at least a kind of repeating unit in the repeating unit of quaternary ammonium salt group; described block chain (B) is formed by following multipolymer: this multipolymer comprises the repeating unit containing the acidic-group protected that repeating unit containing polyoxyalkylene chain and formula I represent
In formula I, R 1, R 2, R 3represent hydrogen atom or C1 ~ C3 alkyl independently of one another, 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 4represent hydrogen atom, C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl, R 5represent C1 ~ C6 alkyl, C6 ~ C10 aryl C1 ~ C6 alkyl or C6 ~ C10 aryl;
Wherein, the repeating unit containing tertiary amino is represented by formula IV,
In formula IV, R 10, R 11, R 12represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Y represent C1 ~ C10 alkylidene group, the (=O) OR that is selected from-C 1b-,-C (=O) NHR 1b-,-OC (=O) R 1b-and-R 2b-OC (=O) R 1b-in group, R 1b, R 2brepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 13, R 14represent C1 ~ C6 alkyl independently of one another;
Repeating unit containing quaternary ammonium salt group is represented by formula (V),
In formula (V), R 15, R 16, R 17represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Y 1represent 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 C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group independently of one another, R 18, R 19, R 20represent the alkyl of C1 ~ C6 independently of one another, Z -represent counter ion;
Repeating unit containing polyoxyalkylene chain is represented by formula VI,
In formula VI, R 21, R 22, R 23represent hydrogen atom or C1 ~ C3 alkyl independently of one another, Z 1represent and be selected from-C (=O) O-,-C (=O) NH-,-OC (=O)-and-R 1d-OC (=O)-in group, R 1drepresent C1 ~ C10 alkylidene group or C1 ~ C10 alkylidene group-O-C1 ~ C10 alkylidene group, R 24represent C2 ~ C4 alkylidene group, R 25represent hydrogen atom or C1 ~ C6 alkyl, m represents the arbitrary integer of 2 ~ 150, R 24o each other can be identical, also can be different.
5. copolymer precursor according to claim 4, is characterized in that, block chain (B) contains the repeating unit that formula III represents further,
In formula III, R 6, R 7, R 8represent hydrogen atom or C1 ~ C3 alkyl independently of one another, R 9represent C1 ~ C10 alkyl or C6 ~ C10 aryl C1 ~ C6 alkyl.
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