CN106189086A - 用于纤维缠绕成型的次中温固化环氧树脂组合物 - Google Patents

用于纤维缠绕成型的次中温固化环氧树脂组合物 Download PDF

Info

Publication number
CN106189086A
CN106189086A CN201610559811.4A CN201610559811A CN106189086A CN 106189086 A CN106189086 A CN 106189086A CN 201610559811 A CN201610559811 A CN 201610559811A CN 106189086 A CN106189086 A CN 106189086A
Authority
CN
China
Prior art keywords
epoxy resin
temperature setting
intermediate temperature
secondary intermediate
fiber winding
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.)
Pending
Application number
CN201610559811.4A
Other languages
English (en)
Inventor
朱小龙
张华川
姚杰雄
李晓阳
王培勇
刘欣
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.)
Lu Chen New Materials Technology Co Ltd
Original Assignee
Lu Chen New Materials Technology 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 Lu Chen New Materials Technology Co Ltd filed Critical Lu Chen New Materials Technology Co Ltd
Priority to CN201610559811.4A priority Critical patent/CN106189086A/zh
Publication of CN106189086A publication Critical patent/CN106189086A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/32—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core on a rotating mould, former or core
    • 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
    • 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
    • C08G59/502—Polyalkylene polyamines
    • 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
    • C08G59/5046—Amines heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

本发明公开了一种用于纤维缠绕成型的次中温固化环氧树脂组合物，由以下重量份的原料组成：环氧树脂80～120份，胺类固化剂20～50份，具有环氧基团的低分子稀释剂0.5～10份，促进剂0.1～3份。本发明制备的环氧树脂组合物室温下操作时间不小于3小时，粘度小于700cP，组合物经适当的固化制度固化后，浇注体冲击强度可达到60KJ/m2，可以使用耐温性差的塑料、橡胶作为内胆或内衬材料，开发适应不同需求的新产品。

Description

用于纤维缠绕成型的次中温固化环氧树脂组合物
技术领域
本发明属于高分子材料领域，具体涉及一种用于纤维缠绕成型的次中温固化环氧树脂组合物，可以使用塑料(尼龙6、ABS、聚乙烯等)作为内胆直接进行缠绕，适用于多种新产品的开发及应用。
背景技术
湿法缠绕成型是指增强材料(如纤维)经过树脂浸渍后直接缠绕在芯模上，经固化后成型的一种复合材料成型方法。适用树脂基体的研制是湿法缠绕成型技术顺利实施的重要保证。在缠绕过程中，为了保证增强纤维充分浸透，要求采用的树脂基体要有较低的粘度，并在缠绕环境温度下保持较长时间的低粘度状态，即具备较长的适用期。
现有湿法缠绕成型所用树脂一般采用高温固化(＞120℃)，产品成型温度高、易收缩造成尺寸稳定性不佳、较大的内应力、对固化设备要求高，成本较高，且对芯模及内衬材料的选择范围较窄，通常选用金属类材料。
发明内容
本发明目的是提供一种用于纤维缠绕成型的次中温固化环氧树脂组合物，解决现有的湿法缠绕成型用树脂固化温度高导致产品成型温度高、易收缩造成尺寸稳定性不佳、较大的内应力、对固化设备要求高，成本较高的问题。
本发明的技术方案为：一种用于纤维缠绕成型的次中温固化环氧树脂组合物，由以下重量份的原料组成：环氧树脂80～120份，胺类固化剂20～50份，具有环氧基团的低分子化合物0.5～10份，促进剂0.1～3份。
进一步地，所述环氧树脂为缩水甘油醚类环氧树脂或脂环族环氧树脂中的一种或两者的混合物。
进一步地，所述缩水甘油醚类环氧树脂为双酚A型缩水甘油醚、双酚F型缩水甘油醚、脂肪族缩水甘油醚或双酚S型缩水甘油醚中的一种或几种的混合物。
进一步地，所述胺类固化剂为脂肪族多元胺、聚亚甲基二胺、脂肪族酰胺多胺、含芳香环脂肪胺、芳香胺、杂环胺或者它们的改性胺类固化剂中一种或几种的混合物。
进一步地，所述具有环氧基团的低分子化合物为单环氧基活性稀释剂、双环氧基活性稀释剂或三环氧基活性稀释剂中的一种或几种的混合物。
进一步地，所述促进剂为叔胺类促进剂。
本发明还公开了一种用于纤维缠绕成型的次中温固化环氧树脂组合物的制备方法，包括以下步骤：
1)按照比例称环氧树脂、固化剂、具有环氧基团的低分子稀释剂和促进剂；
2)向环氧树脂中加入具有环氧基团的低分子稀释剂、胺类固化剂、促进剂，搅拌至均匀，得到用于纤维缠绕成型的次中温固化环氧树脂组合物。
进一步地，当环氧树脂采用缩水甘油醚类环氧树脂和脂环族环氧树脂的混合物时，需要先将缩水甘油醚类环氧树脂和脂环族环氧树脂的混合物在20～50℃加热搅拌0.5～3h，然后加入具有环氧基团的低分子稀释剂、胺类固化剂、促进剂，搅拌至均匀，得到用于纤维缠绕成型的次中温固化环氧树脂组合物。
本发明与现有技术相比具有如下优点：
本发明制备的环氧树脂组合物室温下操作时间不小于3小时，粘度小于700cP，组合物经适当的固化制度固化后，浇注体冲击强度可达到60KJ/m2，可以使用耐温性差的塑料、橡胶作为内胆或内衬材料，开发适应不同需求的新产品。
具体实施方式
实施例1
将85g缩水甘油醚类环氧树脂与5g脂环族环氧树脂混合，加热至40℃搅拌40min，形成透明液态，冷却到室温后加入10g单官能团环氧活性稀释剂、35g改性胺类固化剂以及1g叔胺类促进剂，混合均匀后得到用。纤维缠绕成型的次中温固化环氧树脂组合物，室温下操作时间(粘度小于700cP)为190min，浇注体冲击强度为60.5KJ/m2。
实施例2
将90g缩水甘油醚类环氧树脂与5g脂环族环氧树脂混合，加热至35℃搅拌40min，形成透明液态，冷却到室温后加入5g单官能团环氧活性稀释剂、30g改性胺类固化剂以及0.5g叔胺类促进剂，混合均匀后得到用于纤维缠绕成型的次中温固化环氧树脂组合物，室温下操作时间(粘度小于700cP)为210min，浇注体冲击强度为65.3KJ/m2。
实施例3
将90g缩水甘油醚类环氧树脂、10g单官能团环氧活性稀释剂、30g改性胺类固化剂以及1g叔胺类促进剂在室温下混合均匀后得到用于纤维缠绕成型的次中温固化环氧树脂组合物，室温下操作时间(粘度小于700cP)为240min，浇注体冲击强度为62.7KJ/m2。
实施例4
将120g缩水甘油醚类环氧树脂、10g单官能团环氧活性稀释剂、40g改性胺类固化剂以及1.5g叔胺类促进剂在室温下混合均匀后得到用于纤维缠绕成型的次中温固化环氧树脂组合物，室温下操作时间(粘度小于700cP)为280min，浇注体冲击强度为71.3KJ/m2。。
以上所述实施例仅表达了本申请的具体实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请保护范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请技术方案构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。

Claims (8)

1.一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，由以下重量份的原料组成：环氧树脂80～120份，胺类固化剂20～50份，具有环氧基团的低分子稀释剂0.5～10份，促进剂0.1～3份。
2.根据权利要求1中所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，所述环氧树脂为缩水甘油醚类环氧树脂或脂环族环氧树脂中的一种或两者的混合物。
3.根据权利要求2中所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，所述缩水甘油醚类环氧树脂为双酚A型缩水甘油醚、双酚F型缩水甘油醚、脂肪族缩水甘油醚或双酚S型缩水甘油醚中的一种或几种的混合物。
4.根据权利要求1所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，所述胺类固化剂为脂肪族多元胺、聚亚甲基二胺、脂肪族酰胺多胺、含芳香环脂肪胺、芳香胺、杂环胺或者它们的改性胺类固化剂中一种或几种的混合物。
5.根据权利要求1所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，所述具有环氧基团的低分子稀释剂为单环氧基活性稀释剂、双环氧基活性稀释剂或三环氧基活性稀释剂中的一种或几种的混合物。
6.根据权利要求1所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物，其特征在于，所述促进剂为叔胺类促进剂。
7.根据权利要求1-6任一项所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物的制备方法，其特征在于，包括以下步骤：
1)按照比例称环氧树脂、固化剂、具有环氧基团的低分子稀释剂和促进剂；
2)向环氧树脂中加入具有环氧基团的低分子稀释剂、胺类固化剂、促进剂，搅拌至均匀，得到用于纤维缠绕成型的次中温固化环氧树脂组合物。
8.根据权利要求7所述的一种用于纤维缠绕成型的次中温固化环氧树脂组合物的制备方法，其特征在于，当环氧树脂采用缩水甘油醚类环氧树脂和脂环族环氧树脂的混合物时，需要先将缩水甘油醚类环氧树脂和脂环族环氧树脂的混合物在20～50℃加热搅拌0.5～3h，然后加入具有环氧基团的低分子稀释剂、胺类固化剂、促进剂，搅拌至均匀，得到用于纤维缠绕成型的次中温固化环氧树脂组合物。
CN201610559811.4A 2016-07-15 2016-07-15 用于纤维缠绕成型的次中温固化环氧树脂组合物 Pending CN106189086A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610559811.4A CN106189086A (zh) 2016-07-15 2016-07-15 用于纤维缠绕成型的次中温固化环氧树脂组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610559811.4A CN106189086A (zh) 2016-07-15 2016-07-15 用于纤维缠绕成型的次中温固化环氧树脂组合物

Publications (1)

Publication Number Publication Date
CN106189086A true CN106189086A (zh) 2016-12-07

Family

ID=57475677

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610559811.4A Pending CN106189086A (zh) 2016-07-15 2016-07-15 用于纤维缠绕成型的次中温固化环氧树脂组合物

Country Status (1)

Country Link
CN (1) CN106189086A (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106893263A (zh) * 2017-04-06 2017-06-27 广州均实复合材料科技有限公司 一种树脂体系组合物及采用该组合物制造的耐冲击柔韧性复合材料
CN110183819A (zh) * 2019-03-15 2019-08-30 络合高新材料(上海)有限公司 一种呼吸器用复合气瓶专用环氧树脂胶液及其制备方法
CN111378247A (zh) * 2020-03-20 2020-07-07 山东非金属材料研究所 一种湿法缠绕成型复合材料用环氧树脂组合物及其制备方法
CN113150500A (zh) * 2021-04-30 2021-07-23 中国工程物理研究院化工材料研究所 一种缠绕成型的纤维增强环氧类玻璃高分子复合材料

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977557A (zh) * 2012-12-11 2013-03-20 蓝星(北京)化工机械有限公司 一种室温固化环氧树脂组合物及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977557A (zh) * 2012-12-11 2013-03-20 蓝星(北京)化工机械有限公司 一种室温固化环氧树脂组合物及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王斌，等: ""60℃固化缠绕用环氧树脂体系"", 《材料工程》 *
苏祖君，等: ""湿法缠绕用次中温固化的环氧树脂配方"", 《纤维复合材料》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106893263A (zh) * 2017-04-06 2017-06-27 广州均实复合材料科技有限公司 一种树脂体系组合物及采用该组合物制造的耐冲击柔韧性复合材料
CN110183819A (zh) * 2019-03-15 2019-08-30 络合高新材料(上海)有限公司 一种呼吸器用复合气瓶专用环氧树脂胶液及其制备方法
CN111378247A (zh) * 2020-03-20 2020-07-07 山东非金属材料研究所 一种湿法缠绕成型复合材料用环氧树脂组合物及其制备方法
CN111378247B (zh) * 2020-03-20 2022-05-10 山东非金属材料研究所 一种湿法缠绕成型复合材料用环氧树脂组合物及其制备方法
CN113150500A (zh) * 2021-04-30 2021-07-23 中国工程物理研究院化工材料研究所 一种缠绕成型的纤维增强环氧类玻璃高分子复合材料

Similar Documents

Publication Publication Date Title
JP7242694B2 (ja) エポキシ配合物のための脂環式アミン：エポキシ系のための新規な硬化剤
CN106189086A (zh) 用于纤维缠绕成型的次中温固化环氧树脂组合物
KR102364545B1 (ko) 에폭시 수지 조성물을 경화시키기 위한 배합물
KR102395468B1 (ko) N-히드록실 에틸 피페리딘 (nhep): 에폭시 시스템을 위한 신규 경화제
CN105199081B (zh) 一种用于环氧树脂的固化剂和超低温用环氧胶黏剂
CN103694637A (zh) 一种风电叶片用高韧性真空慢速环氧树脂及其制备方法
AU2016272843B2 (en) Fast cure epoxy resin compositions
CN105408385A (zh) 具有高断裂韧性的可硬化组合物
JP6641283B2 (ja) 速硬化性で高ガラス転移温度のエポキシ樹脂系
CN107922590B (zh) 用于制造复合材料的稳定高玻璃化转变温度环氧树脂系统
CN105331052B (zh) 一种环氧树脂组合物
US10662281B2 (en) Composite panel material
JP6609304B2 (ja) トリエチルアミンテトラアミン及びスズ触媒を用いるエポキシ系
CN110234675A (zh) 用于纤维-基质半成品的快速固化性环氧树脂组合物
CN107778773A (zh) 环氧树脂组合物、其制备方法及应用

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20161207

RJ01 Rejection of invention patent application after publication