WO2018090711A1 - 具有较强热稳定性醇酸树脂及其制备方法 - Google Patents

具有较强热稳定性醇酸树脂及其制备方法 Download PDF

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WO2018090711A1
WO2018090711A1 PCT/CN2017/102180 CN2017102180W WO2018090711A1 WO 2018090711 A1 WO2018090711 A1 WO 2018090711A1 CN 2017102180 W CN2017102180 W CN 2017102180W WO 2018090711 A1 WO2018090711 A1 WO 2018090711A1
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parts
acid
alkyd resin
thermal stability
anhydride
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French (fr)
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任会平
郝兴
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任会平
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the invention belongs to the technical field of coatings, and relates to an alkyd resin with strong thermal stability and a preparation method thereof, in particular to a synthetic alkyd resin, an alkyd resin with strong thermal stability, and the invention also It relates to a preparation method of the alkyd resin.
  • Alkyd resins are environmentally friendly resins prepared from polyols, polybasic acids, solubilizers, neutralizers, and the like.
  • the invention has the advantages of easy availability of raw materials, wide source, simple process and equipment, low pollution, variety and wide application, and the alkyd resin coating prepared by the resin has the characteristics of strong adhesion, high hardness and excellent impact resistance. More and more attention is being paid.
  • Alkyd resin, as one of the most used coating resins has great research and development space, broad application prospects, and huge economic and social benefits.
  • alkyd resins are poor bake color retention, limited outdoor durability, difficulty in achieving very high solids in solvent-based alkyd coatings, and smoke in baking ovens. This can cause air pollution problems
  • the prior art often uses modified alkyd resins such as acrylic acid, styrene, polyurethane, epoxy resin, silicone, inorganic nanoparticles, fluorine, chlorinated rubber, shellac and phosphate.
  • modified alkyd resins such as acrylic acid, styrene, polyurethane, epoxy resin, silicone, inorganic nanoparticles, fluorine, chlorinated rubber, shellac and phosphate.
  • the present invention provides an alkyd resin having strong weather resistance and thermal stability and a preparation method thereof.
  • An alkyd resin having strong weather resistance and thermal stability which is prepared from the following components by weight: 30-50 parts of polybasic acid, 15-25 parts of polyhydric alcohol, 12-20 parts of polybasic acid anhydride, heat stabilizer 4 -10 parts, 10 to 35 parts of a co-solvent, and 2 to 5 parts of a neutralizing agent.
  • a mixture of dibasic acid and polybasic acid is used to improve the dryness, hardness and water resistance of the paint film; various polyols are used to improve the water resistance of the paint film and reduce the production cost; Stabilizers and UV absorbers, the most important innovation is the use of rare earth composite stabilizers and UV absorbers to modify the alkyd resin to improve the high temperature resistance of the film.
  • the polybasic acid anhydride is any one of benzoic acid, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 1,4-cyclohexanedicarboxylic acid, or a combination of any two or more thereof. .
  • the polybasic acid is benzoic acid, adipic acid, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid; the use of these polybasic acids is beneficial to increase the relative molecular mass of the alkyd resin to improve the dryness of the paint film. Rate, hardness and water resistance.
  • the polyol is any one or any two of glycerol, pentaerythritol, sorbitol, trimethylolpropane, ethylene glycol, 1,6-hexanediol, 1,2-propanediol, and neopentyl glycol. More than one combination.
  • the polyol is pentaerythritol, trimethylolpropane, sorbitol, neopentyl glycol.
  • Pentaerythritol is inexpensive, trimethylolpropane improves the hydrolysis resistance of the film, and neopentyl glycol balances some of the functionality.
  • the polybasic acid anhydride is selected from any one of trimellitic anhydride, dimethylolpropionic acid, and dimethylolbutanoic acid, or a combination of any two or more thereof in any ratio.
  • the rare earth composite stabilizer is selected from the group consisting of rare earth stearate and a rare earth salt and a lead salt composite stabilizer, or a combination of any two or more thereof in any ratio.
  • the cosolvent is any one or any two of propylene glycol monobutyl ether, turpentine: xylene (7:3), ethyl acetate, propylene glycol methyl ether acetate, isopropanol, isobutanol, and sec-butanol. The combination above.
  • the co-solvent is ethyl acetate, turpentine: xylene (7:3), propylene glycol monobutyl ether, propylene glycol methyl ether acetate.
  • the neutralizing agent is triethanolamine.
  • the preparation method of the strong thermal stability alkyd resin comprises the following steps:
  • control temperature is 160 ° C
  • the poor drying performance is mainly because the traditional alkyd resin has a relatively low molecular weight, and we use various dibasic acids and polybasic acids such as isophthalic acid to increase the relative molecular weight of the alkyd resin, thereby solving the defect of poor drying of the paint film. .
  • the physicochemical properties of the alkyd resin itself determine its high temperature resistance. We modify it by adding a rare earth composite stabilizer to improve the heat resistance of the resin.
  • the high-performance modified alkyd resin provided by the invention has simple preparation process, low cost and easy availability, and excellent performance. It not only solves the shortcomings of the prior art, but also improves the high temperature resistance and weather resistance, expands its application range, and is suitable for preparing various types of alkyd resin coatings.
  • the thermally stable alkyd resin is prepared from the following components by weight: 5 parts of tetrahydrophthalic anhydride, 8 parts of 1,4-cyclohexanedicarboxylic acid, 8 parts of benzoic acid, 11 parts of adipic acid, and tetrahydrophthalic anhydride 4 Parts, 1,4-cyclohexanedicarboxylic acid 8 parts; pentaerythritol 5 parts, stearic acid rare earth stabilizer 7 parts, trimethylolpropane 4 parts, neopentyl glycol 3 parts; trimellitic anhydride 8 parts, dihydroxyl 7 parts of propyl propionate; turpentine: xylene (7:3), 5 parts, 11 parts of propylene glycol monobutyl ether, 5 parts of propylene glycol methyl ether acetate; 3.5 parts of triethanolamine.
  • the preparation method comprises the following steps:
  • Thermally stable alkyd resin made up of the following parts by weight: 18 parts of tetrahydrophthalic anhydride, 10 parts of benzoic acid, 10 parts of adipic acid, 5 parts of neopentyl glycol; 4 parts of trimellitic anhydride, dimethylol 7 parts of acid; 8 parts of stearic acid rare earth stabilizer, 6 parts of 1,4-cyclohexanedicarboxylic acid; 6 parts of pentaerythritol, 7 parts of trimethylolpropane, 4 parts of 1,2-propanediol, turpentine: xylene (7:3), 7 parts, 11 parts of propylene glycol monobutyl ether, 5 parts of propylene glycol methyl ether acetate, and 3.2 parts of triethanolamine.
  • the preparation method comprises the following steps:
  • Thermally stable alkyd resin made from the following parts by weight: 16 parts of tetrahydrophthalic anhydride, 7 parts of 1,4-cyclohexanedicarboxylic acid, 5 parts of benzoic acid, 6 parts of adipic acid, terephthalic acid 7 parts; 5 parts of pentaerythritol, 4 parts of trimethylolpropane, 3 parts of 1,2-propanediol, 6 parts of neopentyl glycol; 4 parts of dimethylolpropionic acid, sodium of isophthalic acid-5-sulfonate 6 Parts; rare earth stearate and lead salt composite stabilizer 10 parts, turpentine: xylene (7:3), 4 parts, propylene glycol monobutyl ether 8 parts, sec-butanol 6 parts; triethanolamine 4 parts.
  • the preparation method comprises the following steps:
  • the thermally stable alkyd resin is prepared from the following components by weight: 3 parts of tetrahydrophthalic anhydride, 7 parts of 1,4-cyclohexanedicarboxylic acid, 3 parts of benzoic acid, 7 parts of adipic acid, and hexahydrophthalic anhydride 13 Parts: 3 parts of pentaerythritol, 5 parts of trimethylolpropane, 5 parts of 1,2-propanediol, 3 parts of neopentyl glycol; 4 parts of trimellitic anhydride, 8 parts of dimethylolpropionic acid; 9 parts of rare earth composite stabilizer, turpentine : xylene (7:3), 6 parts, 9 parts of propylene glycol monobutyl ether, 7 parts of isobutanol; 2 parts of triethanolamine.
  • the preparation method comprises the following steps:
  • the strong thermal-stable alkyd resin obtained in Examples 1 to 4 and the commercially available alkyd resin (No. PT-001) were respectively prepared into an alkyd resin coating according to the formulation in Table 1, and were prepared. Alkyd resin coatings were tested for surface dryness, dryness, hardness, impact resistance, flexibility, adhesion, water resistance, high temperature resistance, weather resistance and salt water resistance. The results are shown in Table 2.
  • the alkyd resin coating prepared by using the rare earth composite stabilizer modified alkyd resin as a film-forming material is more comprehensive than the alkyd resin coating prepared by using a commercially available alkyd resin as a film-forming material. More excellent performance and higher temperature resistance.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative example (PT-001) Alkyd resin 100 100 100 100 100 103
  • Turpentine: xylene (7:3) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Propylene glycol methyl ether 7 7 7 7 7 7 7 Zinc phosphate 2 2 2 2 2 Bentonite 1 1 1 1 1 1 Titanium dioxide (anatase type) 13 13 13 13 13 13 Drier 1 1 1 1 1

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Abstract

涉及一种具有较强热稳定性醇酸树脂及其制备方法，该树脂由以下重量份的组分制成：多元酸30-50份、多元醇15-25份、多元酸酐12-20份、热稳定剂4-l0份、助溶剂10-35份、中和剂2-5份。该醇酸树脂不仅解决了现有技术的不足，而且提高了耐高温性能和耐候性能，扩大了其应用范围，适用于制备各种类型的醇酸树脂涂料。

Description

一种具有较强热稳定性醇酸树脂及其制备方法 技术领域
本发明属于涂料技术领域，涉及一种具有较强热稳定性醇酸树脂及其制备方法，特别涉及一种用于合成醇酸树脂,一种具有较强热稳定性醇酸树脂,本发明还涉及该醇酸树脂的制备方法。
背景技术
醇酸树脂是由多元醇、多元酸、助溶剂和中和剂等制备而出的环保型树脂。具有原料易得、来源广泛、工艺和设备简单、污染低、品种多样、用途广泛等优势，以该树脂制得的醇酸树脂涂料具有附着力强、硬度高、耐冲击性优良等特点，因此受到越来越多的关注。醇酸树脂作为一种使用量最大的涂料用树脂,具有极大的开发研究空间、广阔的应用前景、巨大的经济和社会效益。
醇酸树脂的主要缺点是相当差的烘烤保色性、有限的户外耐久性、在溶剂型醇酸树脂涂料中也难以达到极高的固体含量，再有就是在烘烤炉中产生烟，这会引起空气污染问题
为了克服上述缺陷，现有技术常采用丙烯酸、苯乙烯、聚氨酯、环氧树脂、有机硅、无机纳米粒子、氟、氯化橡胶、紫胶及磷酸酯等改性醇酸树脂。上述方法只是解决了部分问题，醇酸树脂的综合性能依然存在缺陷，比如：干燥性差，耐高温性差，耐候性差等。
发明内容
为了弥补现有技术的不足，解决醇酸树脂耐候性差，耐高温性差，阻燃性差等缺陷，本发明提供了一种具有较强耐候性和热稳定性醇酸树脂及其制备方法。
为了实现上述目的，本发明所采取的技术方案如下：
一种具有较强耐候性和热稳定性醇酸树脂，由以下重量份的组分制成：多元酸30-50份、多元醇15-25份、多元酸酐12-20份、热稳定剂4-l0份、助溶剂10-35份、中和剂2-5份。
使用了多种二元酸和多元酸的混合物,以提高漆膜的干率、硬度及耐水性能；使用了多种多元醇以提高漆膜的耐水性能和降低生产成本；在配方中加入稀土复合稳定剂和紫外线吸收剂，最主要的创新点在于，使用了稀土复合稳定剂和紫外线吸收剂对醇酸树脂进行改性，以提高漆膜的耐高温性能。
所述多元酸酐为苯甲酸、对苯二甲酸、己二酸、壬二酸、四氢苯酐、六氢苯酐、1,4-环己烷二甲酸中的任意一种或任意两种以上的组合。
优选的，多元酸为苯甲酸、己二酸、四氢苯酐、1,4-环己烷二甲酸；使用这几种多元酸有利于提高醇酸树脂的相对分子质量，以提高漆膜的干率、硬度及耐水性能。
所述多元醇为丙三醇、季戊四醇、山梨醇、三羟甲基丙烷、乙二醇、1,6-己二醇、1,2-丙二醇、新戊二醇中的任意一种或任意两种以上的组合。
优选的，多元醇为季戊四醇、三羟甲基丙烷、山梨醇、新戊二醇。季戊四醇价格低廉，三羟甲基丙烷可以提高漆膜的耐水解性能，新戊二醇则可以平衡部分官能度。
所述多元酸酐选自偏苯三酸酐、二羟甲基丙酸、二羟甲基丁酸中的中的任意一种或任意两种以上按照任意比例的组合。
所述稀土复合稳定剂选自硬脂酸稀土以及稀土盐和铅盐复合型稳定剂中的任意一种或任意两种以上按照任意比例的组合
所述助溶剂为丙二醇单丁醚、松节油:二甲苯(7:3),乙酸乙酯，丙二醇甲醚醋酸酯、异丙醇、异丁醇、仲丁醇中的任意一种或任意两种以上的组合。
优选的，助溶剂为乙酸乙酯，松节油:二甲苯(7:3),丙二醇单丁醚、丙二醇甲醚醋酸酯。
所述中和剂为三乙醇胺。
所述的较强热稳定性醇酸树脂的制备方法，包括以下步骤：
(1)依次将各质量份的多元酸、多元醇、多元酸酐加入到反应釜中，在180～230℃下，酯化反应至透明，保温反应至酸值达35～45mgKOH/g；
(2)降温至160-180℃，加入相应质量份的稀土复合稳定剂和助溶剂反应1-3h；控制温度在160℃，
(3)降温至140-150℃，加入相应质量份的中和剂并保温反应20～30min，
干燥性能差主要是因为传统醇酸树脂分子量相对较低，而我们使用了间苯二甲酸等多种二元酸及多元酸,可以提高醇酸树脂的相对分子量,进而解决漆膜干燥性差的缺陷。醇酸树脂本身的物化性质决定了其耐高温性能差，我们通过添加稀土复合稳定剂的方法对其进行改性，以便提高树脂的耐热性。
国内外学者对醇酸树脂的改性进行了一系列研究，包括丙烯酸改性、苯乙烯改性、环氧树脂改性、聚氨酯改性以及无机纳米材料改性等，但是以上改性方法都是为了改善树脂的硬度、强度、干燥性能以及提高附着力等，但是还没有一种改性方法在提高树脂综合性能的同时可以大幅度提高醇酸树脂的耐高温及耐候性能，本申请以稀土热稳定剂，紫外线吸收剂为改性剂，制备出的改性醇酸树脂耐高温性能优异。
有益效果：本发明提供的高性能改性醇酸树脂制备工艺简单，原料价廉易得，性能优异。不仅解决了现有技术的不足，而且提高了耐高温性能和耐候性能，扩大了其应用范围，适用于制备各种类型的醇酸树脂涂料。
为了更好的了解本发明的技术方案，以下通过具体的实施例进一步详细论述。
具体实施例
实施例1
热稳定性醇酸树脂，由以下重量份的组分制成：四氢苯酐5份、1,4-环己烷二甲酸8份，苯甲酸8份、己二酸11份、四氢苯酐4份、1,4-环己烷二甲酸8份；季戊四醇5份、硬脂酸稀土稳定剂7份，三羟甲基丙烷4份、、新戊二醇3份；偏苯三酸酐8份、二羟甲基丙酸7份；松节油:二甲苯(7:3),5份、丙二醇单丁醚11份、丙二醇甲醚乙酸酯5份；三乙醇胺3.5份。
其制备方法，包括以下步骤：
(1)依次将各质量份的多元醇、多元酸、多元酸酐加入到反应釜中，在220℃下，酯化反应至透明，保温反应至酸值达40mgKOH/g；
(2)降温至160-180℃，加入相应质量份的稀土复合热稳定剂和助溶剂反应1.5h；
(3)降温至140-150℃，加入稀释剂，搅拌均匀，调节固含量至50-55％，出料。
实施例2
热稳定性醇酸树脂，由以下重量份的组分制成：四氢苯酐18份、苯甲酸10份、己二酸10份、新戊二醇5份；偏苯三酸酐4份、二羟甲基丁酸7份；硬脂酸稀土稳定剂8份，1,4-环己烷二甲酸6份、；季戊四醇6份、三羟甲基丙烷7份、1,2-丙二醇4份、松节油:二甲苯(7:3),7份、丙二醇单丁醚11份、丙二醇甲醚乙酸酯5份；三乙醇胺3.2份。
其制备方法，包括以下步骤：
(1)依次将各质量份的多元醇、多元酸、多元酸酐加入到反应釜中，在230℃下，酯化反应至透明，保温反应至酸值达40mgKOH/g；
(2)降温至160-180℃，加入相应质量份的稀土复合热稳定剂和助溶剂反应2h；
(3)降温至140-150℃，加入稀释剂，搅拌均匀，调节固含量至48％，出料。
实施例3
热稳定性醇酸树脂，由以下重量份的组分制成：四氢苯酐16份、1,4-环己烷二甲酸7份、苯甲酸5份、己二酸6份、对苯二甲酸7份；季戊四醇5份、三羟甲基丙烷4份、1,2-丙二醇3份、新戊二醇6份；二羟甲基丙酸4份、间苯二甲酸-5-磺酸钠6份；稀土硬脂酸盐和铅盐复合型稳定剂10份，松节油:二甲苯(7:3),4份、丙二醇单丁醚8份、仲丁醇6份；三乙醇胺4份。
其制备方法，包括以下步骤：
(1)依次将各质量份的多元醇、多元酸、多元酸酐加入到反应釜中，在220℃下，酯化反应至透明，保温反应至酸值达41mgKOH/g；
(2)降温至160-180℃，加入相应质量份的稀土复合热稳定剂和助溶剂反应3h；
(3)降温至140-150℃，加入相应质量份的UV-531并保温反应25min，加入稀释剂，搅拌均匀，调节固含量至50％，出料。
实施例4
热稳定性醇酸树脂，由以下重量份的组分制成：四氢苯酐3份、1,4-环己烷二甲酸7份、苯甲酸3份、己二酸7份、六氢苯酐13份；季戊四醇3份、三羟甲基丙烷5份、1,2-丙二醇5份、新戊二醇3份；偏苯三酸酐4份、二羟甲基丙酸8份；稀土复合稳定剂9份，松节油:二甲苯(7:3),6份、丙二醇单丁醚9份、异丁醇7份；三乙醇胺2份。
其制备方法，包括以下步骤：
(1)依次将各质量份的多元醇、多元酸、多元酸酐加入到反应釜中，在225℃下，酯化反应至透明，保温反应至酸值达40mgKOH/g；
(2)降温至160-170℃，加入相应质量份的稀土复合热稳定剂和助溶剂反应3h；
(3)降温至140-150℃，加入稀释剂，搅拌均匀，调节固含量至52％，出料。
性能测试：
取实施例1～4制得的较强热稳定性醇酸树脂和普通市售醇酸树脂(编号PT-001)，按照表1中的配方分别制成醇酸树脂涂料，并对制成的醇酸树脂涂料进行表干、实干、硬度、抗冲击性、柔韧性、附着力、耐水性能、耐高温性能、耐候性能及耐盐水等性能进行测试，结果如表2所示。
从表2中可以看出，本发明中以稀土复合稳定剂改性的醇酸树脂为成膜物制备的醇酸树脂涂料比以市售醇酸树脂为成膜物制备的醇酸树脂涂料综合性能更加优异，并且具有更高的耐高温性能。
表1醇酸树脂涂料配方
配方(份数) 实施例1 实施例2 实施例3 实施例4 对比例(PT-001)
醇酸树脂 100 100 100 100 103
松节油:二甲苯(7:3) 100 100 100 100 100
丙二醇甲醚 7 7 7 7 7
磷酸锌 2 2 2 2 2
膨润土 1 1 1 1 1
钛白粉(锐钛型) 13 13 13 13 13
催干剂 1 1 1 1 1
表2醇酸树脂涂料性能
Figure PCTCN2017102180-appb-000001

Claims (10)

  1. 一种具有较强热稳定性醇酸树脂及其制备方法，其特征在于：由以下重量份的组分制成：多元酸30-50份、多元醇15-25份、多元酸酐12-20份、热稳定剂4-l0份、助溶剂10-35份、中和剂2-5份。
  2. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述多元酸为苯甲酸、对苯二甲酸、己二酸、壬二酸、四氢苯酐、六氢苯酐、1,4-环己烷二甲酸中的一种或任意两种以上的组合。
  3. 如权利要求2所述的一种具有较强热稳定性醇酸树脂，其特征在于，所述多元酸为苯甲酸、己二酸、四氢苯酐、1,4-环己烷二甲酸。
  4. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述多元醇为丙三醇、季戊四醇、山梨醇、三羟甲基丙烷、新戊二醇中的一种或任意两种以上的组合。
  5. 如权利要求4所述的一种具有较强热稳定性醇酸树脂，其特征在于，所述多元醇为季戊四醇、三羟甲基丙烷、山梨醇、新戊二醇。
  6. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述多元酸酐选自偏苯三酸酐、苯酐、二羟甲基丙酸、二羟甲基丁酸中的任意两种以上按照任意比例的组合。
  7. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述热稳定剂为稀土复合稳定剂
  8. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述助溶剂为丙二醇单丁醚,松节油:二甲苯(7:3),丙二醇甲醚醋酸酯、乙酸乙酯，异丙醇、异丁醇、仲丁醇中的任意一种或任意两种以上的组合。
  9. 如权利要求1所述的一种具有较强热稳定性醇酸树脂，其特征在于：所述中和剂为三乙醇胺。
  10. 如权利要求1所述的一种具有较强热稳定性醇酸树脂的制备方法，其特征在于：包括以下步骤：
    (1)依次将各质量份的多元酸、多元醇、多元酸酐加入到反应釜中，在180～230℃下，酯化反应至透明，保温反应至酸值达35～45mgKOH/g；
    (2)降温至160-180℃，加入相应质量份的热稳定热稳定剂和助溶剂反应1-3h；
    (3)降温至140-150℃，加入相应质量份的中和剂并保温反应20～30min，，搅拌均匀，调节固含量至40～60％，出料。
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