WO2016086631A1 - Preparation method for aqueous cycloaliphatic isocyanate modified polyester photocurable resin - Google Patents

Preparation method for aqueous cycloaliphatic isocyanate modified polyester photocurable resin Download PDF

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WO2016086631A1
WO2016086631A1 PCT/CN2015/080481 CN2015080481W WO2016086631A1 WO 2016086631 A1 WO2016086631 A1 WO 2016086631A1 CN 2015080481 W CN2015080481 W CN 2015080481W WO 2016086631 A1 WO2016086631 A1 WO 2016086631A1
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reaction
acid value
photocurable resin
resistance
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许钧强
康伦国
姚东生
阳京辉
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合众（佛山）化工有限公司
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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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • 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
    • C08G18/83—Chemically modified polymers
    • 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
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic 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
    • 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

Definitions

  • the invention relates to a preparation method of a photocurable polyester resin, in particular to an aqueous alicyclic isocyanate modified polyester photocurable resin, belonging to the technical field of synthetic resins.
  • UV curing has the advantages of fast reaction, room temperature operation, low energy consumption and no solvent and less pollution.
  • the water-based photocurable polyester has a hyperbranched molecular structure, and the hyperbranched polyester is introduced into the UV curing system, which can overcome some shortcomings of the linear oligomer, such as severe shrinkage of the coating film, volatilization of the diluent, toxicity, etc.;
  • One of the representative water-based photocurable polyester coatings in cured coatings is characterized by high gloss, strong adhesion, high fullness and excellent impact resistance, so it is widely used for the protection and decoration of metal and wood surfaces.
  • the aqueous hyperbranched polymer has a highly branched molecular structure and has a narrow relative molecular mass distribution, and has a similar structure to a dendrimer. Since the macromolecule has a compact structure similar to a three-dimensional sphere, the hydrodynamic radius of gyration is small, and the branch The degree of chemistry is very high, and the molecules are not easily entangled, so the viscosity changes little with the increase of the relative molecular mass; and the macromolecule has many functional end groups, which have an important influence on the entire hyperbranched polymer, and can pass through the opposite end.
  • the base modification controls the properties of the hyperbranched polymer, such as the glass transition temperature and solubility in different solvents; therefore, the aqueous photocurable hyperbranched polymer has become a hot topic in polymer science.
  • Tang Liming et al. used photo-curing hyperbranched polymer modified with trimethylolpropane and 2,2-dihydroxymethylpropionic acid as raw materials and excess maleic anhydride;
  • Niu Jianting et al. used acryloyl chloride and maleic acid.
  • the double bond-containing compound such as an acid anhydride chemically modifies the hyperbranched compound to obtain a functional group in which the terminal group is a double bond.
  • Hyperbranched compound; Tong Yiyi, etc. by reacting a hyperbranched polymer with glycidyl methacrylate to introduce a double bond to obtain a U V-curable coating resin.
  • TDI TDI to chemically modify the hyperbranched compound to obtain a photocurable aqueous hyperbranched polyester containing a terminal acryloyl group and a carboxyl group, and then neutralized with NaOH to form a salt for emulsion polymerization to form an anionic self-emulsified emulsion.
  • TDI is a highly toxic chemical with very strong chemical properties and high volatility.
  • the vapor pressure is 3.3Pa at 25°C and the saturated vapor concentration is 30 ⁇ 10 -6 . It has a strong pungent odor and tearing effect, and stimulates breathing after inhalation.
  • TDI can cause human lymphocytes DNA damage and chromosomal aberrations
  • Rodent cell gene mutations and sister chromatid exchange are suspected carcinogens.
  • TDI is resistant to aging and is not suitable for outdoor use.
  • the present invention relates to an aqueous HDI modified polyester photocurable resin, which has a composition of: 1 to 3% by weight of the hyperbranched polyester, including 5 to 12% of hydroxy acrylic monomer, 10 to 18% of alicyclic isocyanate monomer, 0.02 to 0.3% of dibutyltin dilaurate, 10 to 20% of maleic anhydride, 4 to 10% of N,N-dimethylaniline , sodium hydroxide 3 ⁇ 5%, deionized water 40 ⁇ 65%;
  • the hyperbranched polyester by weight percentage, its composition is: 2,2-dimethylolpropionic acid 8 ⁇ 25%, three 1 to 3% of methylolpropane and 0.1 to 0.5% of p-toluenesulfonic acid;
  • the alicyclic isocyanate monomer is one of IPDI, HMDI, H 6 MDI;
  • the hydroxyl group-containing acrylic monomer is acrylic acid
  • the invention provides a preparation method of a water-based alicyclic isocyanate modified polyester photocurable resin, and the preparation process thereof comprises the following steps:
  • the reaction kettle In the reaction kettle, the cycloaliphatic isocyanate monomer and the catalyst dibutyltin dilaurate are added according to the formula amount, the temperature is raised to 30-40 ° C, and the metered hydroxyl group-containing acrylic monomer is added dropwise under stirring, and the reaction is carried out for 0.5 h. After sampling, the isocyanic acid value is sampled, and then sampled every 0.5h. When the isocyanic acid value is detected to be half of the initial value, the hyperbranched polyester prepared in the step a is added according to the formula amount, and the temperature is raised to 50 to 60 ° C. The reaction is continued until the isocyanic acid value is less than 1%, and the temperature is raised to 70 to 80 ° C. When the isocyanic acid value cannot be measured, the next reaction is carried out;
  • the water-based alicyclic isocyanate modified polyester photocurable resin prepared by the invention has good storage stability; the coating film has excellent water resistance, hardness, aging resistance, chemical resistance and resistance under the action of a photoinitiator. It is also polluting, and has the characteristics of high gloss, good wear resistance, strong adhesion, high fullness and excellent impact resistance. It is widely used in wood, metal, zinc alloy, aluminum alloy, magnesium alloy, plastic and other products. Surface radiation coating and protection.
  • a, hyperbranched polyester reference example 1 has step a;
  • the aqueous alicyclic isocyanate modified polyester photocurable resin prepared by the embodiment of the invention is formulated into an aqueous UV varnish, and the formula is as follows: 62-70 parts of water-based alicyclic isocyanate modified polyester photocurable resin, photoinitiator 4.2 Parts, defoamer 0.2 parts, substrate wetting agent 0.3 parts, leveling agent 0.2 parts, make deionized water to 100; and aqueous TDI modified polyester photocurable resin (comparative) prepared according to the above formula
  • the varnish is tested in accordance with the relevant national standards for film performance, and the film is cured by radiation for 10 s. The test results are shown in Table 1.

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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)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a preparation method for aqueous cycloaliphatic isocyanate modified polyester photocurable resin consisting of: 1-3% hyperbranched polyester, 5-12% hydroxyl-containing acrylic acid monomer, 10-18% cycloaliphatic isocyanate monomer, 0.02-0.3% dibutyltin dilaurate, 10-20% maleic anhydride, 4-10% N, N- dimethylbenzene amine, 3-5% sodium hydroxide, 40-65% deionized water; the hyperbranched polyester is synthesized by DMPA and TMP under the act of catalyst; in the present invention, the aqueous cycloaliphatic isocyanate modified polyester light cured resin has a good storage stability; under the effect of photoinitiator, a coating film is of superior water resistance, hardness, aging resistance, cosmetic resistance and stain resistance, concurrently has characteristics of high glossiness, good abrasive resistance, strong adhesive force, high fullness, superior impact resistance and the like, and can be extensively used in radiation coating and for protecting a surface of an article made of wood, metal, zinc alloy, aluminum alloy, magnesium alloy, plastic and the like.

Description

一种水性脂环族异氰酸酯改性聚酯光固化树脂的制备方法Method for preparing waterborne alicyclic isocyanate modified polyester photocurable resin 技术领域Technical field
本发明涉及一种光固化聚酯树脂的制备方法，尤其涉及到一种水性脂环族异氰酸酯改性聚酯光固化树脂，属于合成树脂技术领域。The invention relates to a preparation method of a photocurable polyester resin, in particular to an aqueous alicyclic isocyanate modified polyester photocurable resin, belonging to the technical field of synthetic resins.
背景技术Background technique
近几年，环保型涂料包括高固体分及无溶剂涂料、水性涂料、粉末涂料和光固化涂料取得较快发展。紫外光固化具有快速反应、室温操作、低能消耗和无溶剂少污染等优点。水性光固化聚酯具有超支化分子结构，将超支化聚酯引入到UV固化体系中，可以克服线型低聚物的一些缺点，如涂膜严重收缩、稀释剂挥发、毒性大等；水性光固化涂料中具有代表性之一的水性光固化聚酯涂料，具有光泽高、附着力强、丰满度高、耐冲击性优良等特点，因此广泛用于金属和木器表面的保护和装饰。In recent years, environmentally friendly coatings including high solids and solventless coatings, waterborne coatings, powder coatings and photocurable coatings have achieved rapid development. UV curing has the advantages of fast reaction, room temperature operation, low energy consumption and no solvent and less pollution. The water-based photocurable polyester has a hyperbranched molecular structure, and the hyperbranched polyester is introduced into the UV curing system, which can overcome some shortcomings of the linear oligomer, such as severe shrinkage of the coating film, volatilization of the diluent, toxicity, etc.; One of the representative water-based photocurable polyester coatings in cured coatings is characterized by high gloss, strong adhesion, high fullness and excellent impact resistance, so it is widely used for the protection and decoration of metal and wood surfaces.
水性超支化聚合物具有高度支化的分子结构，具有很窄的相对分子质量分布，与树枝形聚合物有类似的结构，由于大分子具有类似三维球形的紧凑结构，流体力学回转半径小，支化度很高，分子间不易缠结，因此粘度随相对分子质量的增加变化较小；而且大分子带有许多官能性端基，对整个超支化聚合物有很重要的影响，可以通过对端基改性而控制超支化聚合物的性能，如玻璃化温度和在不同溶剂中的溶解度等；因此，水性光固化超支化聚合物已成为高分子科学中的热门课题。The aqueous hyperbranched polymer has a highly branched molecular structure and has a narrow relative molecular mass distribution, and has a similar structure to a dendrimer. Since the macromolecule has a compact structure similar to a three-dimensional sphere, the hydrodynamic radius of gyration is small, and the branch The degree of chemistry is very high, and the molecules are not easily entangled, so the viscosity changes little with the increase of the relative molecular mass; and the macromolecule has many functional end groups, which have an important influence on the entire hyperbranched polymer, and can pass through the opposite end. The base modification controls the properties of the hyperbranched polymer, such as the glass transition temperature and solubility in different solvents; therefore, the aqueous photocurable hyperbranched polymer has become a hot topic in polymer science.
唐黎明等用三甲醇基丙烷和2，2一二羟甲基丙酸为原料、过量的顺丁烯二酸酐改性合成了光固化超支化聚合物；牛建婷等利用丙烯酰氯、顺丁烯二酸酐等含双键的化合物对超支化合物进行化学改性，得到端基为双键的功能型 超支化合物；童身毅等通过在超支化聚合物与甲基丙烯酸缩水甘油酯反应，引入双键，得到可U V固化的涂料树脂。Tang Liming et al. used photo-curing hyperbranched polymer modified with trimethylolpropane and 2,2-dihydroxymethylpropionic acid as raw materials and excess maleic anhydride; Niu Jianting et al. used acryloyl chloride and maleic acid. The double bond-containing compound such as an acid anhydride chemically modifies the hyperbranched compound to obtain a functional group in which the terminal group is a double bond. Hyperbranched compound; Tong Yiyi, etc., by reacting a hyperbranched polymer with glycidyl methacrylate to introduce a double bond to obtain a U V-curable coating resin.
王孝科等用TDI对超支化合物进行化学末端改性，制得含端丙烯酰基、羧基的光固化水性超支化聚酯，再用NaOH中和成盐，用于乳液聚合，可形成阴离子型自乳化乳液。但TDI是剧毒化学品，化学性质非常活泼，挥发性高，25℃时蒸汽压为3.3Pa，饱和蒸汽浓度为30×10-6，具有强烈的刺激性气味和催泪作用，吸入后刺激呼吸***，引起干咳喉痛长期吸入微量二异氰酸酯将引起头痛支气管炎，严重的会导致死亡，并对环境造成严重污染；国际癌症研究机构(IARC)进行的体外试验显示，TDI可引起人的淋巴细胞DNA损伤和染色体畸变啮齿动物细胞基因突变和姐妹染色单体交换，为可疑致癌物质。另外TDI耐老化性，不适合在室外使用。Wang Xiaoke et al. used TDI to chemically modify the hyperbranched compound to obtain a photocurable aqueous hyperbranched polyester containing a terminal acryloyl group and a carboxyl group, and then neutralized with NaOH to form a salt for emulsion polymerization to form an anionic self-emulsified emulsion. . However, TDI is a highly toxic chemical with very strong chemical properties and high volatility. The vapor pressure is 3.3Pa at 25°C and the saturated vapor concentration is 30×10 -6 . It has a strong pungent odor and tearing effect, and stimulates breathing after inhalation. System, causing dry cough and sore throat long-term inhalation of trace amounts of diisocyanate will cause headache bronchitis, which can lead to death and serious environmental pollution; in vitro tests conducted by the International Agency for Research on Cancer (IARC) show that TDI can cause human lymphocytes DNA damage and chromosomal aberrations Rodent cell gene mutations and sister chromatid exchange are suspected carcinogens. In addition, TDI is resistant to aging and is not suitable for outdoor use.
发明内容Summary of the invention
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种水性HDI改性聚酯光固化树脂，按重量百分比计，其组成为：超支化聚酯1～3％、含羟基的丙烯酸单体5～12％、脂环族异氰酸酯单体10～18％、二月桂酸二丁基锡0.02～0.3％、顺酐10～20％、N，N-二甲基苯胺4～10％、氢氧化钠3～5％、去离子水40～65％；所述的超支化聚酯，按重量百分比计，其组成为：2，2-二羟甲基丙酸8～25％、三羟甲基丙烷1～3％、对甲基苯磺酸0.1～0.5％；脂环族异氰酸酯单体为IPDI、HMDI、H6MDI中的一种；所述的含羟基的丙烯酸单体为丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯、丙烯酸-2-羟丁酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯的至少一种。In order to solve the above technical problems, the present invention adopts the following technical solutions: The present invention relates to an aqueous HDI modified polyester photocurable resin, which has a composition of: 1 to 3% by weight of the hyperbranched polyester, including 5 to 12% of hydroxy acrylic monomer, 10 to 18% of alicyclic isocyanate monomer, 0.02 to 0.3% of dibutyltin dilaurate, 10 to 20% of maleic anhydride, 4 to 10% of N,N-dimethylaniline , sodium hydroxide 3 ~ 5%, deionized water 40 ~ 65%; the hyperbranched polyester, by weight percentage, its composition is: 2,2-dimethylolpropionic acid 8 ~ 25%, three 1 to 3% of methylolpropane and 0.1 to 0.5% of p-toluenesulfonic acid; the alicyclic isocyanate monomer is one of IPDI, HMDI, H 6 MDI; the hydroxyl group-containing acrylic monomer is acrylic acid 2-Hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy methacrylate At least one of butyl esters.
本发明提出一种水性脂环族异氰酸酯改性聚酯光固化树脂的制备方法，其制备工艺，包括如下步骤： The invention provides a preparation method of a water-based alicyclic isocyanate modified polyester photocurable resin, and the preparation process thereof comprises the following steps:
a、在反应釜中，按配方量加入2，2-二羟甲基丙酸和三羟甲基丙烷，通入氮气保护，升温至130℃，加入配方量的催化剂对甲基苯磺酸，保温反应4h后关闭氮气，继续反应2h后，冷却到40℃，制得超支化聚酯，备用；a. In the reaction kettle, add 2,2-dimethylolpropionic acid and trimethylolpropane according to the formula amount, pass nitrogen protection, raise the temperature to 130 ° C, and add the formula amount of catalyst p-toluenesulfonic acid. After 4 hours of heat preservation reaction, the nitrogen gas was turned off, the reaction was continued for 2 hours, and then cooled to 40 ° C to obtain a hyperbranched polyester, which was used;
b、在反应釜中，按配方量加入脂环族异氰酸酯单体和催化剂二月桂酸二丁基锡，升温至30～40℃，在搅拌下滴加计量好的含羟基的丙烯酸单体，反应0.5h后开始取样检测异氰酸值，以后每0.5h取样一次，当检测异氰酸值为初始值的一半时，按配方量加入步骤a制备的超支化聚酯，并升温至50～60℃，继续反应至异氰酸值小于1％时，升温至70～80℃，当异氰酸值无法测出时，进行下步反应；b. In the reaction kettle, the cycloaliphatic isocyanate monomer and the catalyst dibutyltin dilaurate are added according to the formula amount, the temperature is raised to 30-40 ° C, and the metered hydroxyl group-containing acrylic monomer is added dropwise under stirring, and the reaction is carried out for 0.5 h. After sampling, the isocyanic acid value is sampled, and then sampled every 0.5h. When the isocyanic acid value is detected to be half of the initial value, the hyperbranched polyester prepared in the step a is added according to the formula amount, and the temperature is raised to 50 to 60 ° C. The reaction is continued until the isocyanic acid value is less than 1%, and the temperature is raised to 70 to 80 ° C. When the isocyanic acid value cannot be measured, the next reaction is carried out;
c、在b步骤反应釜中加入计量好的丁酮进行溶解，同时加入配方量的N，N-二甲基苯胺，升温到80℃，滴加50％顺酐丁酮溶液，控制滴加时间为1h；滴加完毕后，每反应1h开始取样检测体系酸值，当检测体系酸值为初始值的一半时，冷却到50℃；加入NaOH中和反应0.5h，加入去离子水(调固含量为30～40％)，减压真空抽出丁酮，搅拌过滤包装即制得一种乳白色水性脂环族异氰酸酯改性聚酯光固化树脂。c. Add the metered methyl ethyl ketone to the b step reactor for dissolution, add the formula amount of N, N-dimethylaniline, raise the temperature to 80 ° C, add 50% maleic anhydride and butanone solution, and control the dropping time. 1h; after the completion of the addition, the acid value of the detection system is started every 1h, when the acid value of the detection system is half of the initial value, it is cooled to 50 ° C; the neutralization reaction is added for 0.5 h, and deionized water is added. The content is 30-40%), the methyl ethyl ketone is extracted under vacuum under reduced pressure, and a milky white aqueous alicyclic isocyanate modified polyester photocurable resin is obtained by stirring and filtering the package.
本发明制得的水性脂环族异氰酸酯改性聚酯光固化树脂，贮存稳定性好；在光引发剂的作用下涂膜具有优异的耐水性、硬度、耐老化性、耐化品性和耐污染性，同时还具有光泽度高、耐磨性好、附着力强、丰满度高、耐冲击性优良等特点，广泛用于木器、金属、锌合金、铝合金、镁合金、塑料等制品的表面辐射涂装与保护。The water-based alicyclic isocyanate modified polyester photocurable resin prepared by the invention has good storage stability; the coating film has excellent water resistance, hardness, aging resistance, chemical resistance and resistance under the action of a photoinitiator. It is also polluting, and has the characteristics of high gloss, good wear resistance, strong adhesion, high fullness and excellent impact resistance. It is widely used in wood, metal, zinc alloy, aluminum alloy, magnesium alloy, plastic and other products. Surface radiation coating and protection.
具体实施方式detailed description
实施例1：Example 1:
a、在反应釜中，加入13.5份2，2-二羟甲基丙酸和1.5份三羟甲基丙 烷，通入氮气保护，升温至130℃，加入0.1份对甲基苯磺酸，保温反应4h后关闭氮气，继续反应2h后，冷却到40℃，制得超支化聚酯，备用；a. In the reaction kettle, 13.5 parts of 2,2-dimethylolpropionic acid and 1.5 parts of trishydroxymethylpropane were added. The alkane is protected by nitrogen, heated to 130 ° C, 0.1 part of p-toluenesulfonic acid is added, the reaction is kept for 4 hours, the nitrogen is turned off, the reaction is continued for 2 hours, and then cooled to 40 ° C to obtain a hyperbranched polyester, which is ready for use;
b、在反应釜中，加入10.5份IPDI和0.06份二月桂酸二丁基锡，升温至30～40℃，在搅拌下滴加5.2份丙烯酸-2-羟乙酯单体，反应0.5h后开始取样检测异氰酸值，以后每0.5h取样一次，当检测异氰酸值为NCO为15.5～16.0％时，加入步骤a制备的超支化聚酯1.8份，并升温至50～60℃，继续反应至异氰酸值小于1％时，升温至70～80℃，当异氰酸值无法测出时，进行下步反应；b. In the reaction vessel, 10.5 parts of IPDI and 0.06 parts of dibutyltin dilaurate were added, and the temperature was raised to 30-40 ° C. 5.2 parts of 2-hydroxyethyl acrylate monomer was added dropwise with stirring, and sampling was started 0.5 h after the reaction. The isocyanic acid value was detected, and then sampled every 0.5 h. When the isocyanic acid value was detected to be 15.5 to 16.0%, 1.8 parts of the hyperbranched polyester prepared in the step a was added, and the temperature was raised to 50 to 60 ° C to continue the reaction. When the isocyanic acid value is less than 1%, the temperature is raised to 70 to 80 ° C, and when the isocyanic acid value cannot be measured, the next reaction is carried out;
c、在b步骤反应釜中加入3.5份丁酮进行搅拌，溶解完全后，加入5.2份N，N-二甲基苯胺，升温到80℃，滴加50％顺酐丁酮溶液22份，控制滴加时间为1h；滴加完毕后，每反应1h开始取样检测体系酸值，当体系酸值为10～11mgKOH/g时，冷却到50℃；加入3.2份NaOH中和反应0.5h，加入46份去离子水，减压真空抽出丁酮，搅拌过滤包装即制得一种固含量为40.8％乳白色水性HDI改性聚酯光固化树脂。c. Add 3.5 parts of butanone to the b step reactor and stir. After the dissolution is complete, add 5.2 parts of N,N-dimethylaniline, raise the temperature to 80 ° C, and add 22 parts of 50% maleic anhydride solution. The dropping time is 1 h; after the completion of the dropwise addition, the acid value of the detection system is started every 1 hour, and when the acid value of the system is 10-11 mgKOH/g, it is cooled to 50 ° C; 3.2 parts of NaOH is added to neutralize the reaction for 0.5 h, and 46 is added. Part of deionized water, methyl ethyl ketone was vacuumed under reduced pressure, and a filter package was prepared to obtain a milky white HDI modified polyester photocurable resin having a solid content of 40.8%.
实施例2：Example 2:
a、超支化聚酯参照实例1中有步骤a；a, hyperbranched polyester reference example 1 has step a;
b、在反应釜中，加入12份HMDI三聚体和0.06份二月桂酸二丁基锡，升温至30～40℃，在搅拌下滴加5.8份丙烯酸-2-羟丙酯单体，反应0.5h后开始取样检测异氰酸值，以后每0.5h取样一次，当检测异氰酸值为NCO为15.5～16.0％时，加入步骤a制备的超支化聚酯2份，并升温至50～60℃，继续反应至异氰酸值小于1％时，升温至70～80℃，当异氰酸值无法测出时，进行下步反应；b. In the reaction kettle, 12 parts of HMDI trimer and 0.06 parts of dibutyltin dilaurate were added, the temperature was raised to 30-40 ° C, and 5.8 parts of 2-hydroxypropyl acrylate monomer was added dropwise with stirring, and the reaction was carried out for 0.5 h. After sampling, the isocyanic acid value is sampled, and then sampled every 0.5h. When the isocyanic acid value is detected as 15.5 to 16.0%, 2 parts of the hyperbranched polyester prepared in the step a is added, and the temperature is raised to 50 to 60 ° C. Continue the reaction until the isocyanic acid value is less than 1%, and raise the temperature to 70-80 ° C. When the isocyanic acid value cannot be measured, the next step reaction is carried out;
c、在b步骤反应釜中加入4份丁酮进行搅拌，溶解完全后，加入5.2份N，N-二甲基苯胺，升温到80℃，滴加50％顺酐丁酮溶液28份，控制滴加时间为1h；滴加完毕后，每反应1h开始取样检测体系酸值，当体系酸值为10～ 11mgKOH/g时，冷却到50℃；加入3.6份NaOH中和反应0.5h，加入56份去离子水，减压真空抽出丁酮，搅拌过滤包装即制得一种固含量为41.5％乳白色水性HDI改性聚酯光固化树脂。c. Add 4 parts of butanone to the b step reactor and stir. After the dissolution is complete, add 5.2 parts of N,N-dimethylaniline, raise the temperature to 80 ° C, and add 28 parts of 50% maleic anhydride solution. The addition time is 1h; after the addition is completed, the acid value of the detection system is sampled every 1h, when the acid value of the system is 10~ At 11 mg KOH/g, it was cooled to 50 ° C; 3.6 parts of NaOH was added to neutralize the reaction for 0.5 h, 56 parts of deionized water was added, methyl ethyl ketone was vacuum-drawn under reduced pressure, and the filter package was stirred to obtain a solid content of 41.5% of milky white HDI. Modified polyester photocurable resin.
实施例3：Example 3:
把本发明实施例制得的水性脂环族异氰酸酯改性聚酯光固化树脂配制成水性UV清漆，配方如下：水性脂环族异氰酸酯改性聚酯光固化树脂62～70份、光引发剂4.2份，消泡剂0.2份、基材润湿剂0.3份、流平剂0.2份、补去离子水至100；与水性TDI改性聚酯光固化树脂(对比例)按上述配方制成水性UV清漆，按照国家相关标准对涂膜性能进行对比测试，涂膜辐射固化10s，测试结果如表1所示。The aqueous alicyclic isocyanate modified polyester photocurable resin prepared by the embodiment of the invention is formulated into an aqueous UV varnish, and the formula is as follows: 62-70 parts of water-based alicyclic isocyanate modified polyester photocurable resin, photoinitiator 4.2 Parts, defoamer 0.2 parts, substrate wetting agent 0.3 parts, leveling agent 0.2 parts, make deionized water to 100; and aqueous TDI modified polyester photocurable resin (comparative) prepared according to the above formula The varnish is tested in accordance with the relevant national standards for film performance, and the film is cured by radiation for 10 s. The test results are shown in Table 1.
表1：涂膜性能测试结果Table 1: Film performance test results
Figure PCTCN2015080481-appb-000001
Figure PCTCN2015080481-appb-000001
Figure PCTCN2015080481-appb-000002
Figure PCTCN2015080481-appb-000002
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。 While the invention has been described in detail and shown by the embodiments of the claims .

Claims (2)

  1. 一种水性脂环族异氰酸酯改性聚酯光固化树脂，其特征在于：按重量百分比计，其组成为：超支化聚酯1～3％、含羟基的丙烯酸单体5～12％、脂环族异氰酸酯单体10～18％、二月桂酸二丁基锡0.02～0.3％、顺酐10～20％、N，N-二甲基苯胺4～10％、氢氧化钠3～5％、去离子水40～65％；所述的超支化聚酯，按重量百分比计，其组成为：2，2-二羟甲基丙酸8～25％、三羟甲基丙烷1～3％、对甲基苯磺酸0.1～0.5％；脂环族异氰酸酯单体为IPDI、HMDI、H6MDI中的一种；所述的含羟基的丙烯酸单体为丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯、丙烯酸-2-羟丁酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯的至少一种。A water-based alicyclic isocyanate-modified polyester photocurable resin characterized by having a composition of: 1 to 3% by weight of a hyperbranched polyester, 5 to 12% of a hydroxyl group-containing acrylic monomer, and an alicyclic ring 10 to 18% of isocyanate monomer, 0.02 to 0.3% of dibutyltin dilaurate, 10 to 20% of maleic anhydride, 4 to 10% of N,N-dimethylaniline, 3 to 5% of sodium hydroxide, deionized water 40 to 65%; the hyperbranched polyester, in terms of weight percent, has a composition of: 2 to 25% of 2,2-dimethylolpropionic acid, 1 to 3% of trimethylolpropane, and p-methyl Benzenesulfonic acid 0.1-0.5%; alicyclic isocyanate monomer is one of IPDI, HMDI, H 6 MDI; the hydroxyl group-containing acrylic monomer is 2-hydroxyethyl acrylate, 2-hydroxy acrylate At least one of propyl ester, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxybutyl methacrylate.
  2. 一种如权利要求1所述的水性脂环族异氰酸酯改性聚酯光固化树脂的制备方法，其特征在于：所述的制备方法，包括如下步骤：A method for preparing a water-based alicyclic isocyanate-modified polyester photocurable resin according to claim 1, wherein the preparation method comprises the following steps:
    a、在反应釜中，按配方量加入2，2-二羟甲基丙酸和三羟甲基丙烷，通入氮气保护，升温至130℃，加入配方量的催化剂对甲基苯磺酸，保温反应4h后关闭氮气，继续反应2h后，冷却到40℃，制得超支化聚酯，备用；a. In the reaction kettle, add 2,2-dimethylolpropionic acid and trimethylolpropane according to the formula amount, pass nitrogen protection, raise the temperature to 130 ° C, and add the formula amount of catalyst p-toluenesulfonic acid. After 4 hours of heat preservation reaction, the nitrogen gas was turned off, the reaction was continued for 2 hours, and then cooled to 40 ° C to obtain a hyperbranched polyester, which was used;
    b、在反应釜中，按配方量加入脂环族异氰酸酯单体和催化剂二月桂酸二丁基锡，升温至30～40℃，在搅拌下滴加计量好的含羟基的丙烯酸单体，反应0.5h后开始取样检测异氰酸值，以后每0.5h取样一次，当检测异氰酸值为初始值的一半时，按配方量加入步骤a制备的超支化聚酯，并升温至50～60℃，继续反应至异氰酸值小于1％时，升温至70～80℃，当异氰酸值无法测出时，进行下步反应；b. In the reaction kettle, the cycloaliphatic isocyanate monomer and the catalyst dibutyltin dilaurate are added according to the formula amount, the temperature is raised to 30-40 ° C, and the metered hydroxyl group-containing acrylic monomer is added dropwise under stirring, and the reaction is carried out for 0.5 h. After sampling, the isocyanic acid value is sampled, and then sampled every 0.5h. When the isocyanic acid value is detected to be half of the initial value, the hyperbranched polyester prepared in the step a is added according to the formula amount, and the temperature is raised to 50 to 60 ° C. The reaction is continued until the isocyanic acid value is less than 1%, and the temperature is raised to 70 to 80 ° C. When the isocyanic acid value cannot be measured, the next reaction is carried out;
    c、在反应釜中加入计量好的丁酮进行溶解，同时加入配方量的N，N-二甲基苯胺，升温到80℃，滴加50％顺酐丁酮溶液，控制滴加时间为1h；滴加完毕后，每反应1h开始取样检测体系酸值，当检测体系酸值为初始值的一半时，冷却到 50℃；加入NaOH中和反应0.5h，加入去离子水(调固含量为30～40％)，减压真空抽出丁酮，搅拌过滤包装即制得一种乳白色水性脂环族异氰酸酯改性聚酯光固化树脂。 c. Add a metered amount of methyl ethyl ketone to the reaction kettle for dissolution, add the formula amount of N, N-dimethylaniline, raise the temperature to 80 ° C, add 50% maleic anhydride and butanone solution, and control the dropping time to 1 h. After the addition is completed, the acid value of the detection system is started every 1 hour, and when the acid value of the detection system is half of the initial value, it is cooled to 50 ° C; adding NaOH neutralization reaction for 0.5 h, adding deionized water (adjustment content of 30 ~ 40%), vacuum extraction of methyl ethyl ketone under reduced pressure, stirring filter packaging to obtain a milky white aqueous alicyclic isocyanate modified poly Ester photocurable resin.
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