WO2018157747A1 - 一种高固体分丙烯酸树脂的制备方法 - Google Patents

一种高固体分丙烯酸树脂的制备方法 Download PDF

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WO2018157747A1
WO2018157747A1 PCT/CN2018/076795 CN2018076795W WO2018157747A1 WO 2018157747 A1 WO2018157747 A1 WO 2018157747A1 CN 2018076795 W CN2018076795 W CN 2018076795W WO 2018157747 A1 WO2018157747 A1 WO 2018157747A1
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parts
acrylic resin
weight
solvent
acrylate
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PCT/CN2018/076795
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English (en)
French (fr)
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施英
张文泉
朱萌
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无锡阿科力科技股份有限公司
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Priority to US16/489,928 priority Critical patent/US11059923B2/en
Publication of WO2018157747A1 publication Critical patent/WO2018157747A1/zh

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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (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
    • 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
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (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
    • 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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
    • 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
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (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
    • 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
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • Disclosed herein is a method of preparing a high solids acrylic resin for use primarily in the automotive coatings and home improvement coatings.
  • the high solids acrylic resin has excellent comprehensive properties, especially in terms of weather resistance, gloss and film fullness. Therefore, it is well received by the market and is one of the fastest growing varieties in the coating industry. In order to reduce the VOC emissions and increase the solid content of the coating, it is necessary to reduce the viscosity of the coating resin as much as possible. Commonly used measures are: reducing the molecular weight of the resin, lowering the glass transition temperature of the resin and using a reactive diluent. However, these measures have the disadvantage of reducing the performance of the coating, and it is easy to cause damage to the performance of the coating film. In recent years, functional methacrylate monomers have become more and more popular among coating resin manufacturers, effectively reducing viscosity and increasing solid content while ensuring that resin properties are not affected.
  • the method for preparing high solids low viscosity acrylic resin in the literature reports is mainly achieved by adding special functional monomers.
  • Chinese patent CN104672366A introduces a method for synthesizing high-solid and low-viscosity acrylic resin with a functional monomer of tert-carbonate (Cardura E-10), adding 10-20 parts of glycidyl tert-carbonate, and finally acrylic resin.
  • the solid content is up to 70% and the viscosity is 3000-6000 mPa ⁇ s.
  • Another type of functional monomer is an alicyclic acrylate.
  • isobornyl (meth)acrylate and cyclohexyl (meth)acrylate wherein isobornyl (meth)acrylate is widely used and lowered.
  • a monomer having a better viscosity effect such as US Pat. No. 6,606,003, describes a composition and a preparation method of a high solids coating material, using xylene as a solvent, di-tert-butyl peroxide as an initiator, and adding acrylic acid and A.
  • a monomer such as hydroxyethyl acrylate, styrene or isobornyl methacrylate can be used to obtain a coating having a solid content of 50.0% or more.
  • the glycidyl ester of tert-carbonate decreases with the polymer segment during the reaction, and the reactivity of the carboxyl groups present on the macromolecule decreases. It can not fully react with the epoxy group in the glycidyl tert-carbonate, which is easy to cause the water resistance and weather resistance of the coating film to be deteriorated, and the price of glycidyl tert-carbonate is expensive, which further restricts its further research and application.
  • the synthetic raw material of isobornyl (meth)acrylate monomer is processed from natural products and is greatly affected by production and market constraints, so its price is also high and fluctuates greatly.
  • the purpose of the present disclosure is to overcome the deficiencies in the prior art and to provide a method for preparing a high solids acrylic resin having a low viscosity and good leveling property.
  • the method for preparing the high solids acrylic resin comprises the following steps:
  • a preparing the following reaction raw materials: 0.2 to 2 parts by weight of acrylic acid or 0.2 to 2 parts by weight of methacrylic acid, 20 to 40 parts by weight of alkyl acrylate or 20 to 40 parts by weight of alkyl methacrylate, 0 ⁇ 25 parts by weight of styrene, 1.0 to 10.0 parts by weight of hydroxyethyl acrylate or 1.0 to 10.0 parts by weight of hydroxypropyl acrylate, 10.0 to 50.0 parts by mass of bridged-chain acrylate, and chemical formula of bridged-ring structure acrylate for:
  • R, R 1 , R 2 , R 3 , R 4 is hydrogen or methyl, and the k value is 0 or 1;
  • the initiator is benzoyl peroxide, azobisisobutyronitrile, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide or Di-tert-amyl peroxide.
  • the solvent is toluene, xylene, ethylene glycol butyl ether acetate, propylene glycol methyl ether propionate, butyl acetate, cyclohexanone or n-butanol.
  • the bridged ring structure acrylate is:
  • the present disclosure adopts an acrylate containing a bridged ring structure as a functional monomer for the preparation of a high solids acrylic resin, which can effectively reduce the viscosity of the resin, increase the solid content of the resin, and obtain the viscosity of the acrylic resin of the acrylic resin.
  • ⁇ 25S (25 ° C) the solids are 70% to 75%.
  • the acrylic resin of the present disclosure has low viscosity, easy construction, good leveling property, high gloss, good vividness and good film fullness.
  • Methyl methacrylate 12.0 parts
  • a high solids acrylic resin was prepared as follows:
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 17S (25 ° C) and the solid content was 70.0%.
  • Methacrylic acid 0.2 parts
  • N-octyl acrylate 2.0 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent is added: xylene, stirred and heated to reflux temperature (ie, the boiling temperature of xylene);
  • the raw material and the initiator in the above ratio are put into the dropping funnel and stirred, and the dropwise addition is completed at a constant rate within 5 hours, and after the completion of the dropwise addition, the reflux temperature is maintained and stirring is continued for 3 hours;
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 20S (25 ° C), and the solid content was 75.0%.
  • Methyl methacrylate 8.0 parts
  • a high solids acrylic resin was prepared as follows:
  • the solvent ethylene glycol butyl ether acetate, stirred and heated to reflux temperature (ie ethylene glycol butyl ether acetate) Boiling point temperature);
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 15S (25 ° C) and the solid content was 75.0%.
  • a high solids acrylic resin is prepared in the following parts by weight:
  • Methacrylic acid 1.5 parts;
  • Methyl methacrylate 10.0 parts
  • a high solids acrylic resin was prepared as follows:
  • the solvent propylene glycol methyl ether propionate, stirred and heated to reflux temperature (ie the boiling temperature of propylene glycol methyl ether propionate) );
  • the raw material and the initiator in the above ratio are put into the dropping funnel and stirred, and the dropwise addition is completed at a constant rate within 3 hours. After the completion of the dropwise addition, the reflux temperature is maintained and stirring is continued for 4 hours;
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 22 S (25 ° C) and the solid content was 72.5%.
  • N-butyl acrylate 15.0 parts
  • butyl methacrylate 8.0 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent butyl acetate, stirred and heated to reflux temperature (ie, the boiling temperature of butyl acetate);
  • the raw material and the initiator in the above ratio are put into the dropping funnel and stirred, and the dropwise addition is completed at a constant rate within 3 hours. After the completion of the dropwise addition, the reflux temperature is maintained and stirring is continued for 4 hours;
  • the acrylic resin Grignard tube prepared in this example was tested to have a viscosity of 15 S (25 ° C) and a solid content of 70.5%.
  • Methyl methacrylate 12.0 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent cyclohexanone, stirred and heated to reflux temperature (ie, the boiling temperature of cyclohexanone);
  • the raw material and the initiator in the above ratio are put into the dropping funnel and stirred, and the dropwise addition is completed at a constant rate within 5 hours, and the stirring is continued for 4 hours after the completion of the dropwise addition;
  • the acrylic resin Grignard tube prepared in this example was tested to have a viscosity of 25 S (25 ° C) and a solid content of 70.0%.
  • Methyl acrylate 7.0 parts
  • Methyl methacrylate 15.0 parts
  • a high solids acrylic resin was prepared as follows:
  • n-butanol stirred and heated to reflux temperature (ie, the boiling temperature of n-butanol);
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 18S (25 ° C) and the solid content was 70.0%.
  • Methacrylic acid 1.5 parts;
  • N-octyl acrylate 4.0 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent is added: xylene, stirred and heated to reflux temperature (ie, the boiling temperature of xylene);
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 22 S (25 ° C) and the solid content was 70.5%.
  • Methyl methacrylate 21.5 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent is added: xylene, stirred and heated to reflux temperature (ie, the boiling temperature of xylene);
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 25 S (25 ° C) and the solid content was 74.8%.
  • N-octyl acrylate 5.0 parts
  • Methyl methacrylate 15.0 parts
  • a high solids acrylic resin was prepared as follows:
  • a solvent is added: xylene, stirred and heated to reflux temperature (ie, the boiling temperature of xylene);
  • the viscosity of the acrylic resin Grignard tube prepared in this example was 20S (25 ° C) and the solid content was 73.5%.
  • Methyl methacrylate 18.0 parts;
  • a high solids acrylic resin was prepared as follows:
  • the viscosity of the acrylic resin Grignard tube prepared in this comparative example was 65 S (25 ° C) and the solid content was 70.8%.
  • the film properties are shown in Table 1.
  • a high solids acrylic resin was prepared as follows:
  • reaction monomer and the initiator in the above ratio were put into the dropping funnel and stirred, and the dropwise addition was completed at 4 hours after the completion of the dropwise addition, and the stirring was continued at the reflux temperature for 2 hours;
  • the viscosity of the acrylic resin Grignard tube prepared in this comparative example was 20S (25 ° C) and the solid content was 71.0%.
  • Table 1 paint film performance table of different examples

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

Abstract

一种高固体分丙烯酸树脂的制备方法，包括以下步骤：准备丙烯酸或者甲基丙烯酸、丙烯酸烷基酯或者甲基丙烯酸烷基酯、苯乙烯、丙烯酸羟乙酯或者丙烯酸羟丙酯、桥环结构丙烯酸酯、引发剂和溶剂；在反应器中投入溶剂，搅拌并升温至溶剂的沸点温度；在滴液漏斗中投入反应原料和引发剂并搅拌，滴加完毕后保持溶剂的沸点温度并继续搅拌；反应结束后冷却出料。制得的丙烯酸树脂的格氏管粘度为15～25S(25℃)，固体分为70％～75％。

Description

一种高固体分丙烯酸树脂的制备方法 技术领域
本文公开了一种主要在汽车涂料以及家装涂料领域使用的高固体分丙烯酸树脂的制备方法。
背景技术
随着国家对节能环保的日趋重视，2015年2月开始对涂料征收消费税，同时特别指出，对施工状态下挥发性有机物(VOC)含量低于420g/L(含)的涂料免征消费税。这项政策对整个涂料行业提出了更加严格的要求。高固体分涂料因VOC含量低，施工性能好，在施工过程中可达到规定的排放标准，因此研发低溶剂型、高固体分、高性能、低成本的涂料成为目前的发展趋势。
高固体分丙烯酸树脂具有优良的综合性能，特别是在耐候性、光泽及漆膜丰满度等方面具有独特的优越性，因此深受市场欢迎，是目前涂料行业中发展较快的品种之一。为降低VOC的排放，提高涂料的固含量，必须尽可能降低涂料树脂的粘度。常用的措施有：降低树脂分子量，降低树脂玻璃化温度及采用活性稀释剂。但是这些措施具有降低涂料性能的弊端，容易对涂膜性能造成伤害。近年来，功能型甲基丙烯酸酯单体越来越受到涂料树脂生产企业的欢迎，在保证树脂性能不受影响的情况，有效降低粘度，提高固含量。
文献报道中制备高固体分低粘度丙烯酸树脂方法主要是通过添加特殊的功能性单体而得以实现。如中国专利CN104672366A介绍了一种以叔碳酸缩水甘油酯(Cardura E-10)为功能性单体合成高固低黏丙烯酸树脂的方法，添加10-20份的叔碳酸缩水甘油酯，最终丙烯酸树脂的固体分可达70％，黏度3000-6000mPa·s。另一类功能性单体为脂环族丙烯酸酯，常用的有(甲基)丙烯酸异冰片酯、(甲基)丙烯酸环己酯，其中(甲基)丙烯酸异冰片酯是应用较广、降粘 效果较好的一种单体，如美国专利US6069203介绍了一种高固体分涂料的组成成分及制备方法，以二甲苯为溶剂，二叔丁基过氧化物为引发剂，添加丙烯酸、甲基丙烯酸羟乙酯、苯乙烯及甲基丙烯酸异冰片酯等单体，制得固含量50.0％以上的涂料。
这类功能性单体具有良好的降粘效果，亦有它们的局限性所在，叔碳酸缩水甘油酯在反应过程中随着聚合物链段增长，存在于大分子上的羧基反应活性下降，从而不能与叔碳酸缩水甘油酯中环氧基团充分反应，易造成涂膜耐水性、耐候性等变差，而且叔碳酸缩水甘油酯价格昂贵，也大大制约了其进一步的研究应用。(甲基)丙烯酸异冰片酯单体的合成原料莰烯是由天然产物加工而来，受产量和市场制约影响大，因此其价格也较高而且波动较大。
发明内容
以下是对本公开详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开的目的是克服现有技术中存在的不足，提供一种所得产品粘度低、流平性好的高固体分丙烯酸树脂的制备方法。
按照本公开提供的技术方案，所述高固体分丙烯酸树脂的制备方法包括以下步骤：
a、准备以下反应原料：0.2～2重量份的丙烯酸或者0.2～2重量份的甲基丙烯酸，20～40重量份的丙烯酸烷基酯或者20～40重量份的甲基丙烯酸烷基酯，0～25重量份的苯乙烯，1.0～10.0重量份的丙烯酸羟乙酯或者1.0～10.0重量份的丙烯酸羟丙酯，10.0～50.0质量份的桥环结构丙烯酸酯，且桥环结构丙烯酸酯的化学式 为：
Figure PCTCN2018076795-appb-000001
其中，基团R、R 1、R 2、R 3、R 4为氢或者甲基，k值为0或者1；
b、准备0.5～2.0重量份的反应引发剂；
c、准备25～30重量份的反应溶剂；
d、在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂，搅拌并升温至溶剂的沸点温度；
e、在滴液漏斗中投入上述的反应原料及引发剂并搅拌，3～5小时内匀速滴加完毕，滴加完毕后保持溶剂的沸点温度并继续搅拌2～4小时；
f、反应结束后冷却出料。
作为优选：所述引发剂为过氧化苯甲酰、偶氮二异丁腈、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、二叔丁基过氧化物或者二叔戊基过氧化物。
作为优选：所述溶剂为甲苯、二甲苯、乙二醇丁醚醋酸酯、丙二醇甲醚丙酸酯、醋酸丁酯、环己酮或者正丁醇。
作为优选：所述桥环结构丙烯酸酯为：
Figure PCTCN2018076795-appb-000002
Figure PCTCN2018076795-appb-000003
本公开采用了一种含桥环结构的丙烯酸酯作为功能性单体用于高固体分丙烯酸树脂制备中，可有效降低树脂粘度，提高树脂固体分，制得的丙烯酸树脂的格氏管粘度15～25S(25℃)，固体分70％～75％。
本公开的丙烯酸树脂粘度低，易施工，流平性好，光泽高，鲜映性佳，漆膜丰满度好。
具体实施方式
下面结合具体实施例对本公开的技术方案作进一步说明。
实施例1
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：2.0份
丙烯酸异辛酯：2.0份；
甲基丙烯酸甲酯：12.0份；
甲基丙烯酸正丁酯：12.0份；
丙烯酸羟丙酯：10.0份；
Figure PCTCN2018076795-appb-000004
30.0份；
并准备过氧化苯甲酸叔丁酯：2.0份作为反应引发剂；
准备甲苯：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：甲苯，搅拌并升温至回流温度(即甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，3小时内匀速滴加完毕，滴加完毕后保持回流温度并继续搅拌2小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为17S(25℃)，固体分70.0％。
以Desmodur N-3390为固化剂，与实施例1制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例2
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
甲基丙烯酸：0.2份；
丙烯酸正辛酯：2.0份；
甲基丙烯酸乙酯：12.0份；
甲基丙烯酸异丙酯：26.0份；
苯乙烯：5.0份；
丙烯酸羟乙酯：2.0份；
Figure PCTCN2018076795-appb-000005
26.8份；
并准备过氧化-2-乙基己酸叔丁酯：1.0份作为反应引发剂；
准备二甲苯：25.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：二甲苯，搅拌并升温至回流温度(即二甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，5小时内匀速滴加完毕，滴加完毕后保持回流温度并继续搅拌3小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为20S(25℃)，固体分75.0％。
以Desmodur N-3390为固化剂，与实施例2制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例3
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
甲基丙烯酸甲酯：8.0份；
甲基丙烯酸异丁酯：8.0份；
丙烯酸乙酯：4.0份；
苯乙烯：2.0份；
丙烯酸羟丙酯：1.0份；
Figure PCTCN2018076795-appb-000006
50.0份；
并准备二叔丁基过氧化物：1.0份作为反应引发剂；
准备乙二醇丁醚醋酸酯：25.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：乙二醇丁醚醋酸酯，搅拌并升温至回流温度(即乙二醇丁醚醋酸酯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，4小时内匀速滴加完毕，滴加完毕后保持回流温度并继续搅拌4小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为15S(25℃)，固体分75.0％。
以Desmodur N-3390为固化剂，与实施例3制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例4
按如下重量份的配方组份制备高固体分丙烯酸树脂：
甲基丙烯酸：1.5份；
丙烯酸甲酯：11.0份；
甲基丙烯酸甲酯：10.0份；
甲基丙烯酸己酯：9.0份；
苯乙烯：25.0份；
丙烯酸羟乙酯：5.0份；
Figure PCTCN2018076795-appb-000007
10.0份；
并准备二叔戊基过氧化物：1.5份作为反应引发剂；
准备丙二醇甲醚丙酸酯：27.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：丙二醇甲醚丙酸酯，搅拌并升温至回流温度(即丙二醇甲醚丙酸酯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，3小时内匀速滴加完毕，滴加完毕后保持回流温度并继续搅拌4小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为22S(25℃)，固体分72.5％。
以Desmodur N-3390为固化剂，与实施例4制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例5
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
丙烯酸正丁酯：15.0份；
甲基丙烯酸乙酯：16.0份；
甲基丙烯酸丁酯：8.0份；
苯乙烯：4.0份；
丙烯酸羟丙酯：2.0份；
Figure PCTCN2018076795-appb-000008
22.0份；
并准备过氧化苯甲酰：2.0份作为反应引发剂；
准备醋酸丁酯：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：醋酸丁酯，搅拌并升温至回流温度(即醋酸丁酯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，3小时内匀速滴加完毕，滴加完毕后保持回流温度并继续搅拌4小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为15S(25℃)，固体分70.5％。
以Desmodur N-3390为固化剂，与实施例5制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例6
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
丙烯酸异丁酯：4.0份；
甲基丙烯酸甲酯：12.0份；
甲基丙烯酸异丙酯：10.0份；
苯乙烯：8.0份；
丙烯酸羟丙酯：3.0份；
Figure PCTCN2018076795-appb-000009
30.0份；
并准备偶氮二异丁腈：2.0份作为反应引发剂；
准备环己酮：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：环己酮，搅拌并升温至回流温度(即环己酮的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，5小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌4小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为25S(25℃)，固体分70.0％。
以Desmodur N-3390为固化剂，与实施例6制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例7
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
丙烯酸甲酯：7.0份；
丙烯酸异辛酯：4.0份；
甲基丙烯酸甲酯：15.0份；
苯乙烯：10.0份；
丙烯酸羟乙酯：1.0份；
Figure PCTCN2018076795-appb-000010
30.0份；
并准备过氧化苯甲酸叔丁酯：2.0份作为反应引发剂；
准备正丁醇：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：正丁醇，搅拌并升温至回流温度(即正丁醇的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，3小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌2小时；
反应结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为18S(25℃)，固体分70.0％。
以Desmodur N-3390为固化剂，与实施例7制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例8
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
甲基丙烯酸：1.5份；
丙烯酸正辛酯：4.0份；
甲基丙烯酸乙酯：17.0份；
甲基丙烯酸异辛酯：12.0份；
苯乙烯：2.0份；
丙烯酸羟丙酯：2.0份；
Figure PCTCN2018076795-appb-000011
15.0份
Figure PCTCN2018076795-appb-000012
15.0份；
并准备二叔丁基过氧化物：1.5份作为反应引发剂；
准备二甲苯：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：二甲苯，搅拌并升温至回流温度(即二甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，3小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌3小时；
结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为22S(25℃)，固体分70.5％。
以Desmodur N-3390为固化剂，与实施例8制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例9
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.5份；
甲基丙烯酸甲酯：21.5份；
丙烯酸异辛酯：5.0份；
苯乙烯：10.0份；
丙烯酸羟丙酯：5.0份；
Figure PCTCN2018076795-appb-000013
15.0份；
Figure PCTCN2018076795-appb-000014
15.0份；
并准备二叔戊基过氧化物：2.0份作为反应引发剂；
准备二甲苯：25.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：二甲苯，搅拌并升温至回流温度(即二甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，4小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌4小时；
结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为25S(25℃)，固体分74.8％。
以Desmodur N-3390为固化剂，与实施例9制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
实施例10
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
丙烯酸异丁酯：4.0份；
丙烯酸正辛酯：5.0份；
甲基丙烯酸甲酯：15.0份；
甲基丙烯酸异丁酯：12.0份；
丙烯酸羟丙酯：10.0份；
Figure PCTCN2018076795-appb-000015
25.0份；
并准备过氧化苯甲酸叔丁酯：2.0份作为反应引发剂；
准备二甲苯：26.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：二甲苯，搅拌并升温至回流温度(即二甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，4小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌4小时；
结束后冷却出料。
经测试，本实施例中制得的丙烯酸树脂格氏管粘度为20S(25℃)，固体分73.5％。
以Desmodur N-3390为固化剂，与本实施例10制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
对比例1
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份；
甲基丙烯酸甲酯：18.0份；
甲基丙烯酸正丁酯：12.0份；
丙烯酸异辛酯：4.0份；
丙烯酸羟丙酯：10.0份；
苯乙烯：23.0份；
并准备过氧化-2-乙基己酸叔丁酯：2.0份作为反应引发剂；
准备甲苯：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：甲苯，搅拌并升温至回流温度(即甲苯的沸点温度)；
在滴液漏斗中投入上述比例的原料及引发剂并搅拌，4小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌2小时；
反应结束后冷却出料。
经测试，本对比例制得的丙烯酸树脂格氏管粘度为65S(25℃)，固体分70.8％。以Desmodur N-3390为固化剂，与对比例制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
对比例2
按如下重量份的配方组份准备制备高固体分丙烯酸树脂的原料：
丙烯酸：1.0份
甲基丙烯酸甲酯：18.0份
甲基丙烯酸正丁酯：12.0份
丙烯酸异辛酯：4.0份
丙烯酸羟丙酯：10.0份
甲基丙烯酸异冰片酯：23.0份
并准备过氧化-2-乙基己酸叔丁酯：2.0份作为反应引发剂；
准备甲苯：30.0份作为反应溶剂；
按如下方法制备高固体分丙烯酸树脂：
在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂：甲苯，搅拌并升温至回流温度(即甲苯的沸点温度)；
在滴液漏斗中投入上述比例的反应单体及引发剂并搅拌，4小时内匀速滴加完毕，滴加完毕后保持回流温度继续搅拌2小时；
结束后冷却出料。
经测试，本对比例制得的丙烯酸树脂格氏管粘度为20S(25℃)，固体分71.0％。以Desmodur N-3390为固化剂，与对比例2制得的高固体分丙烯酸树脂按OH∶NCO＝1∶1的摩尔比制漆，漆膜性能列于表1。
表1不同实施例的漆膜性能表
Figure PCTCN2018076795-appb-000016
表注：×-差，△-良好，○-优。

Claims (4)

  1. 一种高固体分丙烯酸树脂的制备方法，其包括以下步骤：
    a、准备以下反应原料：0.2～2重量份的丙烯酸或者0.2～2重量份的甲基丙烯酸，20～40重量份的丙烯酸烷基酯或者20～40重量份的甲基丙烯酸烷基酯，0～25重量份的苯乙烯，1.0～10.0重量份的丙烯酸羟乙酯或者1.0～10.0重量份的丙烯酸羟丙酯，10.0～50.0质量份的桥环结构丙烯酸酯，且桥环结构丙烯酸酯的化学式为：
    Figure PCTCN2018076795-appb-100001
    其中，基团R、R 1、R 2、R 3、R 4为氢或者甲基，k值为0或者1；
    b、准备0.5～2.0重量份的反应引发剂；
    c、准备25～30重量份的反应溶剂；
    d、在装有机械搅拌、温度计、回流冷凝管、温控器及滴液漏斗的反应器中投入溶剂，搅拌并升温至溶剂的沸点温度；
    e、在滴液漏斗中投入上述的反应原料及引发剂并搅拌，3～5小时内匀速滴加完毕，滴加完毕后保持溶剂的沸点温度并继续搅拌2～4小时；
    f、反应结束后冷却出料。
  2. 如权利要求1所述的一种高固体分丙烯酸树脂的制备方法，其中，所述引发剂为过氧化苯甲酰、偶氮二异丁腈、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、二叔丁基过氧化物或者二叔戊基过氧化物。
  3. 如权利要求1所述的一种高固体分丙烯酸树脂的制备方法，其中，所述溶剂为甲苯、二甲苯、乙二醇丁醚醋酸酯、丙二醇甲醚丙酸酯、醋酸丁酯、环己酮或者正丁醇。
  4. 如权利要求1所述的一种高固体分丙烯酸树脂的制备方法，其中，所述 桥环结构丙烯酸酯为：
    Figure PCTCN2018076795-appb-100002
    Figure PCTCN2018076795-appb-100003
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