CN111909360B - 一种高弹性环氧固化剂、制备方法以及环氧树脂 - Google Patents
一种高弹性环氧固化剂、制备方法以及环氧树脂 Download PDFInfo
- Publication number
- CN111909360B CN111909360B CN202010810603.3A CN202010810603A CN111909360B CN 111909360 B CN111909360 B CN 111909360B CN 202010810603 A CN202010810603 A CN 202010810603A CN 111909360 B CN111909360 B CN 111909360B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- reaction
- epoxy resin
- elasticity
- epoxy
- 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.)
- Active
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开了一种高弹性环氧固化剂、制备方法以及环氧树脂,涉及环氧树脂技术领域。本发明提供的高弹性环氧固化剂,将柔性分子链引入主链,以此达到了增韧的效果,断裂伸长率达到50%‑100%,又引入了环碳酸酯使得固化剂中含有大量氢键,羟基及胺酯键可提高附着力,提高环氧树脂的耐化学性和力学强度;本发明提供的高弹性环氧固化剂,使用环碳酸酯能有效降低成本,且制得的高弹性环氧固化剂与市售预聚物物理混合可得到不同拉伸伸长率的环氧树脂。
Description
技术领域
本发明涉及环氧树脂技术领域,尤其涉及一种高弹性环氧固化剂、制备方法以及环氧树脂。
背景技术
环氧树脂是一种性能十分优异重要的热固型树脂,由于具有很高的交联密度和特有的分子结构,导致其固化材料脆性大,耐温性及坑冲击性差,限制了其应用发展,因此对环氧树脂的增韧已成为环氧改性的重要研究方向之一。
目前实现环氧增韧的主要方法包括化学法和物理法,比如选择具有长链端氨基聚醚或聚氨酯作为环氧树脂固化剂,采用聚合物共混的方法来制备具有不同冲击韧性及断裂伸长率的弹性体,但随着聚醚及聚氨酯链的加长,降低了交联密度,在提升弹性的同时降低了力学性能。
发明内容
本发明所要解决的技术问题是背景技术中提到的一些缺陷,提供一种性能优异,抗剪切强度高的环氧固化剂,提高产品的耐水性和耐化学性。
为了解决上述问题,本发明提出以下技术方案:
第一方面,本发明提供一种高弹性环氧固化剂,具有如下式16的结构:
式16:
式16中,R为醚类基团或聚醚类基团;R1为芳香族类基团或脂环类基团;R2为芳香族类基团,脂环类基团或C2-C20的烷基。
其进一步地技术方案为,式16中,R选自如下式1-3的一种或几种:
其进一步地技术方案为,式16中,R1选自如下式4-10的一种或几种:
其进一步地技术方案为,式16中,R2选自如下式11-15的一种或几种:
本发明提供一种高弹性环氧固化剂的制备方法,包括以下步骤:
S1,将聚二元醇溶解于溶剂中,在氮气保护下,与异氰酸酯单体反应,聚二元醇与异氰酸酯单体的摩尔比为1:(2-5),反应温度30℃-110℃,反应完全后,冷却至室温,得到反应液A;
S2,将碳酸甘油酯溶解于促进剂中,在氮气保护下,与反应液A反应,反应液A与碳酸甘油酯的摩尔比例为1:(2-5),反应温度30℃-110℃,反应完全后,冷却至室温,得到反应液B;
S3,在氮气保护下,将多元胺与反应液B反应,反应液B与多元胺的摩尔比例为1:(2-5),反应温度30℃-110℃,反应完全后,冷却,即得到高弹性环氧固化剂。
优选地,所述聚二元醇为除水后的聚二元醇,含水量为0-5%。
其进一步地技术方案为,所述溶剂为脂肪烃,芳烃,甲醇,乙醇,乙酸乙酯,乙酸丁酯,丙酮,乙二醇单甲醚,丙二醇甲醚,丙二醇甲醚醋酸酯,N,N二甲基甲酰胺,乙二醇叔丁基醚,丙二醇叔丁基醚,甘油二叔丁基醚中的一种或几种的组合。
其进一步地技术方案为,所述促进剂为三苯基膦,三乙胺,2,4,6-三(二甲氨基甲基)苯酚,水杨酸、苯甲醇、三乙醇胺、2-乙基-4-甲基咪唑、苯酚、2-苯基咪唑中的一种或几种的组合。
其进一步地技术方案为,步骤S1中,聚二元醇溶解于溶剂中,得到0.5wt%-10wt%的聚二元醇溶液。
其进一步地技术方案为,步骤S2中,碳酸甘油酯溶解于促进剂中,得到0.5wt%-10wt%的碳酸甘油酯溶液。
本发明还提供一种环氧树脂,由固化剂与预聚物反应制得;
所述固化剂为上述的高弹性环氧固化剂,或由所述的高弹性环氧固化剂的制备方法制得的高弹性环氧固化剂;
所述预聚物选自双酚A型环氧树脂预聚物,双酚F型环氧树脂预聚物,多酚型缩水甘油醚环氧树脂预聚物,脂肪族缩水甘油醚环氧树脂预聚物,缩水甘油酯型环氧树脂预聚物,缩水甘油胺型环氧树脂预聚物,环氧化烯烃化合物预聚物,海因环氧树脂预聚物中的一种或多种。
与现有技术相比,本发明所能达到的技术效果包括:
本发明提供的高弹性环氧固化剂,将柔性分子链引入主链,以此达到了增韧的效果,断裂伸长率达到50%-100%,又引入了环碳酸酯使得固化剂中含有大量氢键,羟基及胺酯键可提高固化剂与预聚物的附着力,从而提高环氧树脂的耐化学性和力学强度;本发明提供的高弹性环氧固化剂,使用环碳酸酯能有效降低成本,且制得的高弹性环氧固化剂与市售预聚物物理混合可得到不同拉伸伸长率的环氧树脂。
本发明提供的高弹性环氧固化剂的制备方法,通过引入碳酸酯改性环氧固化剂,先合成长链二官环碳酸酯,然后与多元胺反应,制备出的固化剂产品性能优异,抗剪切强度得到极大提高,且环碳酸酯基开环后形成分子间氢键,提高了产品的耐水性和耐化学性。
具体实施方式
下面将对实施例中的技术方案进行清楚、完整地描述。显然,以下将描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施案例一、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(2)结构,聚合度为17;R1具有式(7)结构;R2具有式(11)结构,聚合度为3。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g甲苯-2,4-二异氰酸酯异氰酸酯;称取100g除水后的聚丙二醇(M=1000)溶解于24.5g的乙酸丁酯中,将其加入恒压漏斗,在氮气保护下缓慢滴加至烧瓶内,与甲苯-2,4-二异氰酸酯异氰酸酯反应,反应温度60℃,1小时滴完后保温反应2小时,反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度55℃,0.5小时滴加完后保温反应2小时,反应完成,冷却出料,得到反应液B。
(3).称取35.1g己二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下70℃缓慢滴加至烧瓶内,与己二胺反应,0.5小时滴加完后保温反应2小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例二、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(2)结构,聚合度为17;R1具有式(7)结构;R2具有式(12)结构。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g甲苯-2,4-二异氰酸酯异氰酸酯;称取100g除水后的聚丙二醇(M=1000)溶解于26g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与甲苯-2,4-二异氰酸酯异氰酸酯反应,反应温度60℃,1小时滴完后保温反应2小时,反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度60℃,2小时滴加完后保温反应1小时,反应完成,冷却出料,得到反应液B。
(3).称取40.9g异佛尔酮二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下50℃缓慢滴加至烧瓶内,与异佛尔酮二胺反应,2小时滴加完后保温反应2小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例三、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(1)结构,聚合度为15;R1具有式(7)结构;R2具有式(11)结构,聚合度为3。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g甲苯-2,4-二异氰酸酯异氰酸酯;称取100g除水后的聚丁二醇(M=1000)溶解于24.5g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与甲苯-2,4-二异氰酸酯异氰酸酯反应,反应温度70℃,1小时滴完后保温反应2小时,反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度50℃,1小时滴加完后保温反应3小时,反应完成,冷却出料,得到反应液B。
(3).称取35.1g己二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下80℃缓慢滴加至烧瓶内,与己二胺反应,1小时滴加完后保温反应1小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例四、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(1)结构,聚合度为15;R1具有式(9)结构;R2具有式(11)结构,聚合度为3。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g4,4-亚甲基双(异氰酸苯酯);称取100g除水后的聚丁二醇(M=1000)溶解于28.4g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与4,4-亚甲基二异氰酸酯异氰酸酯反应,反应温度80℃,0.5小时滴完后保温反应1.5小时,反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度60℃,0.5小时滴加完后保温反应1小时,反应完成,冷却出料,得到反应液B。
(3).称取35.1g己二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下60℃缓慢滴加至烧瓶内,与己二胺反应,2小时滴加完后保温反应2小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例五、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(2)结构,聚合度为17;R1具有式(6)结构;R2具有式(11)结构,聚合度为3。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入46.6g异佛尔酮二异氰酸酯异氰酸酯;称取100g除水后的聚丙二醇(M=1000)溶解于22.6g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与异佛尔酮二异氰酸酯异氰酸酯反应,反应温度60℃,1小时滴完后保温反应2小时反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度85℃,0.5小时滴加完后保温反应2小时,冷却出料,得到一种反应液B。
(3).称取27.9g己二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下50℃缓慢滴加至烧瓶内,与己二胺反应,2小时滴加完后保温反应3小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例六、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(2)结构,聚合度为17;R1具有式(7)结构;R2具有式(11)结构,聚合度为3。
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g甲苯-2,4-二异氰酸酯异氰酸酯;称取100g除水后的聚丙二醇(M=1000)溶解于22.6g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与甲苯-2,4-二异氰酸酯异氰酸酯反应,反应温度60℃,1小时滴完后保温反应2小时,反应完成,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度55℃,0.5小时滴加完后保温反应3小时,反应完成,冷却出料,得到反应液B。
(3).称取27.9g己二胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下70℃缓慢滴加烧瓶内,与己二胺反应,0.5小时滴加完后保温反应2小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
实施案例七、
本实施例提供一种高弹性环氧固化剂,结构如下:
其中R具有式(1)结构,聚合度为15;R1具有式(7)结构;R2具有式(12)结构。
上述的高弹性环氧固化剂的制备方法如下:
(1).在装有温度计和搅拌的四口烧瓶内加入36.6g甲苯-2,4-二异氰酸酯;称取100g除水后的聚丁二醇(M=1000)溶解于26g乙酸丁酯中,加入恒压漏斗中,在氮气保护下缓慢滴加至烧瓶内,与甲苯-2,4-二异氰酸酯异氰酸酯反应,反应温度60℃,1小时滴完后保温反应2小时,冷却至室温,得到反应液A。
(2).称取26g碳酸甘油酯并加入25g苯甲醇溶解后装入另一烧瓶内;将上述反应液A加入恒压漏斗中,氮气保护下缓慢滴加至烧瓶内,与碳酸甘油酯混合液反应,反应温度80℃,2小时滴加完后保温反应0.5小时,反应完成,冷却出料,得到反应液B。
(3).称取40.9g异佛尔酮胺装入在另一烧瓶内;将反应液B加入恒压漏斗中,氮气保护下55℃缓慢滴加至烧瓶内,与异佛尔酮胺反应,0.5小时滴加完后保温反应2小时,反应完成,冷却出料,最终得到高弹性环氧固化剂。
性能测试:
1)试样制备
室温下将上述实施案例一至七的高弹性环氧固化剂与E51双酚A树脂预聚物按化学当量比1:1称量并搅拌均匀,在真空脱气除泡后,倒入模具中固化,常温/7d,制成哑铃型的环氧树脂实施例,按标准方法测试性能,结果如表1。
其中,对照例为D1000聚醚胺改性固化剂与E51双酚A树脂预聚物按化学当量比1:1反应得到。
表1为环氧树脂的性能测试结果
从表1的测试结果来看,用本发明制备的一种高弹性环氧固化剂得到的环氧树脂,在室温下固化7d后断裂伸长率可达到100%甚至更高,拉伸强度仍有近15MPa,性能优于进口产品,且成本较低。
在上述实施例中,对各个实施例的描述都各有侧重,某个实施例中没有详细描述的部分,可以参见其他实施例的相关描述。
以上所述,为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到各种等效的修改或替换,这些修改或替换都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以权利要求的保护范围为准。
Claims (6)
1.一种高弹性环氧固化剂,其特征在于,具有如下式16的结构:
式16:
;
式16中,R选自如下式1-3的一种或几种:
;/>;
;
R1选自如下式4-10的一种或几种:
;/>;/>;/>;
;/>;/>;
R2选自如下式11-15的一种或几种:
;/>;/>;/>;
;
所述高弹性环氧固化剂的制备方法,包括以下步骤:
S1,将聚二元醇溶解于溶剂中,在氮气保护下,与异氰酸酯单体反应,聚二元醇与异氰酸酯单体的摩尔比为1:(2-5),反应温度30℃-110℃,反应完全后,冷却至室温,得到反应液A,所述聚二元醇的分子量为1000;
S2,将碳酸甘油酯溶解于促进剂中,在氮气保护下,与反应液A反应,反应液A与碳酸甘油酯的摩尔比例为1:(2-5),反应温度30℃-110℃,反应完全后,冷却至室温,得到反应液B;
S3,在氮气保护下,将多元胺与反应液B反应,反应液B与多元胺的摩尔比例为1:(2-5),反应温度30℃-110℃,反应完全后,冷却,即得到高弹性环氧固化剂。
2.如权利要求1所述的高弹性环氧固化剂,其特征在于,所述溶剂为脂肪烃,芳烃,甲醇,乙醇,乙酸乙酯,乙酸丁酯,丙酮,乙二醇单甲醚,丙二醇甲醚,丙二醇甲醚醋酸酯,N,N-二甲基甲酰胺,乙二醇叔丁基醚,丙二醇叔丁基醚,甘油二叔丁基醚中的一种或几种的组合。
3.如权利要求1所述的高弹性环氧固化剂,其特征在于,所述促进剂为三苯基膦、三乙胺、2,4,6-三(二甲氨基甲基)苯酚、水杨酸、苯甲醇、三乙醇胺、2-乙基-4-甲基咪唑、苯酚、2-苯基咪唑中的一种或几种的组合。
4.如权利要求1所述的高弹性环氧固化剂,其特征在于,步骤S1中,聚二元醇溶解于溶剂中,得到0.5wt%-10wt%的聚二元醇溶液。
5.如权利要求1所述的高弹性环氧固化剂,其特征在于,步骤S2中,碳酸甘油酯溶解于促进剂中,得到0.5wt%-10wt%的碳酸甘油酯溶液。
6.一种环氧树脂,其特征在于,由固化剂与预聚物反应制得;
所述固化剂为权利要求1-5任一项所述的高弹性环氧固化剂;
所述预聚物选自双酚A型环氧树脂预聚物,双酚F型环氧树脂预聚物,多酚型缩水甘油醚环氧树脂预聚物,脂肪族缩水甘油醚环氧树脂预聚物,缩水甘油酯型环氧树脂预聚物,缩水甘油胺型环氧树脂预聚物,环氧化烯烃化合物预聚物,海因环氧树脂预聚物中的一种或多种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010810603.3A CN111909360B (zh) | 2020-08-11 | 2020-08-11 | 一种高弹性环氧固化剂、制备方法以及环氧树脂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010810603.3A CN111909360B (zh) | 2020-08-11 | 2020-08-11 | 一种高弹性环氧固化剂、制备方法以及环氧树脂 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111909360A CN111909360A (zh) | 2020-11-10 |
CN111909360B true CN111909360B (zh) | 2023-08-01 |
Family
ID=73284458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010810603.3A Active CN111909360B (zh) | 2020-08-11 | 2020-08-11 | 一种高弹性环氧固化剂、制备方法以及环氧树脂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111909360B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115637125B (zh) * | 2021-07-20 | 2023-09-12 | 中蓝晨光化工研究设计院有限公司 | 一种环保型环氧树脂胶粘剂及其制备方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6607646B2 (en) * | 2001-09-12 | 2003-08-19 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent |
CN101348561A (zh) * | 2008-08-01 | 2009-01-21 | 中国林业科学研究院林产化学工业研究所 | 端氨基聚醚水性环氧固化剂的制备方法 |
CN101775137B (zh) * | 2010-03-15 | 2012-06-13 | 华中科技大学 | 一种水性非异氰酸酯聚氨酯及其制备方法 |
CN102731779B (zh) * | 2011-12-29 | 2014-02-26 | 湖北航天化学技术研究所 | 一种杂化非异氰酸酯聚氨酯的合成方法 |
WO2014158705A1 (en) * | 2013-03-13 | 2014-10-02 | 3M Innovative Properties Company | Methods of making low shrinkage and expandable compositions and expandable monomers |
CN103333323B (zh) * | 2013-06-13 | 2015-09-02 | 武汉市科达云石护理材料有限公司 | 高韧性高活性环氧树脂固化剂及其制备方法 |
FR3018815B1 (fr) * | 2014-03-19 | 2016-03-04 | Bostik Sa | Prepolymere de polyurethane a terminaisons cyclocarbonate de faible viscosite et son utilisation dans la fabrication d'une composition adhesive multicomposant |
CN105061709B (zh) * | 2015-08-26 | 2018-02-27 | 华南理工大学 | 一种基于甲苯二异氰酸酯二聚体的聚氨酯固化剂及其制法 |
CN105524426B (zh) * | 2016-01-15 | 2018-03-30 | 上海雄润树脂有限公司 | 一种非异氰酸酯聚氨酯碳纳米管改性环氧树脂复合材料及其制备方法 |
WO2018118767A1 (en) * | 2016-12-22 | 2018-06-28 | Avery Dennison Corporation | Convertible pressure sensitive adhesives comprising urethane (meth) acrylate oligomers |
CN107141446B (zh) * | 2017-04-20 | 2019-08-30 | 江西科技师范大学 | 氨基甲酸酯基硫醇类环氧固化剂及其制备方法和应用 |
CN108409943A (zh) * | 2018-03-27 | 2018-08-17 | 郑州轻工业学院 | 聚氨酯改性三甲基己二胺韧性固化剂及其制备方法 |
CN109912781B (zh) * | 2019-01-31 | 2021-08-20 | 铃鹿复合建材(上海)有限公司 | 一种环氧固化剂 |
CN111440292A (zh) * | 2020-03-06 | 2020-07-24 | 长春工业大学 | 一种封闭型异氰酸酯交联剂及其制备方法 |
-
2020
- 2020-08-11 CN CN202010810603.3A patent/CN111909360B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN111909360A (zh) | 2020-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4002598A (en) | Polyether urea epoxy curing agent | |
JP2660742B2 (ja) | 貯蔵安定な反応樹脂混合物、その製造及びその用途 | |
US4178427A (en) | Polyether urea epoxy curing agent | |
US4632970A (en) | Epoxy resin composition | |
EP0675144B1 (en) | Flexibilized polyepoxide resins incorporating poly-N-methylated secondary amines | |
CN111909360B (zh) | 一种高弹性环氧固化剂、制备方法以及环氧树脂 | |
CN116891712A (zh) | 用于环氧粘合剂的封闭的聚氨酯增韧剂 | |
KR890003002B1 (ko) | 열경화성 폴리(옥사졸리돈 및 우레탄)조성물 및 그 제법 | |
US5138016A (en) | Isocyanurate-free oxazolidone compound made from epoxy and a hindered isocyanate compound and a novel catalyst for their production | |
US5053465A (en) | Epoxy polyurethane polyureas from epoxy resin, blocked isocyanate prepolymer and polyetherpolyamine | |
EP3274391B1 (en) | Epoxy systems having improved fracture toughness | |
US9650542B2 (en) | Use of polypropyleneimine as curing agent for epoxide resins | |
US6350826B1 (en) | Epoxy vinyl ester and urethane vinyl ester derived from low and high MW glycols | |
KR102566314B1 (ko) | 에폭시 화합물, 이를 포함하는 에폭시 수지 조성물 및 이를 포함하는 일액형 에폭시 접착제 조성물 | |
KR102578045B1 (ko) | 신규한 글리시딜 산 무수물기반 폴리올 화합물, 이로부터 제조된 개질된 폴리우레탄 공중합체와 이를 포함하는 접착제 조성물 및 이로부터 제조된 경화물 | |
EP3786206B1 (en) | Urea terminated butadiene polymers and butadiene acrylonitrile copolymers | |
JPH07126241A (ja) | 新規のポリアミン、その製造方法並びにその用途 | |
KR20170120322A (ko) | 저온 환경에서 우수한 물성을 갖는 우레탄 에폭시 하이브리드 접착제 조성물 | |
Pazhanikumar et al. | Synthesis, characterization and applications of polyurethane aryl cyanate ester resin | |
US11996211B1 (en) | Polyurea-based solid electrolyte and preparation method thereof | |
KR102600560B1 (ko) | 에폭시 수지 조성물 및 이를 포함하는 일액형 에폭시 접착제 조성물 | |
CN115490851B (zh) | 一种植物油基非异氰酸酯聚氨酯树脂及其制备方法 | |
EP4155336A1 (en) | Carbonate-containing epoxy resin, manufacturing method thereof, epoxy curable product prepared thereby and method for degrading epoxy curable product | |
CN117645571A (zh) | 一种改性咪唑潜伏型环氧树脂固化剂及其制备方法和应用 | |
CN114502647A (zh) | 环氧树脂组合物及固化物 |
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 | ||
TA01 | Transfer of patent application right | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20230619 Address after: Floor 8, Building B, Feiyang Science Park, No. 8, Longchang Road, Xin'an Street, Bao'an District, Shenzhen, Guangdong 518100 Applicant after: Shenzhen Bao'an New Materials Research Institute Address before: 518000 8th floor, building B, Feiyang Xingye technology plant, Liuxian 2nd Road, Xin'an street, Bao'an District, Shenzhen City, Guangdong Province Applicant before: SHENZHEN FEIYANG XINGYE TECHNOLOGY CO.,LTD. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |