CN105601887A - 一种脂环胺固化剂及其制备方法 - Google Patents

一种脂环胺固化剂及其制备方法 Download PDF

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CN105601887A
CN105601887A CN201511030382.3A CN201511030382A CN105601887A CN 105601887 A CN105601887 A CN 105601887A CN 201511030382 A CN201511030382 A CN 201511030382A CN 105601887 A CN105601887 A CN 105601887A
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curing agent
amine
anacardol
aliphatic cyclic
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宋学良
毕丽杰
张利春
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SHANGHAI MEIDONG BIOMATERIALS CO Ltd
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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
    • 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
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/42—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups or hydroxy groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
    • C07C37/003—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by hydrogenation of an unsaturated part
    • 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
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供了一种脂环胺固化剂，其结构式如下：

Description

一种脂环胺固化剂及其制备方法
技术领域
本发明属于化工领域，涉及一种高分子材料，具体涉及一种环氧树脂固化剂，特别是一种腰果酚脂环胺固化剂及其制备方法。
背景技术
胺类固化剂与空气中的CO2反应生成不能与环氧基起反应的碳酸铵盐而引起气泡的发生。脂肪胺对皮肤有一定刺激作用，其蒸汽毒性很强。现有腰果酚固化剂色深，固化速度较慢。
发明内容
本发明的目的在于提供一种脂环胺固化剂及其制备方法，所述的这种脂环胺固化剂及其制备方法要解决现有技术中的胺类固化剂使用过程中容易产生气泡，而且固化时间长的技术问题。
本发明提供了一种腰果酚脂环胺固化剂，其结构式如下：
n＝1～100。
(I)
本发明还提供了上述腰果酚脂环胺固化剂的制备方法，包括如下步骤：
1)一个制备十五烷基酚的步骤，以腰果酚为原料，通入氢气，加入催化剂，在3～5MPa的压力下60～90℃进行反应，获得十五烷基酚；
2)在十五烷基酚中加入聚甲醛或者甲醛、脂肪胺或者芳香胺，所述的脂肪胺为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、或多乙烯多胺；；所述的十五烷基酚、聚甲醛或者甲醛、脂肪胺的摩尔比为1:1～2:1～2；在60～80条件下进行反应，1～4小时后，获得中间体酚醛胺；
3)将步骤2)获得的中间体酚醛胺减压脱水后，再加入催化剂，在3～5MPa的压力下90～110℃进行反应，1～3小时后获得通式(I)所示的脂环族的腰果酚改性固化剂。
进一步的，所述的催化剂为雷尼镍。
本发明以腰果酚为原料，通过雷尼镍氢化腰果酚，首先得到十五烷基酚，再用甲醛及乙二胺(或二乙烯三胺，三乙烯四胺，四乙烯五胺，多乙烯多胺，等脂肪胺)连接胺类，合成中间体酚醛胺，再将中间体酚酚醛胺能过雷尼镍氢化苯环得到一种固体的，浅色，可快速固化的，高附加值的在高温下使用的脂环族的腰果酚改性固化剂。
本发明的反应过程如下所示：
本发明通过改性脂肪胺再氢化得到脂环胺。由于脂环胺分子量大，不易挥发，在室温很快固化环氧树脂，固化反应为放热反应，热量能进一步促使环氧树脂与固化剂反应，其使用期较短。
本发明和已有技术相比，其技术效果是积极和明显的。本发明首先能过雷尼镍氢化腰果酚，以保证在氢化腰果酚合成中间体过程中颜色较浅，不变深；再将中间体氢化得到脂环胺，以保证该脂环胺具有较浅的颜色，且该脂环胺具有的性质为固体，浅色，可快速固化，附加值高。
具体实施方式
实施例1
按照重量称取腰果酚300克，加入4克雷尼镍，在3.6MPa下通往氢气进行氢化，80℃保温5小时，得到氢化腰果酚，再将该氢化腰果酚中加入乙二胺60克，甲醛32.5克，70℃反应3小时，减压脱水后，再加入4克雷尼镍，在3.6MPa下通入氢气进行氢化，100℃下2小时过滤得到目标产物。产物特征：浅黄色固体，胺值360mgKOH/g，固含95％，表干1.5h，实干3h。常温储存3年不变色。
实施例2
按照重量称取腰果酚300克，加入4克雷尼镍，在3.6MPa下通往氢气进行氢化，80℃保温5小时，得到氢化腰果酚，再将该氢化腰果酚中加入二乙烯三胺101克，聚甲醛32.5克，70℃反应3小时，减压脱水后，再加入4克雷尼镍，在3.6MPA下通入氢气进行氢化，100℃下反应2小时过滤得到目标产物。产物特征：浅黄色固体，胺值390mgKOH/g，固含95％，表干1.5h，实干2h。常温储存3年不变色。
实施例3
按照重量称取腰果酚300克，加入4克雷尼镍，在3.6MPa下通往氢气进行氢化，80℃保温5小时，得到氢化腰果酚，再将该氢化腰果酚中加入多乙烯多胺160克，聚甲醛32.5克，70℃反应3小时，减压脱水后，再加入4克雷尼镍，在3.6MPA下通入氢气进行氢化，100℃下反应2小时过滤得到目标产物。产物特征：浅黄色固体，胺值360，固含95％，表干1.5h，实干3h。产物特征：浅色固体，胺值460mgKOH/g，固含95％，表干1h，实干2h。常温储存3年不变色。
实施例4
按照重量称取腰果酚300克，加入4克雷尼镍，在3.6MPa下通往氢气进行氢化，80℃保温5小时，得到氢化腰果酚，再将该氢化腰果酚中四乙烯五胺189.31克，聚甲醛32.5克，70℃反应3小时，减压脱水后，再加入4克雷尼镍，在3.6MPa下通入氢气进行氢化，100℃下反应2小时过滤得到目标产物。产物特征：白色固体，胺值300mgKOH/g，固含95％，表干1h，实干2h。常温储存3年不变色。

Claims (3)

1.一种脂环胺固化剂，其特征在于，其结构式如下：
n＝1～100。
2.权利要求1所述的一种脂环胺固化剂的制备方法，其特征在于包括如下步骤：
1)一个制备十五烷基酚的步骤，以腰果酚为原料，通入氢气，加入催化剂，在3～5MPa的压力下60～90℃进行反应，获得十五烷基酚；
2)在十五烷基酚中加入聚甲醛或者甲醛、脂肪胺，所述的脂肪胺为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、或多乙烯多胺；；所述的十五烷基酚、聚甲醛或者甲醛、脂肪胺的摩尔比为1:1～2:1～2；在60～80条件下进行反应，1～4小时后，获得中间体酚醛胺；
3)将步骤2)获得的中间体酚醛胺减压脱水后，再加入催化剂，在3～5MPa的压力下90～110℃进行反应，1～3小时后获得通式(I)所示的脂环族的腰果酚改性固化剂。
3.根据权利要求2所述的一种脂环胺固化剂的制备方法，其特征在于：所述的催化剂为雷尼镍。
CN201511030382.3A 2015-12-31 2015-12-31 一种脂环胺固化剂及其制备方法 Pending CN105601887A (zh)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN112236411A (zh) * 2018-04-10 2021-01-15 赢创运营有限公司 生产酚醛胺的方法
CN112920061A (zh) * 2021-01-25 2021-06-08 上海经天新材料科技有限公司 一种氨基腰果酚固化剂的制备方法
CN113277952A (zh) * 2021-04-23 2021-08-20 岳阳昌德新材料有限公司 一种双(c12-14烷基聚氧乙烯基)仲胺的制备方法
CN114436867A (zh) * 2022-02-18 2022-05-06 浙江万盛股份有限公司 一种二氨基环己醇衍生物及其制备方法和应用
CN114621058A (zh) * 2022-04-07 2022-06-14 涉县津东经贸有限责任公司 一种饱和腰果酚催化加氢制备方法
CN114989028A (zh) * 2021-07-06 2022-09-02 深圳飞扬兴业科技有限公司 一种腰果酚改性天冬树脂及其制备方法、聚脲涂料

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CN103059269A (zh) * 2013-01-16 2013-04-24 华东理工大学 一种复配改性的脂肪胺固化剂
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JPS51119099A (en) * 1975-03-17 1976-10-19 Minnesota Mining & Mfg Setting agent composed of polyaminophenol and epoxy resin and method for setting epoxy resin
CN101333286A (zh) * 2007-06-26 2008-12-31 上海经天新材料科技有限公司 腰果酚改性胺环氧固化剂
CN102898884A (zh) * 2012-09-26 2013-01-30 江苏三木集团有限公司 环保型低voc防腐涂料用腰果胺环氧固化剂及其制备方法
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112236411A (zh) * 2018-04-10 2021-01-15 赢创运营有限公司 生产酚醛胺的方法
CN112920061A (zh) * 2021-01-25 2021-06-08 上海经天新材料科技有限公司 一种氨基腰果酚固化剂的制备方法
CN113277952A (zh) * 2021-04-23 2021-08-20 岳阳昌德新材料有限公司 一种双(c12-14烷基聚氧乙烯基)仲胺的制备方法
CN114989028A (zh) * 2021-07-06 2022-09-02 深圳飞扬兴业科技有限公司 一种腰果酚改性天冬树脂及其制备方法、聚脲涂料
CN114989028B (zh) * 2021-07-06 2024-06-04 深圳飞扬骏研新材料股份有限公司 一种腰果酚改性天冬树脂及其制备方法、聚脲涂料
CN114436867A (zh) * 2022-02-18 2022-05-06 浙江万盛股份有限公司 一种二氨基环己醇衍生物及其制备方法和应用
CN114436867B (zh) * 2022-02-18 2024-09-17 浙江万盛股份有限公司 一种二氨基环己醇衍生物及其制备方法和应用
CN114621058A (zh) * 2022-04-07 2022-06-14 涉县津东经贸有限责任公司 一种饱和腰果酚催化加氢制备方法
CN114621058B (zh) * 2022-04-07 2022-11-22 涉县津东经贸有限责任公司 一种饱和腰果酚催化加氢制备方法

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