CN106905504A - 水性紫外光固化聚氨酯树脂及其制备方法和应用 - Google Patents

水性紫外光固化聚氨酯树脂及其制备方法和应用 Download PDF

Info

Publication number
CN106905504A
CN106905504A CN201710176972.XA CN201710176972A CN106905504A CN 106905504 A CN106905504 A CN 106905504A CN 201710176972 A CN201710176972 A CN 201710176972A CN 106905504 A CN106905504 A CN 106905504A
Authority
CN
China
Prior art keywords
polyurethane resin
parts
waterborne polyurethane
curable waterborne
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710176972.XA
Other languages
English (en)
Other versions
CN106905504B (zh
Inventor
苏敏超
刘伟
苏杰龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongshan Qian Chemical Materials Co Ltd
Original Assignee
Zhongshan Qian Chemical Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongshan Qian Chemical Materials Co Ltd filed Critical Zhongshan Qian Chemical Materials Co Ltd
Priority to CN201710176972.XA priority Critical patent/CN106905504B/zh
Publication of CN106905504A publication Critical patent/CN106905504A/zh
Application granted granted Critical
Publication of CN106905504B publication Critical patent/CN106905504B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6662Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6659Compounds of group C08G18/42 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本发明涉及一种水性紫外光固化聚氨酯树脂及其制备方法和应用。该水性紫外光固化聚氨酯树脂,以重量份计,包括如下原料组分:二异氰酸酯25~40份、蓖麻油1~5份、多元醇20~30份、环氧丙烯酸酯5~10份、2,2‑二羟甲基丙酸5~10份、季戊四醇三丙烯酸酯10~15份、1,4‑丁二醇1~5份、催化剂0.0057~0.006份、阻聚剂0.002~0.005份、封端剂0.004~0.005份。本发明的水性紫外光固化聚氨酯树脂,通过采用特定的单体作为原料组分,能够使制得的树脂具有光固化速率快、生产效率高、涂膜固化后光泽高、硬度高,附着力、柔韧性好等优点,综合性能优异。

Description

水性紫外光固化聚氨酯树脂及其制备方法和应用
技术领域
本发明涉及高分子材料,特别是涉及一种水性紫外光固化聚氨酯树脂及其制备方法和应用。
背景技术
近年来,随着全球对环境保护的重视和绿色化工技术的发展,各国开始对VOC含量限制,水性紫外光固化聚氨酯树脂(水性UV聚氨酯树脂)是以水替代有机溶剂作为分散介质,具有明显的环保价值,且采用紫外光固化技术具有固化速度快、可室温下操作、耗能低、涂层性能优异等优点。水性UV聚氨酯树脂可以应用于涂料、胶粘剂、水性皮革涂饰剂、织物整理剂等方面,越来越受到人们的重视。
然而,目前已有的水性紫外光固化聚氨酯树脂,很难兼顾优越的机械性能和良好的耐水性、耐溶剂性,并且存在交联密度低、光固化速率慢等缺点。而且,如单纯应用水性紫外光固化聚氨酯树脂,还存在着耐候性、耐热性较差、粘接强度低等缺点,由此限制了水性紫外光固化聚氨酯树脂的推广和应用。
发明内容
基于此,有必要提供一种固含量高、光固化速率快、涂膜固化后光泽、硬度、附着力、柔韧性、耐水、耐溶剂等综合性能优异的水性紫外光固化聚氨酯树脂。
一种水性紫外光固化聚氨酯树脂,以重量份计,包括如下原料组分:
本发明的水性紫外光固化聚氨酯树脂,通过采用特定的单体作为原料组分,能够使制得的树脂具有固含量高、光固化速率快、生产效率高、涂膜后光泽高、硬度高,附着力、柔韧性好等优点。其原理如下:
首先,本发明综合采用环氧丙烯酸酯与蓖麻油对水性聚氨酯树脂进行改性。其中,环氧丙烯酸酯兼具环氧树脂模量高、强度高和耐化学性好、热稳定性好等优点,以及丙烯酸酯较好的耐水性、物理学性能和耐候性能且成本低廉的特点。蓖麻油则是一种可再生的植物油,来源丰富。蓖麻油的主要成分是高级脂肪酸的甘油三酸酯,脂肪酸中80%~90%是蓖麻油酸(9-烯基-12羟基十八酸),蓖麻油羟值163mgKOH/g,含羟基4.94%,羟基摩尔数为345。根据羟值推算,蓖麻油含70%的三官能度和30%的二官能度,羟基平均官能度为2.7,蓖麻油的这种特定的结构能够使其在聚氨酯树脂的合成中既能作为软段,增加柔韧性,又能起到交联剂的作用,提高聚氨酯树脂的交联度,提高漆膜的耐水,耐溶剂和力学等性能。此外蓖麻油的支链还含有大量的不饱和碳碳双键,可以为其进一步接枝改性提供活性点,进一步提高涂膜的性能。
其次,在前述聚氨酯树脂的基础上,引入2,2-二羟甲基丙酸,制备含羧基的聚氨酯预聚物,然后再在端基引入季戊四醇三丙烯酸酯,制备多重双键封端的水性聚氨酯丙烯酸酯,由此大大提高体系中的双键含量,保证树脂的光固化速度和生产效率。同时,树脂具有较高的固含量,可以减少树脂涂膜后热烘干或红外干燥等复杂工艺的时间,提高生产效率。
在其中一个实施例中,该水性紫外光固化聚氨酯树脂,以重量份计,包括如下原料组分:
在其中一个实施例中,所述多元醇的分子量为500~1500g/mol。
在其中一个实施例中,所述多元醇为聚醚二元醇、聚四氢呋喃醚二元醇、聚己内酯二元醇、聚碳酸酯二元醇中的一种或多种。
在其中一个实施例中,所述二异氰酸酯为异佛尔酮二异氰酸、二苯甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯中的一种或多种。
在其中一个实施例中,所述环氧丙烯酸酯的分子量为450~460g/mol,固含量为100%。
在其中一个实施例中,所述阻聚剂为4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基、2,2,6,6-四甲基哌啶-1-氧自由基、对苯二酚中的一种或多种;所述封端剂为一元醇。优选为甲醇和/或无水乙醇。
在其中一个实施例中,还包括重量份为4~5份的叔胺,优选为三乙胺或三乙醇胺,以及和6~8份的水。进一步在树脂中加入叔胺和水,可以进行成盐乳化,能够提高树脂的储存稳定性。
本发明还提供所述的水性紫外光固化聚氨酯树脂的制备方法,包括如下步骤:
(1)含羧基的聚氨酯预聚体的制备:
于所述二异氰酸酯中加入蓖麻油和部分催化剂,于45~55℃反应1.5~2h;
然后于反应液中加入溶解有剩余所述催化剂的多元醇,升温至75~80℃反应2~2.5h;
然后降温至40~50℃,于反应液中加入所述1,4-丁二醇和环氧丙烯酸酯,再升温至70~75℃反应1~1.5;
然后降温至40~50℃,于反应液中加入所述,2-二羟甲基丙酸,再升温至70~75℃反应2~2.5h,得所述含羧基的聚氨酯预聚体;
(2)水性紫外光固化聚氨酯树脂的制备:
将所述含羧基的聚氨酯预聚体降温至40~50℃后,于反应液中加入溶解有所述阻聚剂的季戊四醇三丙烯酸酯,升温至60~70℃反应2~3h;
然后加入所述封端剂,当NCO含量小于0.2wt%后,终止反应,即得所述水性紫外光固化聚氨酯树脂。
在其中一个实施例中,在步骤(2)中,当NCO含量小于0.2wt%后,将反应物降温至40℃以下,加入所述叔胺和水进行成盐乳化。
在其中一个实施例中,所述成盐乳化的方法为:于1100~1300r/min速度下搅拌0.5~1h,pH值控制在6~8。
本发明还提供一种水性聚氨酯涂料,以重量百分比计,包括如下组分:
与现有技术相比,本发明具有以下有益效果:
1、本发明的水性紫外光固化聚氨酯树脂,通过采用特定的单体作为原料组分,能够使制得的树脂具有光固化速率快、生产效率高、涂膜固化后光泽高、硬度高,附着力、柔韧性好等优点,综合性能优异。
2、本发明的水性紫外光固化聚氨酯树脂,具有较高的固含量,可以在树脂涂膜后减少热烘干或红外干燥等复杂工艺的时间,提高生产效率。
3、本发明的水性紫外光固化聚氨酯树脂的制备方法,工艺简单易操作,且过程中不需要添加大量的有机溶剂,具有很好的环保意义。
具体实施方式
以下结合具体实施例对本发明的水性紫外光固化聚氨酯树脂及其制备方法和应用作进一步详细的说明。
实施例1
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将28份甲苯二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加2份蓖麻油和0.0004份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶有0.0056份二月桂酸二丁基锡的28份聚碳酸酯二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h;
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的6份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将7份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往步骤4)预聚体中滴加溶有阻聚剂(4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基,0.004份)的14份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入0.0045份小分子一元醇(甲醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往步骤5)预聚体中加入5份三乙胺和7份去离子水进行成盐乳化,在1200r/min速度下反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为83%。
上述步骤中,所述组份均需要严格除水。
实施例2
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将36份二环己基甲烷二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加1份蓖麻油和0.0002份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶0.0057份有二月桂酸二丁基锡的23份聚醚二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h。
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的5份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将6份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往上述预聚体中滴加溶有阻聚剂(2,2,6,6-四甲基哌啶-1-氧自由基,0.003份)的12份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入0.0045份小分子一元醇(无水乙醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往上述预聚体中加入4份三乙胺和9份去离子水进行成盐乳化,在1100r/min速度下搅拌反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为84%。
上述步骤中,所述组份均需要严格除水。
实施例3
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将28份甲苯二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加2份蓖麻油和0.0004份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶0.0054份有二月桂酸二丁基锡的28份聚四氢呋喃二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h;
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的6份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将7份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往上述预聚体中滴加溶有阻聚剂(4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基,0.005份)的14份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入0.004份小分子一元醇(甲醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往上述预聚体中加入5份三乙胺和7份去离子水进行成盐乳化,在1300r/min速度下搅拌反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为82%。
上述步骤中,所述组份均需要严格除水。
实施例4
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将33份异佛尔酮二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加2份蓖麻油和0.0004份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶0.0055份有二月桂酸二丁基锡的25份聚己内酯二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h。
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的5份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将6份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往上述预聚体中滴加溶有阻聚剂(对苯二酚,0.002份)的13份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入0.005份小分子一元醇(无水乙醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往上述预聚体中加入6份三乙胺和6份去离子水进行成盐乳化,在1100r/min速度下搅拌反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为83%。
上述步骤中,所述组份均需要严格除水。
实施例5
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将27份1,6-六亚甲基二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加2份蓖麻油和0.0004份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶0.0053份有二月桂酸二丁基锡的28份聚醚二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h。
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的6份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将7份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往上述预聚体中滴加溶有阻聚剂(4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基,0.004份)的15份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入0.0045份小分子一元醇(无水乙醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往上述预聚体中加入5份三乙胺和7份去离子水进行成盐乳化,在1200r/min速度下搅拌反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为85%。
上述步骤中,所述组份均需要严格除水。
实施例6
本实施例一种水性紫外光固化聚氨酯树脂,其原料及制备方法如下:
1)在氮气保护下,将33份异佛尔酮二异氰酸酯置于装有机械搅拌器、滴液漏斗和回流冷凝管的四口烧瓶中,升温至30~40℃,开始滴加2份蓖麻油和0.0004份二月桂酸二丁基锡,滴完后在50±2℃反应1.5~2h。
2)在温度为50~55℃下,滴加溶0.0055份有二月桂酸二丁基锡的25份聚醚二元醇(分子量为1000g/mol),在1h内滴加完,滴完后升温至75~80℃,反应2~2.5h。
3)降温至40~50℃,滴加3份1,4-丁二醇和溶有少量丙酮的5份环氧丙烯酸酯,在1h内滴加完毕。升高温度至70~75℃反应1~1.5h。
4)降温至40~50℃,再将6份2,2-二羟甲基丙酸(DMPA)溶于少量N-甲基吡咯烷酮,一次性直接加入到反应釜中,升高温度至70~75℃反应2~2.5h,反应过程中通过加入少量丙酮以控制反应体系的粘度,得到含羧基的聚氨酯预聚体。
5)降温至40~50℃,边搅拌边往上述预聚体中滴加溶有阻聚剂(对苯二酚,0.004份)的13份季戊四醇三丙烯酸酯(PETA),在1h内滴加完;滴加完后升温至60~70℃,反应2~3h后加入,0.0045份小分子一元醇(无水乙醇)封端反应0.5~1h,然后测定异氰酸根的含量(用二正丁胺法),当-NCO含量小于0.2wt.%后终止反应,得到不饱和丙烯酸酯封端的蓖麻油和环氧聚氨酯改性聚氨酯丙烯酸酯预聚体。
6)降温至40℃以下,往上述预聚体中加入6份三乙醇胺和6份去离子水进行成盐乳化,在1300r/min速度下搅拌反应1h得到蓖麻油和环氧聚氨酯改性水性UV树脂,pH值控制在7.0左右,其固含量为82%。
上述步骤中,所述组份均需要严格除水。
对比例1
本对比例一种水性紫外光固化聚氨酯树脂,其原料及制备方法类似实施例1,区别在于:未采用所述环氧丙烯酸酯。
对比例2
本对比例一种水性紫外光固化聚氨酯树脂,其原料及制备方法类似实施例1,区别在于:未采用所述蓖麻油。
实施例7
将实施例1-6和对比例1-2制备得到的水性紫外光固化聚氨酯树脂分别按照如表1配方制成水性聚氨酯涂料。
表1
原料 用量
水性紫外光固化聚氨酯树脂/g 10
季戊四醇三丙烯酸酯/g 0.05
磷酸酯附着力促进剂/g 0.15
光引发剂1173/g 0.4
流平剂/g 0.1
消泡剂/g 0.03
水/g 3
上述水性聚氨酯涂料的制备方法为:准确按照配方称取各组分原料,搅拌分散,即得,其中,所述流平剂、消泡剂可采用本领域的常规种类。
对由实施例1-6和对比例1-2制备得到的水性紫外光固化聚氨酯树脂制得的水性聚氨酯涂料进行性能检测,检测方法为:将水性聚氨酯涂料涂在马口铁上,再放在80℃的烘箱烘10min,再在光固化机上固化(建议固化机光强400mJ/cm2,20m/s速度),可得到固化漆膜;测试结果如表2所示:
表2
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。

Claims (10)

1.一种水性紫外光固化聚氨酯树脂,其特征在于,以重量份计,包括如下原料组分:
2.根据权利要求1所述的水性紫外光固化聚氨酯树脂,其特征在于,以重量份计,包括如下原料组分:
3.根据权利要求1所述的水性紫外光固化聚氨酯树脂,其特征在于,所述多元醇的分子量为500~1500g/mol。
4.根据权利要求3所述的水性紫外光固化聚氨酯树脂,其特征在于,所述多元醇为聚醚二元醇、聚四氢呋喃醚二元醇、聚己内酯二元醇、聚碳酸酯二元醇中的一种或多种。
5.根据权利要求1所述的水性紫外光固化聚氨酯树脂,其特征在于,所述二异氰酸酯为异佛尔酮二异氰酸、二苯甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯中的一种或多种。
6.根据权利要求1所述的水性紫外光固化聚氨酯树脂,其特征在于,所述环氧丙烯酸酯的分子量为450~460g/mol,固含量为100%。
7.根据权利要求1-6任一项所述的水性紫外光固化聚氨酯树脂,其特征在于,所述催化剂为二月桂酸二丁基锡;所述阻聚剂为4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基、2,2,6,6-四甲基哌啶-1-氧自由基、对苯二酚中的一种或多种;所述封端剂为一元醇。
8.根据权利要求1-6任一项所述的水性紫外光固化聚氨酯树脂,其特征在于,还包括重量份为4~5份的叔胺,以及6~8份的水。
9.权利要求1-8任一项所述的水性紫外光固化聚氨酯树脂的制备方法,其特征在于,包括如下步骤:
(1)含羧基的聚氨酯预聚体的制备:
于所述二异氰酸酯中加入蓖麻油和部分催化剂,于45~55℃反应1.5~2h;
然后于反应液中加入溶解有剩余所述催化剂的多元醇,升温至75~80℃反应2~2.5h;
然后降温至40~50℃,于反应液中加入所述1,4-丁二醇和环氧丙烯酸酯,再升温至70~75℃反应1~1.5h;
然后降温至40~50℃,于反应液中加入所述2,2-二羟甲基丙酸,再升温至70~75℃反应2~2.5h,得所述含羧基的聚氨酯预聚体;
(2)水性紫外光固化聚氨酯树脂的制备:
将所述含羧基的聚氨酯预聚体降温至40~50℃后,于反应液中加入溶解有所述阻聚剂的季戊四醇三丙烯酸酯,升温至60~70℃反应2~3h;
然后加入所述封端剂,当NCO含量小于0.2wt%后,终止反应,即得所述水性紫外光固化聚氨酯树脂。
10.一种水性聚氨酯涂料,其特征在于,以重量百分比计,包括如下组分:
CN201710176972.XA 2017-03-22 2017-03-22 水性紫外光固化聚氨酯树脂及其制备方法和应用 Active CN106905504B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710176972.XA CN106905504B (zh) 2017-03-22 2017-03-22 水性紫外光固化聚氨酯树脂及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710176972.XA CN106905504B (zh) 2017-03-22 2017-03-22 水性紫外光固化聚氨酯树脂及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN106905504A true CN106905504A (zh) 2017-06-30
CN106905504B CN106905504B (zh) 2020-03-31

Family

ID=59194692

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710176972.XA Active CN106905504B (zh) 2017-03-22 2017-03-22 水性紫外光固化聚氨酯树脂及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN106905504B (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108219101A (zh) * 2017-12-28 2018-06-29 滁州金桥德克新材料有限公司 一种耐化学性优异的双重固化聚氨酯丙烯酸酯及其制备方法
CN108456290A (zh) * 2017-12-28 2018-08-28 滁州金桥德克新材料有限公司 一种双重固化聚氨酯丙烯酸酯树脂及其制备方法
CN109942781A (zh) * 2019-04-01 2019-06-28 东北林业大学 一种uv固化蓖麻油基水性聚氨酯分散体及其制备方法与应用
CN113683741A (zh) * 2021-08-19 2021-11-23 中山市钧纬新材料科技有限公司 UV-Monocoat用水性UV树脂及其制备方法
CN114015014A (zh) * 2021-12-09 2022-02-08 南雄市沃太化工有限公司 一种弹性拉丝光固化树脂及其制备方法,以及弹性拉丝胶
CN114560993A (zh) * 2022-03-15 2022-05-31 阜阳师范大学 一种查尔酮封端的光敏性水性聚氨酯/环氧丙烯酸酯的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177553A (zh) * 2007-11-30 2008-05-14 华南理工大学 一种复合型紫外光固化水性涂料及其制备方法
CN102585693A (zh) * 2012-03-09 2012-07-18 常熟市协新冶金材料有限公司 制备环氧丙烯酸酯改性水性聚氨酯涂料的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177553A (zh) * 2007-11-30 2008-05-14 华南理工大学 一种复合型紫外光固化水性涂料及其制备方法
CN102585693A (zh) * 2012-03-09 2012-07-18 常熟市协新冶金材料有限公司 制备环氧丙烯酸酯改性水性聚氨酯涂料的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAIBIN LI ETC.: ""Preparation and properties of castor oil/pentaerythritol triacrylate-based UV curable waterborne polyurethane acrylate"", 《PROGRESS IN ORGANIC COATINGS》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108219101A (zh) * 2017-12-28 2018-06-29 滁州金桥德克新材料有限公司 一种耐化学性优异的双重固化聚氨酯丙烯酸酯及其制备方法
CN108456290A (zh) * 2017-12-28 2018-08-28 滁州金桥德克新材料有限公司 一种双重固化聚氨酯丙烯酸酯树脂及其制备方法
CN109942781A (zh) * 2019-04-01 2019-06-28 东北林业大学 一种uv固化蓖麻油基水性聚氨酯分散体及其制备方法与应用
CN113683741A (zh) * 2021-08-19 2021-11-23 中山市钧纬新材料科技有限公司 UV-Monocoat用水性UV树脂及其制备方法
CN114015014A (zh) * 2021-12-09 2022-02-08 南雄市沃太化工有限公司 一种弹性拉丝光固化树脂及其制备方法,以及弹性拉丝胶
CN114560993A (zh) * 2022-03-15 2022-05-31 阜阳师范大学 一种查尔酮封端的光敏性水性聚氨酯/环氧丙烯酸酯的制备方法
CN114560993B (zh) * 2022-03-15 2023-08-15 阜阳师范大学 一种查尔酮封端的光敏性水性聚氨酯/环氧丙烯酸酯的制备方法

Also Published As

Publication number Publication date
CN106905504B (zh) 2020-03-31

Similar Documents

Publication Publication Date Title
CN106905504A (zh) 水性紫外光固化聚氨酯树脂及其制备方法和应用
CN106397719B (zh) 蓖麻油基超支化uv固化聚氨酯丙烯酸酯及其制备方法和应用
CN105601880B (zh) 蓖麻油基聚氨酯丙烯酸酯及制备方法和应用
CN106866929A (zh) 一种多官能度蓖麻油基光固化树脂及其制备方法和应用
CN107759757B (zh) 一种超支化聚氨酯丙烯酸酯的制备方法及紫外光固化涂料
CN101880358B (zh) 水分散性聚氨酯-乙烯基单体聚合物组合物
CN107418501A (zh) 植物油基多元醇型可生物降解uv固化胶黏剂及制备方法
CN107903373B (zh) 一种uv固化水性超支化聚氨酯丙烯酸酯及其制备方法
CN107446457A (zh) 无溶剂法制备水性丙烯酸改性聚氨酯杂化树脂
CN108456290A (zh) 一种双重固化聚氨酯丙烯酸酯树脂及其制备方法
CN108017761B (zh) 一种丙烯酸类单体改性的聚氨酯乳液、其制法及其用途
CN102702469B (zh) 可紫外光固化的水性聚氨酯分散体及其制备方法
TWI595027B (zh) 聚氨酯(甲基)丙烯酸酯寡聚物及包含該寡聚物之可固化組成物
CN106957406B (zh) 一种杯芳烃型光固化聚氨酯树脂及其制备的自修复涂层
CN106519182A (zh) 一种机硅改性聚氨酯丙烯酸酯低聚物及制备方法
CN111410732B (zh) 一种水性uv树脂及其制备方法
CN105601828A (zh) 蓖麻油基聚氨酯-丙烯酸酯乳液的制备方法
CN115521437B (zh) 一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法
CN108314770A (zh) 二氧化碳基水性聚氨酯分散体、制备方法及二氧化碳基水性聚氨酯压敏胶
CN109293871B (zh) 一种自流平水性含氟聚氨酯丙烯酸树脂及其制备方法、水性光固化涂料
CN108329342B (zh) 一种有机硅偶联剂及其制备方法和应用
CN106103376A (zh) 涂覆有不可辐射固化的丙烯酸类硬质‑软质嵌段共聚物的光纤
Ali et al. Bio‐based photo‐curable polyurethane composites
CN105542121B (zh) 紫外光固化聚氨酯丙烯酸酯及其制备方法
EP3572474B1 (en) Biomaterial-based uv coating composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant