CN111171282A - 一种合成聚氨酯-环氧丙烯酸酯的方法 - Google Patents

一种合成聚氨酯-环氧丙烯酸酯的方法 Download PDF

Info

Publication number
CN111171282A
CN111171282A CN202010091724.7A CN202010091724A CN111171282A CN 111171282 A CN111171282 A CN 111171282A CN 202010091724 A CN202010091724 A CN 202010091724A CN 111171282 A CN111171282 A CN 111171282A
Authority
CN
China
Prior art keywords
reacting
epoxy
acrylate
hydroxyl
epoxy resin
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
CN202010091724.7A
Other languages
English (en)
Other versions
CN111171282B (zh
Inventor
姜健
石雅琳
郑直
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.)
Liming Research Institute of Chemical Industry Co Ltd
Original Assignee
Liming Research Institute of Chemical Industry 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 Liming Research Institute of Chemical Industry Co Ltd filed Critical Liming Research Institute of Chemical Industry Co Ltd
Priority to CN202010091724.7A priority Critical patent/CN111171282B/zh
Publication of CN111171282A publication Critical patent/CN111171282A/zh
Application granted granted Critical
Publication of CN111171282B publication Critical patent/CN111171282B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular 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
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/58—Epoxy resins
    • 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
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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

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)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本发明公开了一种合成聚氨酯‑环氧丙烯酸酯的方法，其特征是：将聚酯多元醇与异氰酸酯反应形成NCO封端的预聚体，然后通过NCO基团与环氧树脂侧链上的羟基和羟基丙烯酸酯中的羟基反应制得中间体，在环氧树脂侧链引入柔性脂肪结构碳碳单键、碳氧醚键以及氨酯键，中间体与丙烯酸反应得到柔韧性好的聚氨酯改性环氧丙烯酸酯。本发明合成的聚氨酯‑环氧丙烯酸酯，断裂伸长率可达到40％以上，较大程度上提高了环氧树脂的柔韧性。原材料廉价易得，扩大了环氧丙烯酸树脂的应用领域，如可应用于光固化油墨，塑胶涂料等。

Description

一种合成聚氨酯-环氧丙烯酸酯的方法
技术领域
本发明属于有机高分子技术领域，涉及一种改性环氧丙烯酸酯的方法。
背景技术
在UV涂料用预聚物中，环氧丙烯酸酯的光固化速度在各类低聚物中是最快的，而且其固化后的涂膜具有硬度高、光泽度好、耐热性等特点，并且环氧丙烯酸酯原料来源广，价格低廉，合成工艺简单，但是存在粘度大、柔韧性差、脆性大等缺点。要拓宽其应用，必须对其进行一定程度的改性。主要改性的方法包括：聚氨酯改性、多元醇改性、有机酸或者酸酐改性、有机硅改性、磷改性等。
专利CN101205290和硕士论文(费玉梅，紫外光固化异佛尔酮二异氰酸酯改性环氧丙烯酸酯的合成与应用，河北工业大学)中均采用环氧丙烯酸酯与IPDI反应，改性的树脂固化成膜后断裂伸长率从2％提高到了7％以上，柔韧性仍然较低。
专利CN108341921的报道中，为了提高环氧丙烯酸酯的柔韧性，先使用端羧基的聚丁二烯与环氧树脂反应，再与丙烯酸反应得到柔韧性较好的环氧丙烯酸树脂，最后与异氰酸酯和丙烯酸羟基酯的半加成产物反应，得到了柔韧性较好的聚氨酯改性环氧丙烯酸酯，以改性的树脂为主体配制的紫外光固化油墨成功应用于柔性印制板的上标识的印制。
发明内容
本发明的目的是克服环氧丙烯酸酯预聚物柔韧性差的缺点，提供一种合成聚氨酯-环氧丙烯酸酯的方法，该方法的技术方案是：将聚酯多元醇与异氰酸酯反应形成NCO封端的预聚体，然后通过NCO基团与环氧树脂侧链上的羟基和羟基丙烯酸酯中的羟基反应制得中间体，在环氧树脂侧链引入柔性脂肪结构碳碳单键、碳氧醚键以及氨酯键，中间体与丙烯酸反应从而得到柔韧性好的聚氨酯改性环氧丙烯酸酯。
Figure BSA0000201643330000021
一种合成聚氨酯-环氧丙烯酸酯的方法，包括以下步骤：
(1)聚酯多元醇与异氰酸酯反应制得-NCO基团含量为50％～55％的预聚体；优选聚酯多元醇与异氰酸酯的摩尔比为1∶2.0～2.1，反应温度为70-80℃，反应时间为1～1.5h，催化剂T12(二月桂酸二丁基烯)的添加质量为0.01％。
(2)将预聚体与环氧树脂和羟基丙烯酸酯的混合物，在70～80℃，反应3～5h，当反应物中-NCO基团为零时，反应结束，得到聚氨酯增韧改性的环氧树脂，即中间体。优选羟基丙烯酸酯与环氧树脂的羟基摩尔比为3～5∶1。预聚体与混合物(羟基丙烯酸酯和环氧树脂)的质量比优选为0.45～0.48∶1。
(3)将中间体与丙烯酸，在90～110℃，反应4～6h，当酸值小于5mgKOH/g时，反应结束，得到聚氨酯-环氧丙烯酸酯。中间体与丙烯酸的质量比优选为：5.5～5.7∶1。体系优选加入在阻聚剂和催化剂。
所述聚酯多元醇可为聚己二酸己二醇酯、聚己二酸乙二醇酯、聚己二酸一缩二乙二醇酯、聚己二酸甲基丙二醇酯、聚己二酸甲基戊二醇酯、聚己二酸新戊二醇酯、聚己二酸丁二醇酯或聚己内酯等中的一种或者至少两种的组合。
所述异氰酸酯可为甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二苯基甲烷二异氰酸酯等中的一种或者至少两种的组合。
所述催化剂可为四乙基溴化铵，苄基三甲基氯化铵或三苯基磷等中的一种或者至少两种的组合。
所述阻聚剂可为对羟基苯甲醚、对二苯酚、对叔丁氧基苯酚或2，6-二叔丁基-4-甲基苯酚中的一种或者至少两种的组合。
本发明所提供的改性双酚A环氧丙烯酸酯与已报道的聚氨酯改性的双酚A环氧丙烯酸酯相比，柔韧性有了进一步的提高，断裂伸长率可达到40％以上，较大程度上提高了环氧树脂的柔韧性。原材料廉价易得，扩大了环氧丙烯酸树脂的应用领域，如可应用于光固化油墨，塑胶涂料等。
具体实施方式
通过以下实施例对本发明作进一步说明，但并不构成对本发明的限制。
实施例1
向反应器中加入聚己二酸己二醇酯(EJ477)100g，六亚甲基二异氰酸酯(HDI)16.8g，0.01gT12，在N2保护下，加热搅拌，在70-80℃反应1h后测试NCO基团的含量，达到理论值后加入环氧树脂(环氧当量185～195g/eq，248.3g)，羟基丙烯酸乙酯(9.7g)，温度控制在70-80℃，反应3h测试NCO基团含量，当含量等于0时，加入丙烯酸(67.2g)，对甲氧基苯酚(0.20g)，四丁基溴化铵(1.0g)，在100-105℃反应4h测试酸值，当酸值小于5mgKOH/g时，停止反应，得到改性环氧丙烯酸酯a。
实施例2
向反应器中加入聚己二酸一缩二乙二醇酯(PCBZ)100g，甲苯二异氰酸酯(TDI)17.4g，0.01gT12，在N2保护下，加热搅拌，在70-80℃反应1h后测试NCO基团的含量，达到理论值后加入环氧树脂(环氧当量185～195g/eq，248.3g)，羟基丙烯酸乙酯(9.7g)，温度控制在70-80℃，反应3h测试NCO基团含量，当含量等于0时，加入丙烯酸(67.2g)，对甲氧基苯酚(0.20g)，四丁基溴化铵(1.0g)，在100-105℃反应4h测试酸值，当酸值小于5mgKOH/g时，停止反应，得到改性环氧丙烯酸酯b。
实施例3
向反应器中加入聚己二酸丁二醇酯(LM2456)100g，异佛尔酮二异氰酸酯(IPDI)22.2g，0.01gT12，在N2保护下，加热搅拌，温度控制在70-80℃，反应1h后测试NCO基团的含量，达到理论值后加入环氧树脂(环氧当量185～195g/eq，248.3g)，羟基丙烯酸乙酯(9.7g)，温度控制在70-80℃，反应3h测试NCO基团含量，当含量等于0时，加入丙烯酸(67.2g)，对甲氧基苯酚(0.20g)，四丁基溴化铵(1.0g)，在100-105℃反应4h测试酸值，当酸值小于5mgKOH/g时，停止反应，得到改性环氧丙烯酸酯c。
实施例4
向反应器中加入聚己内酯(PCL220N)100g，六亚甲基二异氰酸酯(HDI)16.8g，0.01gT12，在N2保护下，加热搅拌，温度控制在70-80℃，反应1h后测试NCO基团的含量，达到理论值后加入环氧树脂(环氧当量185～195g/eq，248.3g)，羟基丙烯酸乙酯(9.7g)，温度控制在70-80℃，反应3h测试NCO基团含量，当含量等于0时，加入丙烯酸(67.2g)，对甲氧基苯酚(0.20g)，四丁基溴化铵(1.0g)，在100-105℃反应4h测试酸值，当酸值小于5mgKOH/g时，停止反应，得到改性环氧丙烯酸酯d。
对比例1
将248g环氧丙烯酸酯(羟值：243)、29.8g异佛尔酮二异氰酸酯(IPDI)、0.14g对苯二酚、0.14g叔丁氧基苯酚，0.03gT12、0.26g次磷酸投入到装有搅拌器、温度计的三口烧瓶中，搅拌升温至70-80℃保温反应，至NCO≤0.2，降温出料得低聚物e。
将上述实施例1-5，对比例1中所得的改性环氧丙烯酸酯配制成涂料A-E，进行性能测试，涂料的各组分及重量百分比如下：
改性环氧丙烯酸酯预聚物：80％
活性稀释剂：15％
光引发剂：4％
其它助剂：1％
粘度采用BROOKFIELD DV-2+Pro型粘度计测试，铅笔硬度按GB/T 6739-2006标准方法测定，断裂伸长率按GB/T 528-2009测定。具体的测试结果如表1所示。表1数据表明，多元醇的引入，明显改善了环氧丙烯酸酯的柔韧性，相比单独使用异氰酸酯改性的环氧丙烯酸酯，断裂伸长率提高5倍以上。
表1涂料性能
Figure BSA0000201643330000051

Claims (10)

1.一种合成聚氨酯-环氧丙烯酸酯的方法，其特征是：将聚酯多元醇与异氰酸酯反应形成NCO封端的预聚体，然后通过NCO基团与环氧树脂侧链上的羟基和羟基丙烯酸酯中的羟基反应制得中间体，在环氧树脂侧链引入柔性脂肪结构碳碳单键、碳氧醚键以及氨酯键，中间体与丙烯酸反应得到柔韧性好的聚氨酯改性环氧丙烯酸酯。
2.根据权利要求1所述的方法，其特征是包括以下步骤：
(1)聚酯多元醇与异氰酸酯反应制得-NCO基团含量为50％～55％的预聚体；
(2)将预聚体与环氧树脂和羟基丙烯酸酯的混合物，在70～80℃，反应3～5h，当反应物中-NCO基团为零时，反应结束，得中间体；
(3)将中间体与丙烯酸，在90～110℃，反应4～6h，当酸值小于5mgKOH/g时，反应结束，得到聚氨酯-环氧丙烯酸酯。
3.根据权利要求2所述的方法，其特征是：步骤(1)聚酯多元醇与异氰酸酯的摩尔比为1∶2.0～2.1，反应温度为70～80℃，反应时间为1～1.5h，添加质量分数为0.01％的催化剂T12。
4.根据权利要求2所述的方法，其特征是：步骤(2)羟基丙烯酸酯与环氧树脂的羟基摩尔比为3～5∶1。
5.根据权利要求2所述的方法，其特征是：步骤(2)预聚体与混合物的质量比为0.45～0.48∶1。
6.根据权利要求2所述的方法，其特征是：中间体与丙烯酸的质量比为：5.5～5.7∶1。
7.根据权利要求2所述的方法，其特征是：步骤(3)体系中加有阻聚剂和催化剂。
8.根据权利要求5所述的方法，其特征是：所述催化剂是指四乙基溴化铵，苄基三甲基氯化铵或三苯基磷中的一种或几种；所述阻聚剂数字对羟基苯甲醚、对二苯酚、对叔丁氧基苯酚或2，6-二叔丁基-4-甲基苯酚中的一种或几种。
9.根据权利要求1所述的方法，所述异氰酸酯是指甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二苯基甲烷二异氰酸酯及其组合。
10.根据权利要求1所述的方法，所述聚酯多元醇是指聚己二酸己二醇酯、聚己二酸乙二醇酯、聚己二酸一缩二乙二醇酯、聚己二酸甲基丙二醇酯、聚己二酸甲基戊二醇酯、聚己二酸新戊二醇酯、聚己二酸丁二醇酯或聚己内酯中的一种或几种。
CN202010091724.7A 2020-01-22 2020-01-22 一种合成聚氨酯-环氧丙烯酸酯的方法 Active CN111171282B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010091724.7A CN111171282B (zh) 2020-01-22 2020-01-22 一种合成聚氨酯-环氧丙烯酸酯的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010091724.7A CN111171282B (zh) 2020-01-22 2020-01-22 一种合成聚氨酯-环氧丙烯酸酯的方法

Publications (2)

Publication Number Publication Date
CN111171282A true CN111171282A (zh) 2020-05-19
CN111171282B CN111171282B (zh) 2022-02-08

Family

ID=70625237

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010091724.7A Active CN111171282B (zh) 2020-01-22 2020-01-22 一种合成聚氨酯-环氧丙烯酸酯的方法

Country Status (1)

Country Link
CN (1) CN111171282B (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825834A (zh) * 2020-07-31 2020-10-27 肇庆福田化学工业有限公司 一种低粘度紫外光固化改性聚酯丙烯酸酯及制备方法
CN112980384A (zh) * 2021-04-08 2021-06-18 湖北海星瑞新材料科技有限公司 一种钢丝绳索节浇铸胶水及其制备方法
CN113024770A (zh) * 2021-04-08 2021-06-25 湖北海星瑞新材料科技有限公司 一种高强度高韧性乙烯基酯树脂的制备方法
CN114149565A (zh) * 2021-11-30 2022-03-08 江苏三木化工股份有限公司 一种可光固化的超支化聚氨酯-环氧丙烯酸酯的制备方法
CN114230766A (zh) * 2021-12-22 2022-03-25 江苏三木化工股份有限公司 一种耐污型聚氨酯改性环氧丙烯酸酯的制备方法
CN114276514A (zh) * 2021-07-28 2022-04-05 上海康达新材料科技有限公司 一种聚氨酯-丙烯酸杂化树脂和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661317A1 (en) * 1993-12-23 1995-07-05 Basf Corporation Coating containing urethane and acrylic resin mixture for improved resistance to chipping
US6441103B1 (en) * 2000-09-21 2002-08-27 Ppg Industries Ohio, Inc. Aminoplast-based crosslinkers and powder coating compositions containing such crosslinkers
CN101698698A (zh) * 2009-05-31 2010-04-28 北京高盟化工有限公司 一种uv光固化油墨用树脂的制备方法
CN102079810A (zh) * 2010-12-15 2011-06-01 北京航空航天大学 光固化聚氨酯-丙烯酸-环氧树脂胶粘剂的合成和应用
CN106947053A (zh) * 2017-03-28 2017-07-14 深圳市道尔顿电子材料有限公司 一种改性聚氨酯丙烯酸酯共聚物、光刻胶及其制备方法
CN108341921A (zh) * 2018-03-27 2018-07-31 佛山市三求光固材料股份有限公司 聚氨酯改性柔性环氧丙烯酸树脂、其制备方法、光固化标识油墨以及柔性印制电路板
CN109957086A (zh) * 2017-12-14 2019-07-02 惠州市长润发涂料有限公司 一种高性能低成本的聚氨酯丙烯酸酯树脂的合成方法
JP2020015449A (ja) * 2018-07-26 2020-01-30 中日産業株式会社 台車

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661317A1 (en) * 1993-12-23 1995-07-05 Basf Corporation Coating containing urethane and acrylic resin mixture for improved resistance to chipping
US6441103B1 (en) * 2000-09-21 2002-08-27 Ppg Industries Ohio, Inc. Aminoplast-based crosslinkers and powder coating compositions containing such crosslinkers
CN101698698A (zh) * 2009-05-31 2010-04-28 北京高盟化工有限公司 一种uv光固化油墨用树脂的制备方法
CN102079810A (zh) * 2010-12-15 2011-06-01 北京航空航天大学 光固化聚氨酯-丙烯酸-环氧树脂胶粘剂的合成和应用
CN106947053A (zh) * 2017-03-28 2017-07-14 深圳市道尔顿电子材料有限公司 一种改性聚氨酯丙烯酸酯共聚物、光刻胶及其制备方法
CN109957086A (zh) * 2017-12-14 2019-07-02 惠州市长润发涂料有限公司 一种高性能低成本的聚氨酯丙烯酸酯树脂的合成方法
CN108341921A (zh) * 2018-03-27 2018-07-31 佛山市三求光固材料股份有限公司 聚氨酯改性柔性环氧丙烯酸树脂、其制备方法、光固化标识油墨以及柔性印制电路板
JP2020015449A (ja) * 2018-07-26 2020-01-30 中日産業株式会社 台車

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
辛浩波，等: ""丙烯酸酯、环氧树脂对聚氨酯胶黏剂性能影响的研究"", 《化工科技》 *
龙一浪: ""E-20环氧树脂丙烯酸酯的合成及表征"", 《2017中国粉末涂料与涂装行业年会论文集》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825834A (zh) * 2020-07-31 2020-10-27 肇庆福田化学工业有限公司 一种低粘度紫外光固化改性聚酯丙烯酸酯及制备方法
CN112980384A (zh) * 2021-04-08 2021-06-18 湖北海星瑞新材料科技有限公司 一种钢丝绳索节浇铸胶水及其制备方法
CN113024770A (zh) * 2021-04-08 2021-06-25 湖北海星瑞新材料科技有限公司 一种高强度高韧性乙烯基酯树脂的制备方法
CN113024770B (zh) * 2021-04-08 2023-02-24 湖北海星瑞新材料科技有限公司 一种高强度高韧性乙烯基酯树脂的制备方法
CN114276514A (zh) * 2021-07-28 2022-04-05 上海康达新材料科技有限公司 一种聚氨酯-丙烯酸杂化树脂和应用
CN114276514B (zh) * 2021-07-28 2023-10-27 上海康达新材料科技有限公司 一种聚氨酯-丙烯酸杂化树脂和应用
CN114149565A (zh) * 2021-11-30 2022-03-08 江苏三木化工股份有限公司 一种可光固化的超支化聚氨酯-环氧丙烯酸酯的制备方法
CN114230766A (zh) * 2021-12-22 2022-03-25 江苏三木化工股份有限公司 一种耐污型聚氨酯改性环氧丙烯酸酯的制备方法

Also Published As

Publication number Publication date
CN111171282B (zh) 2022-02-08

Similar Documents

Publication Publication Date Title
CN111171282B (zh) 一种合成聚氨酯-环氧丙烯酸酯的方法
CN112048051B (zh) 一种聚氨酯丙烯酸酯树脂及其制备方法
US5248752A (en) Polyurethane (meth)acrylates and processes for preparing same
EP0471765B1 (en) Polyester chain-extended vinyl ether urethane oligomers
JPH0598211A (ja) 高性能ポリウレタン塗料用組成物およびその製造方法
EA019063B1 (ru) Ненасыщенные полиэфируретановые преполимеры и их применение
CN110835398A (zh) 一种松香基水性聚氨酯乳液的制备方法
CA1225786A (en) Process for the production of polyurethane urea elastomers
CN111410732A (zh) 一种水性uv树脂及其制备方法
US4123421A (en) Stable tertiary amine containing terminally unsaturated polyurethane resins
KR19990077019A (ko) 반응성 프리폴리머성 유기 화합물의 용도
KR102599861B1 (ko) 부식 저항성 코팅에 유용한 디사이클로펜타디엔 개질 에스테르 올리고머
CN115490828A (zh) 改性聚噁唑烷酮预聚物及基于其的耐高温光固化胶粘剂
CN115677997A (zh) 一种低粘度uv光固化超支化聚酯丙烯酸酯树脂及其制备方法与应用
CN110922603B (zh) 一种不同链段改性的光固化树脂及其制备方法和应用
US5004794A (en) Isocyanate prepolymers
JP3889858B2 (ja) ウレタン・不飽和オルガノオリゴマーとその製造方法
JPH0149370B2 (zh)
CN110452360A (zh) 硬度75a丝网刮刀用强极性支化聚氨酯弹性体及其制备方法
CN114031743B (zh) 自引发小分子扩链剂、自引发聚氨酯丙烯酸酯预聚物及制备方法
CN109265649B (zh) 一种自乳化型辐射固化组合物及其制备方法
JPS5996119A (ja) ラジカル重合性プレポリマ−の製法
CN115010901A (zh) 一种低粘度耐水解光固化聚氨酯树脂及其制备方法和应用
CN115612096A (zh) 一类聚噁唑烷酮预聚物及其制备方法与应用
CN117417508A (zh) 一种聚氨酯树脂及其制备方法和应用

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