WO2018103265A1 - 一种聚丙烯酸酯流平剂、制备方法及其应用 - Google Patents

一种聚丙烯酸酯流平剂、制备方法及其应用 Download PDF

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WO2018103265A1
WO2018103265A1 PCT/CN2017/083532 CN2017083532W WO2018103265A1 WO 2018103265 A1 WO2018103265 A1 WO 2018103265A1 CN 2017083532 W CN2017083532 W CN 2017083532W WO 2018103265 A1 WO2018103265 A1 WO 2018103265A1
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group
acrylate
meth
leveling agent
monomer
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PCT/CN2017/083532
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English (en)
French (fr)
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王志军
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海门埃夫科纳化学有限公司
王志军
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Publication of WO2018103265A1 publication Critical patent/WO2018103265A1/zh

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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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3

Definitions

  • the invention relates to a leveling agent, in particular to a polyacrylate leveling agent based on reversible addition-fragmentation chain transfer (RAFT) polymerization, a preparation method and application thereof, and can be used as a leveling agent in coatings and inks. .
  • RAFT reversible addition-fragmentation chain transfer
  • polyacrylate is suitable as a leveling agent for coating systems, which is uniformly distributed on the surface of the coating film due to limited compatibility with the resin system, and a new interface layer having uniform surface tension is formed on the surface of the coating film. Further, a smooth and smooth coating film is obtained.
  • the disadvantage of the polyacrylate leveling agent is that its incompatibility with the resin system increases with the increase of the molecular weight of the polymer, which may cause turbidity of the coating and haze of the coating film; and high molecular weight polyacrylic acid. The higher viscosity of the ester leveling agent can cause operational problems for the paint manufacturer.
  • the molecular weight distribution of the polymer can be at a very narrow level by active controlled radical polymerization, and the molecular weight distribution index can be adjusted to 1.5; the narrower molecular weight distribution can improve the viscosity and incompatibility of the high molecular weight polyacrylate.
  • the polymer prepared by active controlled radical polymerization can satisfy the polymerization of the second monomer to form a block copolymer due to the retention of the active terminal, thereby satisfying The need for polyacrylate leveling agents in the diversity of polymer chain structures. Therefore, the use of the above method to develop a novel polyacrylate leveling agent to overcome the defects of orange peel, shrinkage, and the like, and to have industrial production prospects, is a hot spot in the field.
  • the technical solution adopted by the present invention is: a polyacrylate leveling agent, and the chemical structure of the polyacrylate leveling agent is:
  • Monomer A is selected from the group consisting of chemical structures One or more of the monomers;
  • R 1 is hydrogen or methyl;
  • R 2 is a linear, branched or cyclic alkyl group having from 1 to 22 carbon atoms;
  • the monomer B is one or more selected from the group consisting of ethylenically unsaturated compound monomers having a substituted functional group.
  • the a and b are independently of each other an integer from 1 to 1000.
  • said R 2 is a linear or branched alkyl group having from 1 to 22 carbon atoms.
  • the B is selected from the group consisting of chemical structures a combination of one or more of the monomers, R 3 is hydrogen or methyl, R 4 is a nitrogen-containing heterocyclic group or a group wherein n is an integer from 0 to 25, R 5 is O or N, and R 6 is a hydroxyl group, a carboxyl group, a sulfonic acid group, an aminoalkyl group, a polyoxyethylene group and/or a polyoxypropylene group, and a short carbon chain. Fluoroalkyl or polysiloxane based.
  • R 6 is a fluorine-containing alkyl group or a polysiloxane group.
  • the monomer B is obtained by esterification of a hydroxyl terminated polysiloxane with acryloyl chloride or acrylic acid, and has a molecular weight of 500 to 5,000.
  • a and b are each independently an integer of 1 to 500.
  • Another object of the present invention is to provide a method for preparing the above polyacrylate leveling agent, which comprises the following steps:
  • Monomer A and monomer B are initiated by an azo initiator, and RAFT polymerization can be carried out in the presence of a regulator; the chemical structure of the regulator is:
  • R 9 and R 7 are each independently alkyl, R 8 is phenyl, cyano, carboxyl or ester; Z is phenyl, alkyl, alkylthio, phenoxy, alkane An oxy group, an alkylamino group or a nitrogen-containing heterocyclic group.
  • a further object of the present invention is to provide a polyacrylate leveling agent for use in a coating or ink.
  • the polyacrylate leveling agent of the present invention is formed by polymerization of a specific monomer A and monomer B, especially in the chemical structure formula.
  • a controlled radical polymerization of RAFT activity is carried out to prepare a narrow molecular weight distribution polyacrylate leveling agent;
  • R 9 and R 7 are each independently an alkyl group, and R 8 is a phenyl group, a cyano group, Carboxyl or ester group;
  • Z is phenyl, alkyl, alkylthio, phenoxy, alkoxy, alkylamino or nitrogen-containing heterocyclic group;
  • the leveling agent thus obtained is used in a coating or ink system It can significantly improve the coating coating and anti-cratering ability, improve the wetting effect of the substrate; it is more likely to impart a smooth and scratch-resistant effect on the coating film; the preparation method is simple and easy to mass-produce.
  • the polyacrylate leveling agent of the invention has the chemical structure of the polyacrylate leveling agent:
  • R 1 is hydrogen or methyl.
  • R 2 is a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, and the difference in structure may affect the performance of the acrylate leveling agent.
  • the monomer A can be exemplified by methyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, or isobutyl (meth)acrylate.
  • tert-butyl (meth)acrylate hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (a) One or more of isobornyl acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate, and the like.
  • B is one or more selected from the group consisting of ethylenically unsaturated compound monomers having a substituted functional group, and the specific structural formula is: One or more of the monomers; R 3 is hydrogen or methyl, R 4 is a nitrogen-containing heterocyclic group or has the formula a group wherein n is an integer from 0 to 25, R 5 is O or N, and R 6 is a hydroxyl group, a carboxyl group, a sulfonic acid group, an aminoalkyl group, a polyoxyethylene group and/or a polyoxypropylene group, and a short carbon chain. Fluoroalkyl, polysiloxane based.
  • the monomer B can be exemplified by a hydroxyl group-containing (meth) acrylate, a carboxyl group-containing (meth) acrylate, a sulfonic acid group-containing (meth) acrylate, a polyoxyethylene group and/or a poly propylene oxide ( Methyl) acrylate, aminoalkyl-containing (meth)acrylamide, polysiloxane-containing (meth) acrylate, C 1 -C 4 fluoroalkyl-containing (meth) acrylate, and vinyl One or more of a nitrogen-containing heterocyclic ring or the like.
  • Examples of the hydroxyl group-containing (meth) acrylate are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • Examples of the carboxyl group-containing (meth) acrylate are (meth)acrylic acid and the like; examples of the sulfonic acid group-containing (meth) acrylate are (meth)acrylic acid propyl propyl sulfonate and the like;
  • Examples of alkyl (meth) acrylates are N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate and (meth)acrylic acid - N,N-diethylaminopropyl ester, etc.; examples of aminoalkyl-containing (meth)acrylamides are N,N-dimethylaminopropyl (meth)acrylamide, etc.; containing poly
  • the polar group such as a hydroxyl group, a carboxyl group or an amino group can improve the compatibility of the polyacrylate leveling agent and the binder resin, and enhance the wettability of the coating material to the substrate and the recoatability of the coating film.
  • Monomer B may further be a polysiloxane-based or short-chain fluoroalkyl-modified (meth) acrylate. Both the polysiloxane group and the short-chain fluoroalkyl group can greatly reduce the surface tension of the acrylate polymer, thereby resisting shrinkage and improving the wetting of the substrate, and at the same time imparting smooth and scratch-resistant properties to the coating film. Since it is known that a typical long-chain perfluoro compound having a perfluoro chain length C 8 ( eight carbon atoms) can form a refractory product such as perfluorooctanoic acid (PFOA), it is preferred to use a fluorinated short carbon based on environmental protection needs.
  • PFOA perfluorooctanoic acid
  • Chain (C 1 -C 4 ) fluorine-containing compound such as (meth)acrylic acid-2,2,2-trifluoroethyl ester, (meth)acrylic acid-2,2,3,3,3-pentafluoropropene Ester and (meth)acrylic acid-2,2,3,4,4,4-hexafluorobutyl ester, etc.).
  • R 6 is preferably a fluorine-containing alkyl group; when R 6 is preferably a polysiloxane group, at this time, it is prepared by esterification reaction of a terminal hydroxyl polysiloxane with acryloyl chloride or acrylic acid, and the obtained polysiloxane containing silicon
  • the molecular weight of the (meth) acrylate of the alkane is between 500 and 5,000.
  • a and b are independently an integer of from 1 to 1000 independently of each other, and are preferably an integer of from 1 to 5,000 independently of each other, and are independently an integer of from 1 to 200; usually by reaction time and reactant content. Make adjustments. It can be a random copolymer, a gradient copolymer or a block copolymer.
  • the preparation method of the above polyacrylate leveling agent comprises the following steps: monomer A and monomer B are initiated by an azo initiator, and RAFT activity controlled radical polymerization is carried out in the presence of a regulator (reversible addition-fragmentation) Chain transfer polymerization) to prepare a narrow molecular weight distribution polyacrylate leveling agent; the chemical structure of the regulator (or referred to as RAFT agent) is:
  • R 6 and R 7 are each independently alkyl, R 8 is phenyl, cyano, carboxy or ester; Z is phenyl, alkyl, alkylthio, phenoxy, alkoxy, alkane An amino group or a nitrogen-containing heterocyclic group.
  • the structural formula (II) is a dithioester compound; when Z is an alkylthio group, the structural formula (II) is a trithioester compound; when Z is a phenoxy group Or an alkoxy group, the structural formula (II) is a xanthate compound; when Z is an alkylamino group or a nitrogen-containing heterocyclic ring, the structural formula (II) is a dithiocarbamate compound.
  • the method is simple, easy to purify, high in yield, and has industrial prospects.
  • the regulator is preferably a trithioester compound, such as with Etc.; the best is (referred to as trithioester D, the synthesis method can refer to US 7659345). Since the azo initiator and the regulator are added during the reaction, the chemical structure of the polyacrylate leveling agent can be M may be a fragment of an initiator or a fragment of a modulator, preferably M is a fragment of the RAFT agent.
  • the above polyacrylate leveling agents can be used in coatings or ink systems, at least with the ability to significantly improve coating coating and crater resistance.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of n-butyl acrylate and hydroxyethyl methacrylate, P1) and a preparation method thereof, specifically:
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of tert-butyl acrylate and hydroxyethyl methacrylate, P1-1), which is basically the same as that in the first embodiment, except that :
  • the input was 40.5 g of t-butyl acrylate.
  • Product yield 56%
  • GPC results THF, PS standard
  • Mn 6310 g / mol
  • molecular weight distribution coefficient PDI 1.34, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of n-hexyl acrylate and hydroxyethyl methacrylate, P1-2), and the preparation method thereof is basically the same as that in the first embodiment, and the difference is only in:
  • the input was 40.5 g of n-hexyl acrylate.
  • Product yield 71%
  • GPC results THF, PS standard
  • Mn 8430 g / mol
  • PDI 1.32, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of 2-ethyl-butyl acrylate and hydroxyethyl methacrylate, P1-3), the preparation method thereof and the basic method in the first embodiment Consistently, the only difference is that 40.5 g of 2-ethyl-butyl acrylate is charged.
  • Product yield 48%
  • GPC results THF, PS standard
  • Mn 5780 g/mol
  • PDI 1.31, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of cyclohexyl acrylate and hydroxyethyl methacrylate, P1-4), which is basically the same as that in the first embodiment, except that :
  • the input was 40.5 g of cyclohexyl acrylate.
  • Product yield 67%
  • GPC results THF, PS standard
  • Mn 8150 g/mol
  • molecular weight distribution coefficient PDI 1.35, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and N-N-dimethylaminoethyl acrylate, P2-1), the preparation method thereof and the method in the embodiment 6
  • the difference is basically the same: the input is 36.7 g of acrylic acid-N,N-dimethylaminoethyl ester.
  • Product yield 68%
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and propyl propyl sulfonate, P2-2), and the preparation method thereof is basically the same as that in the embodiment 6. The only difference is that 36.7 g of propyl 3-sulfonate is used.
  • Product yield 78%
  • GPC results THF, PS standard
  • Mn 11320 g / mol
  • molecular weight distribution coefficient PDI 1.34, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and polyethylene glycol monomethyl ether methacrylate, P2-3), the preparation method thereof and the method in the sixth embodiment
  • Product yield 54%
  • GPC results THF, PS standard
  • Mn 6550 g/mol
  • PDI 1.31, viscous liquid.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and N,N-dimethylaminopropyl acrylamide, P2-4), the preparation method thereof and the embodiment 6
  • the basic agreement is the same: the input is 36.7gN, N-dimethylaminopropyl acrylamide.
  • the present embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and 2,2,2-trifluoroethyl acrylate, P2-7), the preparation method thereof and the embodiment 6
  • the input is 36.7g of 2,2,2-trifluoroethyl acrylate.
  • Product yield 58%
  • GPC results THF, PS standard
  • Mn 6260 g / mol
  • molecular weight distribution coefficient PDI 1.35, viscous liquid.
  • This embodiment provides a polyacrylate leveling agent (random copolymer of hexyl methacrylate and 2,2,2-trifluoroethyl acrylate and polysiloxane methacrylate, P2-8)
  • Product yield 82%
  • the present embodiment provides a polyacrylate leveling agent (block copolymer of n-butyl acrylate and 4-vinyl pyridine, P3) and a preparation method thereof, specifically:
  • the present embodiment provides a polyacrylate leveling agent (block copolymer of 2-ethylhexyl acrylate and 2-hydroxypropyl acrylate, P4) and a preparation method thereof, specifically:
  • the embodiment provides a polyacrylate leveling agent (block copolymer of tert-butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate, P5) and a preparation method thereof, and specific for:
  • the embodiment provides a polyacrylate leveling agent (block copolymer of tert-butyl acrylate and polysiloxane methacrylate, P6) and a preparation method thereof, specifically:
  • test procedure for leveling is:
  • Table 1 is a data sheet for adding the leveling agents of Examples 1 to 18, respectively, and without adding a leveling agent.
  • test procedure for anti-cratering is:
  • Table 2 is a data sheet for separately adding a leveling agent containing a polysiloxane or a fluorine-containing alkyl group in the examples, and not adding a leveling agent.
  • Example blank P2-6 P2-7 P2-8 P-5 P-6 Commercial products shrinkage cavity 5 2 2 1 2 2 3
  • the low surface tension property thereof imparts smoothness and wiping resistance to the coating film.
  • the procedure is consistent with the leveling test procedure and the slip test is performed using the Ray Ran microprocessor system.
  • the machine carried a weight of 200 grams through the coating and measured the coefficient of dynamic friction (COF).
  • Table 3 is a table of dynamic friction coefficients for adding the leveling agent in the examples and the commercially available products, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明涉及一种聚丙烯酸酯流平剂、制备方法及其应用，所述聚丙烯酸酯流平剂的化学结构通式为：通式(I)；单体A为选自化学结构通式为式（III）中的一种或多种的组合；R1为氢或者甲基；R2为碳原子数为1～22的直链、支链或环烷基；单体B为选自含有取代官能团的烯键不饱和化合物中的一种或多种的组合。单体A和单体B在化学结构通式为通式(II)的调聚剂存在下，进行RAFT活性可控自由基聚合，制备得到窄分子量分布的聚丙烯酸酯流平剂。这样制得的流平剂在应用于涂料或油墨体系中时能够显著提高涂层涂布和抗缩孔的能力，提高底材的湿润作用；更可能赋予涂膜平滑、耐擦拭的作用；其制备方法简单，易于大规模生产。

Description

一种聚丙烯酸酯流平剂、制备方法及其应用 技术领域
本发明涉及一种流平剂，具体涉及一种基于可逆加成-断裂链转移(RAFT)聚合的聚丙烯酸酯流平剂、制备方法及其应用，可作为流平剂应用在涂料和油墨中。
背景技术
涂料在干燥成膜的过程中：一方面随着溶剂的蒸发，涂膜表面和内部之间会由于温度、密度和表面张力的差异形成Benard旋涡，进而导致涂膜表面出现桔皮；另一方面，涂料中不溶性胶粒和外界存在的污染物会导致形成表面张力梯度，结果在涂膜表面形成缩孔。桔皮和缩孔属于流平缺陷，其破坏了涂料的装饰和防护功能。因此，需要添加流平剂来克服以上的缺陷，促使涂料在干燥过程中形成一个平整、光滑、均匀的涂膜。
已经证实聚丙烯酸酯适合作为流平剂应用于涂料体系，其由于和树脂体系具有受限的相容性而均匀分布在涂膜表面，在涂膜表面形成一个新的表面张力均一的界面层，进而获得一个平整光滑的涂膜。但聚丙烯酸酯流平剂的缺点是其与树脂体系的不相容性会随着聚合物分子量的增大而提高，可能会导致涂料出现浑浊和涂膜出现雾影；并且高分子量的聚丙烯酸酯流平剂粘度较高，会使涂料生产者带来操作上的麻烦。
已知以上缺点的解决办法是制备支化聚合物和使用活性可控自由基聚合制备聚丙烯酸酯流平剂。US6710127公开了聚丙烯酸酯类支化共聚物作为流平剂，该种支化聚合物由于存在大分子侧链，尽管具有很高的分子量，但是很小的基本分子链长度保证其具有较低的粘度。然而，这些支化聚合物的缺点是需要制备大分子单体，其制备步骤繁多，分离提纯困难，成本昂贵，不利于大规模工业化生产。而通过活性可控自由基聚合可以将聚合物的分子量分布处在很窄的水平，其分子量分布指数能够抵于1.5；更窄的分子量分布能够改进高分子量聚丙烯酸酯的粘度和不相容性，更好地发挥聚丙烯酸酯作为流平剂的性能；此外通过活性可控自由基聚合制备的聚合物由于保留有活性末端，能够引发第二单体的聚合形成嵌段共聚物，因此能够满足聚丙烯酸酯流平剂在聚合物链结构多样性上的需求。因此，利用上述方法开发新颖的聚丙烯酸酯流平剂以克服桔皮、缩孔等缺陷，并使其具有工业化生产前景，是该领域研发的热点。
发明内容
本发明目的是为了克服现有技术的不足而提供一种聚丙烯酸酯流平剂。
为达到上述目的，本发明采用的技术方案是：一种聚丙烯酸酯流平剂，所述聚丙烯酸酯流平剂的化学结构通式为：
Figure PCTCN2017083532-appb-000001
通式(I)中，
单体A为选自化学结构通式为
Figure PCTCN2017083532-appb-000002
单体中的一种或多种；R1为氢或者甲基；R2为碳原子数为1～22的直链、支链或环烷基；
单体B为选自含有取代官能团的烯键不饱和化合物单体中的一种或多种。
优化地，所述a和b相互独立地为1至1000的整数。
优化地，所述R2为碳原子数为1～22的直链或支链烷基。
优化地，所述B选自化学结构通式为
Figure PCTCN2017083532-appb-000003
单体中的一种或多种的组合，R3为氢或者甲基，R4为含氮杂环基团或者通式为
Figure PCTCN2017083532-appb-000004
的基团，n为0～25的整数，R5为O或者N，R6为羟基、羧基、磺酸基、氨基烷基、聚氧化乙烯基和/或聚氧化丙烯基、短碳链含氟烷基或聚硅氧烷基。
进一步地，当R4通式为
Figure PCTCN2017083532-appb-000005
的基团时，R6为含氟烷基或聚硅氧烷基。
进一步地，当R6为聚硅氧烷基时，单体B由端羟基聚硅氧烷与丙烯酰氯或丙烯酸进行酯化反应制得，其分子量为500～5000。
进一步地，所述a和b相互独立地为1至500的整数。
优化地，它为无规共聚物、梯度共聚物或者嵌段共聚物。
本发明的又一目的在于提供一种上述聚丙烯酸酯流平剂的制备方法，它包括以下步骤：
单体A和单体B由偶氮引发剂引发，在调控剂的存在下进行RAFT聚合即可；所述调控剂的化学结构通式为：
Figure PCTCN2017083532-appb-000006
通式(II)中，R9和R7相互独立地为烷基，R8为苯基、氰基、羧基或酯基；Z为苯基、烷基、烷硫基、苯氧基、烷氧基、烷氨基或含氮杂环基团。
本发明的再一目的在于提供一种上述聚丙烯酸酯流平剂在涂料或油墨中的应用
由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明聚丙烯酸酯流平剂，由特定的单体A和单体B聚合形成，尤其是在化学结构通式为
Figure PCTCN2017083532-appb-000007
的调聚剂存在下，进行RAFT活性可控自由基聚合，制备得到窄分子量分布的聚丙烯酸酯流平剂；R9和R7相互独立地为烷基，R8为苯基、氰基、羧基或酯基；Z为苯基、烷基、烷硫基、苯氧基、烷氧基、烷氨基或含氮杂环基团；这样制得的流平剂在应用于涂料或油墨体系中时能够显著提高涂层涂布和抗缩孔的能力，提高底材的湿润作用；更可能赋予涂膜平滑、耐擦拭的作用；其制备方法简单，易于大规模生产。
具体实施方式
本发明聚丙烯酸酯流平剂，所述聚丙烯酸酯流平剂的化学结构通式为：
Figure PCTCN2017083532-appb-000008
A为选自化学结构通式为
Figure PCTCN2017083532-appb-000009
单体中的一种或多种；R1为氢或甲基。R2为碳原子数为1～22的直链、支链或环烷基，其结构的不同可能影响丙烯酸酯流平剂的性能。单体A可以举例为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸十八烷基酯和(甲基)丙烯酸二十二烷基酯等中的一种或多种。
B为选自含有取代官能团的烯键不饱和化合物单体中的一种或多种，其具体结构通式为：
Figure PCTCN2017083532-appb-000010
单体中的一种或多种；R3为氢或者甲基，R4为含氮杂环基团或通式为
Figure PCTCN2017083532-appb-000011
的基团，n为0～25的整数，R5为O或者N，R6为羟基、羧基、磺酸基、氨基烷基、聚氧化乙烯基和/或聚氧化丙烯基、短碳链含氟烷基、聚硅氧烷基。单体B可以举例为含羟基的(甲基)丙烯酸酯、含羧基的(甲基)丙烯酸酯、含磺酸基的(甲基)丙烯酸酯、含聚氧化乙烯和/或聚氧化丙烯的(甲基)丙烯酸酯、含氨基烷基的(甲基)丙烯酰胺、含聚硅氧烷的(甲基)丙烯酸酯、含C1-C4氟烷基的(甲基)丙烯酸酯和乙烯基含氮杂环等中的一种或多种。其中，含羟基的(甲基)丙烯酸酯的实例为(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯和(甲基)丙烯酸-4-羟基丁酯等；含羧基的(甲基)丙烯酸酯的实例为(甲基)丙烯酸等；含磺酸基的(甲基)丙烯酸酯的实例为(甲基)丙烯酸-3-磺酸丙酯等；含氨基烷基的(甲基)丙烯酸酯的实例为(甲基)丙烯酸-N，N-二甲氨基乙酯、(甲基)丙烯酸-N，N-二甲氨基丙酯和(甲基)丙烯酸-N，N-二乙氨基丙酯等；含氨基烷基的(甲基)丙烯酰胺的实例为N，N-二甲基氨基丙基(甲基)丙烯酰胺等；含聚氧化乙烯和/或聚氧化丙烯的(甲基)丙烯酸酯的实例是分子量在300～5000之间的聚乙二醇和/或聚丙二醇单甲醚(甲基)丙烯酸酯等；乙烯基含氮杂环的实例为4-乙烯基吡啶、2-乙烯基吡啶、1-乙烯基咪唑、2-乙烯基吡嗪等。这是因为含有的羟基、羧基、氨基等极性基团能够改善聚丙烯酸酯流平剂和基料树脂的相容性，加强涂料对底材的润湿性以及涂膜的重涂性。
单体B进一步可以是聚硅氧烷基或短链氟烷基改性的(甲基)丙烯酸酯。聚硅氧烷基和短链氟烷基都可以大幅降低丙烯酸酯聚合物的表面张力，从而起到抗缩孔、提高底材润湿的作用，同时能够赋予涂膜平滑、耐擦拭的性能。由于已知典型的全氟链长度C8(碳原子数为8个)的长链全氟化合物能够形成难降解的产物如全氟辛酸(PFOA)，基于环境保护的需要，优选使用基于氟化短碳链(C1-C4)的含氟化合物(如(甲基)丙烯酸-2，2，2-三氟乙酯、(甲基)丙烯酸-2，2，3，3，3-五氟丙酯和(甲基)丙烯酸-2，2，3，4，4，4-六氟丁酯等)。即R6优选为含氟烷基；当R6优选为聚硅氧烷基时，此时它是通过端羟基聚硅氧烷与丙烯酰氯或丙烯酸的酯化反应制备，得到的含聚硅氧烷的(甲基)丙烯酸酯的分子量在500～5000之间。
式中，a和b相互独立地为1至1000的整数，相互独立地优选为1-5000的整数，相互独立地最优为1-200的整数；通常可以通过反应时间、反应物含量对其进行调节。它可以为无规共聚物、梯度共聚物或者嵌段共聚物。
上述聚丙烯酸酯流平剂的制备方法，它包括以下步骤：单体A和单体B由偶氮引发剂引发，在调控剂的存在下进行RAFT活性可控自由基聚合(可逆加成-断裂链转移聚合)制备得到窄分子量分布的聚丙烯酸酯流平剂；所述调控剂(或者称为RAFT试剂)的化学结构通式为：
Figure PCTCN2017083532-appb-000012
式中，R6和R7相互独立地为烷基，R8为苯基、氰基、羧基或酯基；Z为苯基、烷基、烷硫基、苯氧基、烷氧基、烷氨基或含氮杂环基团。当Z为苯基或烷基时，结构通式(II)为二硫代酯化合物；当Z为烷硫基时，结构通式(II)为三硫代酯化合物；当Z为苯氧基或烷氧基时，结构通式(II)为黄原酸酯化合物；当Z为烷氨基或含氮杂环时，结构通式(II)为二硫代氨基甲酸酯化合物。该方法简单易行、易于提纯、收率高，并有工业化的前景。调控剂优选为三硫代酯化合物，如
Figure PCTCN2017083532-appb-000013
和
Figure PCTCN2017083532-appb-000014
等；最优的是
Figure PCTCN2017083532-appb-000015
(简称三硫代酯D，合成方法可参考US 7659345)。由于在反应过程中加入了偶氮引发剂和调控剂，聚丙烯酸酯流平剂的化学结构通式为可以为
Figure PCTCN2017083532-appb-000016
M可能是引发剂的片段，也可能是调控剂的片段，优选M是RAFT试剂的片段。
上述聚丙烯酸酯流平剂可应用在涂料或油墨体系中，至少具有显著提高涂层涂布和抗缩孔的能力。
下面将结合实施例对本发明进行进一步说明。
实施例1
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸正丁酯和甲基丙烯酸羟乙酯的无规共聚物，P1)及其制备方法，具体为：
在附有冷凝管、温度计和顶置式搅拌器的250mL四口烧瓶中投入40g醋酸丁酯、40.5g丙烯酸正丁酯、28.1g甲基丙烯酸羟乙酯、2.05g三硫代酯D和0.46g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h；随后，在100℃下进行减压蒸馏除去全 部溶剂和未反应的单体。产品产率：63％，GPC结果(THF，PS标样)：Mn＝7950g/mol、分子量分布系数PDI＝1.37、粘性液体。
实施例2
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸叔丁酯和甲基丙烯酸羟乙酯的无规共聚物，P1-1)，其制备方法与实施例1中的基本一致，不同仅在于：投入的是40.5g丙烯酸叔丁酯。产品产率：56％，GPC结果(THF，PS标样)：Mn＝6310g/mol、分子量分布系数PDI＝1.34、粘性液体。
实施例3
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸正己酯和甲基丙烯酸羟乙酯的无规共聚物，P1-2)，其制备方法与实施例1中的基本一致，不同仅在于：投入的是40.5g丙烯酸正己酯。产品产率：71％，GPC结果(THF，PS标样)：Mn＝8430g/mol、分子量分布系数PDI＝1.32、粘性液体。
实施例4
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸2-乙基-丁基酯和甲基丙烯酸羟乙酯的无规共聚物，P1-3)，其制备方法与实施例1中的基本一致，不同仅在于：投入的是40.5g丙烯酸2-乙基-丁基酯。产品产率：48％，GPC结果(THF，PS标样)：Mn＝5780g/mol、分子量分布系数PDI＝1.31、粘性液体。
实施例5
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸环己酯和甲基丙烯酸羟乙酯的无规共聚物，P1-4)，其制备方法与实施例1中的基本一致，不同仅在于：投入的是40.5g丙烯酸环己酯。产品产率：67％，GPC结果(THF，PS标样)：Mn＝8150g/mol、分子量分布系数PDI＝1.35、粘性液体。
实施例6
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和丙烯酸的无规共聚物，P2)，其制备方法与实施例1中的基本一致，不同的是：向四口烧瓶中投入45g二甲苯、39.4g甲基丙烯酸己酯、36.7g丙烯酸、2.05g三硫代酯D和0.46g偶氮二异丁腈。产率：75％，GPC结果(THF，PS标样)：Mn＝10460g/mol，分子量分布系数PDI＝1.41，粘性液体。
实施例7
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和丙烯酸-N，N-二甲氨基乙酯的无规共聚物，P2-1)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g丙烯酸-N，N-二甲氨基乙酯。产品产率：68％，GPC结果(THF，PS标样)：Mn＝9450g/mol、分子量分布系数PDI＝1.39、粘性液体。
实施例8
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和丙烯酸-3-磺酸丙酯的无规共聚物，P2-2)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g丙烯酸-3-磺酸丙酯。产品产率：78％，GPC结果(THF，PS标样)：Mn＝11320g/mol、分子量分布系数PDI＝1.34、粘性液体。
实施例9
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和聚乙二醇单甲醚甲基丙烯酸酯的无规共聚物，P2-3)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g聚乙二醇单甲醚甲基丙烯酸酯(Mn＝400g/mol)。产品产率：54％，GPC结果(THF，PS标样)：Mn＝6550g/mol、分子量分布系数PDI＝1.31、粘性液体。
实施例10
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和N，N-二甲基氨基丙基丙烯酰胺的无规共聚物，P2-4)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7gN，N-二甲基氨基丙基丙烯酰胺。产品产率：81％，GPC结果(THF，PS标样)：Mn＝14660g/mol、分子量分布系数PDI＝1.41、粘性液体。
实施例11
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和乙烯基咪唑的无规共聚物，P2-5)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g乙烯基咪唑。产品产率：59％，GPC结果(THF，PS标样)：Mn＝7560g/mol、分子量分布系数PDI＝1.32、粘性液体。
实施例12
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和聚硅氧烷甲基丙烯酸酯的无规共聚物，P2-6)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g聚硅氧烷甲基丙烯酸酯(Mn＝1000g/mol)。产品产率：73％，GPC结果(THF，PS标样)：Mn＝10120 g/mol、分子量分布系数PDI＝1.43、粘性液体。
实施例13
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和丙烯酸-2，2，2-三氟乙酯的无规共聚物，P2-7)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是36.7g丙烯酸-2，2，2-三氟乙酯。产品产率：58％，GPC结果(THF，PS标样)：Mn＝6260g/mol、分子量分布系数PDI＝1.35、粘性液体。
实施例14
本实施例提供一种聚丙烯酸酯流平剂(甲基丙烯酸己酯和丙烯酸-2，2，2-三氟乙酯以及聚硅氧烷甲基丙烯酸酯的无规共聚物，P2-8)，其制备方法与实施例6中的基本一致，不同仅在于：投入的是22.7g丙烯酸-2，2，2-三氟乙酯和25.3g聚硅氧烷甲基丙烯酸酯(Mn＝1000g/mol)。产品产率：82％，GPC结果(THF，PS标样)：Mn＝13120g/mol、分子量分布系数PDI＝1.45、粘性液体。
实施例15
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸正丁酯和4-乙烯基吡啶的嵌段共聚物，P3)及其制备方法，具体为：
在附有冷凝管、温度计和顶置式搅拌器的250mL四口烧瓶中投入70g丙二醇甲醚醋酸酯、67.5g丙烯酸正丁酯，2.05g三硫代酯D和0.46g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h；之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体得聚丙烯酸正丁酯(产率：51％，GPC结果(THF，PS标样)：Mn＝6350g/mol、分子量分布系数PDI＝1.20，粘性液体)；
随后，在附有冷凝管、温度计、顶置式搅拌器的250mL四口烧瓶中投入80g丙二醇甲醚醋酸酯、60g上述的聚丙烯酸正丁酯(Mn＝6350g/mol)、52.9g 4-乙烯基吡啶和0.78g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h；之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体即可。产率：47％，GPC结果(THF，PS标样)：Mn＝8930g/mol、分子量分布系数PDI＝1.39、粘性液体。
实施例16
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸-2-乙基己酯和丙烯酸-2-羟基丙酯的嵌段共聚物，P4)及其制备方法，具体为：
在附有冷凝管、温度计和顶置式搅拌器的250mL四口烧瓶中投入60g丙二醇甲醚醋酸酯、78.8g丙烯酸-2-乙基己酯、2.05g三硫代酯D和0.46g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h。之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体得聚丙烯酸-2-乙基己酯(产率：69％，GPC结果(THF，PS标样)：Mn＝10350g/mol、分子量分布系数PDI＝1.27、粘性液体。)；
随后，在附有冷凝管、温度计、顶置式搅拌器的250mL四口烧瓶中投入50g丙二醇甲醚醋酸酯、60g上述聚丙烯酸-2-乙基己酯(Mn＝10350g/mol)、43.3g丙烯酸-2-羟基丙酯和0.47g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h；之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体。产率：72％，GPC结果(THF，PS标样)：Mn＝15200g/mol，分子量分布系数PDI＝1.43，粘性液体。
实施例17
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸叔丁酯和丙烯酸-2，2，3，4，4，4-六氟丁酯的嵌段共聚物，P5)及其制备方法，具体为：
在附有冷凝管、温度计和顶置式搅拌器的250mL四口烧瓶中投入60g丙二醇甲醚醋酸酯、56.3g丙烯酸叔丁酯、2.05g三硫代酯D和0.46g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h。之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体得聚丙烯酸叔丁酯(产率：58％，GPC结果(THF，PS标样)：Mn＝6170g/mol、分子量分布系数PDI＝1.19、粘性液体)。
随后，在附有冷凝管、温度计、顶置式搅拌器的250mL四口烧瓶中投入60g丙二醇甲醚醋酸酯，60g上述聚丙烯酸叔丁酯(Mn＝6170g/mol)，28.8g丙烯酸-2，2，3，4，4，4-六氟丁酯和0.79g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h。之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体。产率：52％，GPC结果(THF，PS标样)：Mn＝7780g/mol，分子量分布系数PDI＝1.31，粘性液体。
实施例18
本实施例提供一种聚丙烯酸酯流平剂(丙烯酸叔丁酯和聚硅氧烷甲基丙烯酸酯的嵌段共聚物，P6)及其制备方法，具体为：
在附有冷凝管、温度计和顶置式搅拌器的250mL四口烧瓶中投入60g丙二醇甲醚醋酸酯、68.7g丙烯酸叔丁酯、2.05g三硫代酯D和0.46g偶氮二异丁腈，开动搅拌，采用N2/真空脱 气3次，并在N2、75℃下聚合4h。之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体得聚丙烯酸叔丁酯(产率：71％，GPC结果(THF，PS标样)：Mn＝7980g/mol、分子量分布系数PDI＝1.19、粘性液体)。
随后，在附有冷凝管、温度计、顶置式搅拌器的250mL四口烧瓶中投入60g丙二醇甲醚醋酸酯，50g上述聚丙烯酸叔丁酯(Mn＝7980g/mol)，28.8g聚硅氧烷甲基丙烯酸酯(Mn＝1000g/mol)和0.79g偶氮二异丁腈，开动搅拌，采用N2/真空脱气3次，并在N2、75℃下聚合4h。之后，在100℃下进行减压蒸馏除去全部溶剂和未反应的单体。产率：61％，GPC结果(THF，PS标样)：Mn＝10300g/mol，分子量分布系数PDI＝1.31，粘性液体。
将实施例1至实施例18分别进行涂布实验，测试其流平性、抗缩孔性和平滑性，具体为：
1、流平性的测试步骤为：
(1)将1753羟基丙烯酸树脂(40g)、二甲苯(5g)和丙二醇甲醚醋酸酯(5g)混合均匀，配制成清漆；
(2)在玻璃容器中精确称取流平剂(0.05g，并以不添加流平剂的样品作为空白样)，
(3)在加过助剂的玻璃容器中精确称取清漆，
(4)将上述称取的样品放入SK450振荡机进行振荡混合5分钟，
(5)振荡完毕，立刻取出，
(6)加入N3390交联剂(80g)配制成可固化的漆，
(7)将配制好的清漆样刮涂于无色透明聚酯薄膜上，
(8)常温干燥，
(9)评判涂膜平整度和透明情况，并做记录，结果见表1所示。
表1为分别添加实施例1至实施例18中流平剂、及不添加流平剂的数据表
Figure PCTCN2017083532-appb-000017
Figure PCTCN2017083532-appb-000018
表1中，评判流平性能的数字越小，说明其流平性能越佳；相应地，数字越大，说明其流平性能越差。从表中可看出使用RFAT方法制备的聚丙烯酸酯流平剂的流平性能优于市售产品，并且含直链烷烃的聚丙烯酸酯的流平性能稍优于含支链烷烃的聚丙烯酸酯；同时含聚硅氧烷或含氟的聚丙烯酸酯流平性能最佳，但是因为极性低的缘故，其清澈度稍差。
2、抗缩孔性的测试步骤为：
(1)将1753羟基丙烯酸树脂(40g)、二甲苯(5g)和丙二醇甲醚醋酸酯(5g)混合均匀，配制成清漆，
(2)在玻璃容器中精确称取流平剂(0.05g，并以不添加流平剂的样品作为空白样)，
(3)在加过助剂的玻璃容器中精确称取清漆和EFKA-2018(0.15g)，
(4)将上述称取的样品放入SK450振荡机进行振荡混合5分钟，
(5)振荡完毕，立刻取出，
(6)加入N3390交联剂(80g)配制成可固化的漆，
(7)将配制好的清漆样刮涂于无色透明聚酯薄膜上，
(8)常温干燥，
(9)评判涂膜抗缩孔情况，并做记录。
表2为分别添加实施例中含聚硅氧烷或含氟烷基的流平剂、及不添加流平剂的数据表
实施例 空白 P2-6 P2-7 P2-8 P-5 P-6 市售产品
缩孔 5 2 2 1 2 2 3
表2中，评判抗缩孔性能的数字越小，说明其抗缩孔性能越佳；相应地，数字越大，说明其抗缩孔性能越差。从表中可看出由于聚硅氧烷和含氟烷基的强烈降低表面张力的作用，其制备的聚丙烯酸酯流平剂的抗缩孔性能优于市售产品，特别是同时引入聚硅氧烷和含氟烷基时，其抗缩孔性能最佳。
3、平滑、耐擦拭性能
由于本发明中的聚丙烯酸酯流平剂中引入了聚硅氧烷和含氟烷基，其具有的低表面张力性质能够赋予涂膜平滑、耐擦拭的性能。操作步骤和流平性测试步骤一致，并使用Ray Ran微处理器系统进行滑移测试。机器载着200克的重量穿过涂层并测定动态摩擦系数(COF)。
表3为分别添加实施例中流平剂、及市售产品的动态摩擦系数表
  动态COF 空白 市售产品 P2-6 P2-7 P2-8 P5 P6
1 0.25％ 1.05 0.57 0.43 0.47 0.38 0.45 0.39
2 0.5％ 1.25 0.55 0.43 0.46 0.37 0.44 0.38
3 1.0％ 1.65 0.54 0.42 0.45 0.36 0.44 0.37
结果表明，实施例中的聚丙烯酸酯流平剂的平滑、耐擦拭性能优于市售产品。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (14)

  1. 一种聚丙烯酸酯流平剂，所述聚丙烯酸酯流平剂的化学结构通式为：
    Figure PCTCN2017083532-appb-100001
    其特征在于：通式(I)中，
    单体A为选自化学结构通式为
    Figure PCTCN2017083532-appb-100002
    的化合物中的一种或多种的组合；其中，R1为氢或者甲基；R2为碳原子数为1～22的直链、支链或环烷基；
    单体B为选自含有取代官能团的烯键不饱和化合物中的一种或多种的组合；
    a和b相互独立地为1至1000的整数。
  2. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：所述R2为碳原子数为1～22的直链或支链烷基。
  3. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：所述B选自化学结构通式为
    Figure PCTCN2017083532-appb-100003
    的化合物中的一种或多种的组合，
    其中，
    R3为氢或者甲基，
    R4为含氮杂环基团或者化学结构通式为
    Figure PCTCN2017083532-appb-100004
    的基团，n为0～25的整数，
    R5为O或者N，
    R6为羟基、羧基、磺酸基、氨基烷基、聚氧化乙烯基和/或聚氧化丙烯基、短碳链含氟烷基或聚硅氧烷基。
  4. 根据权利要求3所述的聚丙烯酸酯流平剂，其特征在于：R4为化学结构通式为
    Figure PCTCN2017083532-appb-100005
    的基团，R6为含氟烷基或聚硅氧烷基。
  5. 根据权利要求4所述的聚丙烯酸酯流平剂，其特征在于：R6为聚硅氧烷基，单体B由端羟基聚硅氧烷与丙烯酰氯或丙烯酸进行酯化反应制得，其分子量为500～5000。
  6. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：所述a和b相互独立地为1至500 的整数。
  7. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：它为无规共聚物、梯度共聚物或者嵌段共聚物。
  8. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：单体A为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸十八烷基酯和(甲基)丙烯酸二十二烷基酯等中的一种或多种的组合。
  9. 根据权利要求1所述的聚丙烯酸酯流平剂，其特征在于：单体B为含羟基的(甲基)丙烯酸酯、含羧基的(甲基)丙烯酸酯、含磺酸基的(甲基)丙烯酸酯、含聚氧化乙烯和/或聚氧化丙烯的(甲基)丙烯酸酯、含氨基烷基的(甲基)丙烯酰胺、含聚硅氧烷的(甲基)丙烯酸酯、含C1-C4氟烷基的(甲基)丙烯酸酯和乙烯基含氮杂环等中的一种或多种的组合。
  10. 根据权利要求9所述的聚丙酸酯流平剂，其特征在于：单体B是聚硅氧烷基或短链氟烷基改性的(甲基)丙烯酸酯。
  11. 一种如权利要求1至10中任一所述聚丙烯酸酯流平剂的制备方法，其特征在于，它包括以下步骤：
    单体A和单体B由偶氮引发剂引发，在调控剂的存在下进行RAFT聚合；所述调控剂的化学结构通式为：
    Figure PCTCN2017083532-appb-100006
    通式(II)中，
    R9和R7相互独立地为烷基，R8为苯基、氰基、羧基或酯基；Z为苯基、烷基、烷硫基、苯氧基、烷氧基、烷氨基或含氮杂环基团。
  12. 根据权利要求11所述的制备方法，其特征在于，
    Z为苯基或烷基，所述调控剂为二硫代酯化合物；
    或，Z为烷硫基，所述调控剂为三硫代酯化合物；
    或，Z为苯氧基或烷氧基，所述调控剂为黄原酸酯化合物；
    或，Z为烷氨基或含氮杂环，所述调控剂为二硫代氨基甲酸酯化合物。
  13. 根据权利要求12所述的制备方法，其特征在于，所述调控剂为
    Figure PCTCN2017083532-appb-100007
    Figure PCTCN2017083532-appb-100008
  14. 权利要求1至10中任一所述聚丙烯酸酯流平剂在涂料或油墨中的应用。
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