CN112724371A - 硬化剂及其制备方法 - Google Patents
硬化剂及其制备方法 Download PDFInfo
- Publication number
- CN112724371A CN112724371A CN202010092757.3A CN202010092757A CN112724371A CN 112724371 A CN112724371 A CN 112724371A CN 202010092757 A CN202010092757 A CN 202010092757A CN 112724371 A CN112724371 A CN 112724371A
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- CN
- China
- Prior art keywords
- hardener
- glycidyl ether
- substituted
- unsubstituted
- anhydride
- 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
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 45
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- 238000000034 method Methods 0.000 claims abstract description 18
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- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 8
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 7
- -1 trans-1 Chemical compound 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
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- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 5
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
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- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 3
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims description 3
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- JOHUAELJNSBTGS-UHFFFAOYSA-N cyclohexanecarbonyl cyclohexanecarboxylate Chemical compound C1CCCCC1C(=O)OC(=O)C1CCCCC1 JOHUAELJNSBTGS-UHFFFAOYSA-N 0.000 claims description 3
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 claims description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 claims description 2
- XXTSORKWEILSGE-UHFFFAOYSA-N CCCCCC=CCOCC=CCCCCC Chemical compound CCCCCC=CCOCC=CCCCCC XXTSORKWEILSGE-UHFFFAOYSA-N 0.000 claims description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
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- HZIFNFBYOMRJRX-UHFFFAOYSA-N 2-methyl-3-nonyloxirane Chemical compound CCCCCCCCCC1OC1C HZIFNFBYOMRJRX-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开一种硬化剂的制备方法，其包含：酯化步骤：混合多元醇与多元酸酐，以得到酯基乳化剂(A)；扩链步骤：混合酯基乳化剂(A)与双官能性环氧树脂，以得到聚合物中间体(B)；以及混合反应聚合物中间体(B)与多胺化合物，以得到硬化剂(C)。通过本发明的步骤流程以及特定比例，提供了无须额外添加挥发性有机化合物的硬化剂制备方法，并提供具有良好性能的硬化产物。
Description
技术领域
本发明涉及一种硬化剂及其制备方法，特别是涉及一种用于水性环氧树脂涂料的硬化剂及其制备方法。
背景技术
环氧树脂组成物硬化产物具有优异的机械性质、抗蚀性、密接性等，因而广泛应用于涂料、黏结剂、积层板、电子零件等领域；环氧树脂具有抗化学药品性，也对大多数基材有良好的黏附力。然而，一般现有技术的环氧树脂难溶于水，只溶于有机溶剂如醇类、酮类及芳烃类等，且通常必须在使用大量有机溶剂条件下才能获得应用。
随着人们开始重视健康及环境污染问题，挥发性有机溶剂和挥发性有机化合物(VOC)对人体及环境的影响便受到了高度关注。具体而言，挥发性有机化合物(VOC)可根据美国环境保护协会(EPA)方法24列举为挥发性溶剂，或在欧盟指令(European UnionDirective)2004/42/EC中记载为VOC的有机化合物，举例而言，甲醇、乙醇、丙醇、异丙醇、乙酰氧基硅烷、2-甲氧基乙醇等。因此，不含挥发性(NOC)或低挥发性的有机化合物已成为环氧树脂材料的相关研究方向。
美国专利号4,197,389公开了一种硬化剂的制备方法：使至少一种聚环氧化物化合物与至少一种聚亚烷基聚醚多元醇反应以形成随后与多胺反应的加成物。美国专利第5,489,630号揭露一种可与水相容的多胺-环氧树脂加成物，其通过使聚(环氧烷)单胺或二胺与聚环氧化物反应以形成中间物，然后所述中间物随后与过量的多胺反应。美国专利第6,013,757号揭露了由长链二羧酸和氨基烷基哌嗪的反应制备的水性聚酰胺硬化剂。美国专利第6,127,459号公开了借由多胺和环氧树脂反应，从而产生胺端基中间体，并将胺端基中间体与含酸端基聚亚烷基二醇的化合物(I)、(II)、(III)反应，产生胺基端硬化剂。
然而，相关现有技术的制备过程中仍是使用了相当含量的有机溶剂，为克服前述的缺陷，制备水兼容的不含溶剂的硬化剂，并提供具有良好性能的硬化产物，已成为该项事业所欲解决的重要课题之一。
发明内容
本发明所要解决的技术问题在于，针对现有技术的不足提供一种用于水性环氧树脂涂料的硬化剂及其制备方法。
为了解决上述的技术问题，本发明所采用的一技术方案是，提供一种硬化剂的制备方法，其包含：酯化步骤：以1.1：1当量比混合一多元醇与一多元酸酐，进行一酯化反应以得到一酯基乳化剂(A)；扩链步骤：以0.05：1当量比混合所述酯基乳化剂(A)与一双官能性环氧树脂进行扩链，得到一聚合物中间体(B)；以及使所述聚合物中间体(B)与一多胺化合物以0.2：1当量比混合反应，以得到一硬化剂(C)：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基团；R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18脂族、脂环族或芳族基团；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
优选地，所述多元醇具有以下化学式：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基或羟甲基。更进一步来说，聚乙二醇可选自：PEG200、PEG400、PEG 1000、PEG 2000、PEG 3000、PEG 6000以及PEG 8000。
优选地，所述多元酸酐是选自由丁二酸酐、顺丁烯二酐、邻苯二甲酸酐、反-1,2-环己羧酸酐、四氢苯酐、甲基六氢苯酐所组成的群组之至少一者。
优选地，所述双官能性环氧树脂可选自由二羟基酚的二缩水甘油醚、支化或线型脂肪族缩水甘油醚、环氧酚醛树脂或脂环族环氧树脂所组成的群组之至少一者。
优选地，所述多胺化合物是选自由间亚二甲苯基二胺、1,3-二(氨基甲基)环己烷、2-甲基-1,5-戊烷二胺、1,3-戊烷二胺、乙二胺、二亚乙基三胺、三亚乙基四胺、聚环氧丙烷二胺、2,2(4),4-三甲基1,6-己烷二胺、异佛尔酮二胺、2,4-甲苯二胺、1,6-己二胺、1,2-二氨基环己烷以及对二氨基二环己基甲烷(PACM)所组成的群组之至少一者。
优选地，所述酯化步骤是在氮气气氛下进行反应，所述多元酸酐与所述多元醇，反应温度是介于110至130℃，反应时间是3小时。
优选地，使所述聚合物中间体(B)与多胺化合物反应是在70℃的温度下反应4小时。
优选地，本发明的硬化剂的制备方法，还进一步包括：使所述硬化剂(C)与一单官能性环氧化合物进行封端反应，并与去离子水混和得到一硬化剂(D)：
其中，R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18脂族、脂环族或芳族基团；其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环；R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基。
优选地，所述单官能性环氧化合物是选自1,2-己烯化氧、1,2-庚烯化氧、异庚烯化氧、1,2-辛烯化氧、1,2-十二碳烯单氧化物、1,2-十五碳烯化氧、丁二烯单氧化物、异戊间二烯单氧化物、苯乙烯化氧、甲基缩水甘油醚、乙基缩水甘油醚、苯基缩水甘油醚醚、正丁基缩水甘油醚、甲苯基缩水甘油醚、异丙基缩水甘油醚、苯甲基缩水甘油醚、缩水甘油氧基丙基三甲氧基甲硅烷、辛基缩水甘油醚、壬基缩水甘油醚、癸基缩水甘油醚、十二碳烷基缩水甘油醚、C12、C14烷基单缩水甘油醚、对-第三丁基苯基缩水甘油醚以及邻-甲苯基缩水甘油醚所组成的群组之至少一者。
为了解决上述的技术问题，本发明所采用的另外一技术方案是，提供一种硬化剂，其是由前述硬化剂的制备方法所制成。
本发明的其中一有益效果在于，本发明所提供的硬化剂及其制备方法，其能通过本发明的步骤流程、以及特定比例的技术方案，以提供无须额外添加挥发性有机化合物的硬化剂制备方法，制备水兼容的不含溶剂的硬化剂，并提供具有良好性能的硬化产物。
为使能更进一步了解本发明的特征及技术内容，请参阅以下有关本发明的详细说明与附图，然而所提供的附图仅用于提供参考与说明，并非用来对本发明加以限制。
附图说明
图1为本发明硬化剂的制造方法的流程图。
图2为本发明硬化剂的NMR图谱。
图3为本发明硬化剂的FT-IR图谱。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开有关“硬化剂及其制备方法”的实施方式，本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用，本说明书中的各项细节也可基于不同观点与应用，在不悖离本发明的构思下进行各种修改与变更。另外，本发明的附图仅为简单示意说明，并非依实际尺寸的描绘，事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容，但所公开的内容并非用以限制本发明的保护范围。
应当可以理解的是，虽然本文中可能会使用到“第一”、“第二”、“第三”等术语来描述各种组件或者部分，但这些组件或者部分不应受这些术语的限制。这些术语主要是用以区分一组件与另一组件，或者一部分与另一部分。另外，本文中所使用的术语“或”，应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
冠词“一”在本文中用于表示一个或多于一个(即至少一个)该冠词的语法对象。例如，“一环氧基”是指一个环氧基或多于一个环氧基。若说明书指出一组分或要素“可能”、“可以”、“可”被包括或具有某一特征，该特定组分或要素不是必须被包括或具有该特征。
本说明书中所使用的术语“重量份”表示每百份的橡胶(或树脂)中，添加剂所占的含量(parts per hundreds of rubber(or resin)，PHR)。术语“wt％”代表重量百分比。
除非另有说明，术语“聚合物”独立地包括聚合物、低聚物、共聚物、三元共聚物、嵌段共聚物、链段共聚物、预聚物、接枝共聚物，和其任何混合物或结合物。术语“树脂”独立地包括聚合物、低聚物、共聚物、三元共聚物、嵌段共聚物、链段共聚物、预聚物、接枝共聚物，和其任何混合物或结合物。
应了解，术语“独立地选自”意指可选择相同或不同值用于单一化合物中给定变量之多种情况。术语“经取代或未经取代”意指指定部分之氢基团经指定取代基之基团代替，前提是取代产生稳定或化学上可行之化合物。本发明所设想之取代基之组合较佳是彼等使得形成稳定或化学上可行之化合物者。
参阅图1所示，本发明提供一种硬化剂的制备方法，其包含：步骤S100(酯化步骤)，多元酸酐与多元醇进行酯化反应，得到酯基乳化剂；步骤S200(扩链步骤)，酯基乳化剂与双官能性环氧化合物反应，得到聚合物中间体；步骤S300，聚合物中间体与多胺化合物反应，得到硬化剂，以及步骤S400(封端步骤)，硬化剂与单官能性环氧化合物反应。
具体来说，步骤S100是在氮气气氛下，以1.1：1当量比混合一多元醇与一多元酸酐，并在介于110至130℃的温度下反应3小时，使多元醇与多元酸酐发生酯化反应，以得到一酯基乳化剂(A)，其具有化学式：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
进一步来说，本发明所使用的多元醇具有以下化学式：
更详细而言，其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基，较佳地，多元醇聚合物较佳是分子量介于200至8000。高分子量的聚乙二醇PEG可选自：PEG200、PEG400、PEG 1000、PEG 2000、PEG 3000、PEG 6000以及PEG 8000。
进一步来说，多元酸酐具有以下化学式：
其中，R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
举例来说，多元酸酐是选自由丁二酸酐(succinic anhydride，SA)、顺丁烯二酐(maleic anhydride，MA)、邻苯二甲酸酐(phthalic anhydride，PA)、反-1,2-环己羧酸酐(cyclohexanedicarboxylic anhydride，CDA)、四氢苯酐(tetrahydrophthalicanhydride，TPA)、甲基六氢苯酐(methylhexahydrophthalic anhydride，MHHPA)以及所组成的群组之至少一者。
S200扩链步骤：以0.05：1当量比混合所述酯基乳化剂(A)与一双官能性环氧树脂进行扩链反应，扩链步骤的反应条件是先于110至130℃的温度反应1小时，再于130至150℃的温度反应2小时，得到一聚合物中间体(B)，其具有化学式：
其中，R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基；m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
双官能性环氧树脂，意指该树脂的一分子内具有两个或多个环氧基团，例如经由烯烃的氧化反应、羟基基团的缩水甘油基醚化反应、一级或二级胺的缩水甘油基胺化反应、或羧酸的缩水甘油基酯化反应形成的环氧基团。本发明的双官能性环氧树脂具有以下化学式：
其中，n为自然数，n＝1-10，R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基。
举例来说，双官能性环氧树脂可选自双酚型的二缩水甘油醚、支化或线型脂肪族缩水甘油醚、环氧酚醛树脂或脂环族环氧树脂所组成的群组之至少一者。
更进一步来说，二羟酚的二缩水甘油醚例如能够通过将表卤代醇与二羟酚在碱存在下反应来生产。举例来说，二羟酚可以是选自2，2-双(4-羟基苯基)丙烷(双酚-A)、2,2-双(4-羟基-3-叔丁基苯基)丙烷、1,1-双(4-羟基苯基)乙烷、1,1-双(4-羟基苯基)异丁烷、双(2-羟基-1-萘基)甲烷、1,5-二羟基萘以及1,1-双(4-羟基-3-烷基苯基)乙烷所组成的群组之至少一者。
脂族缩水甘油醚可选自1,4-丁二醇、新戊二醇、环己烷二甲醇、己二醇、聚丙二醇、和类似二醇的二缩水甘油醚，三羟甲基乙烷和三羟甲基丙烷的三缩水甘油醚。脂环族环氧树脂的实例如：3,4-环氧基环己基甲基-(3,4-环氧)环己烷羧酸酯、二脂环族二醚二环氧[2-(3,4-环氧)环己基-5,5-螺(3,4-环氧)-环己烷-m-二恶烷]、双(3,4-环氧-环己基甲基)己二酸酯、双(3,4-环氧-环己基)己二酸酯以及乙烯基环己烯二氧化物[4-(1,2-环氧乙基)-1,2-环氧环己烷]。
S300使聚合物中间体(B)与多胺化合物以0.2：1当量比混合，在70℃的温度下反应4小时，以得到一硬化剂(C)，具有化学式：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基；R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18脂族、脂环族或芳族基团；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
更进一步来说，多胺化合物是选自由间亚二甲苯基二胺、1,3-二(氨基甲基)环己烷、2-甲基-1,5-戊烷二胺、1,3-戊烷二胺、乙二胺、二亚乙基三胺、三亚乙基四胺、聚环氧丙烷二胺、2,2(4),4-三甲基1,6-己烷二胺、异佛尔酮二胺、2,4-甲苯二胺、1,6-己二胺、1,2-二氨基环己烷以及对二氨基二环己基甲烷(PACM)所组成的群组之至少一者。
除此之外，视需求进一步进行S400封端步骤，将硬化剂(C)与单官能性环氧化合物在70℃的温度下反应2小时，再降温至60℃，于200rpm的速度下与去离子水搅拌混和1小时，得到一硬化剂(D)：
其中，RX如前所示化学示(R0及R5如前所述)，R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18的脂族、脂环族或芳族基团；R3是选自2-100个碳原子的支化或线性烷基、脂环族、聚氧烷基或链烯基基团所组成的群组之至少一者。
更详细来说，单官能性环氧化合物作为封端剂，可以是连接到环氧官能团上的脂族、脂环族或芳族化合物。让一级胺的氢反应减少了由大气温度与一级胺的氢反应形成氨基甲酸酯的机会。除了通过反应消耗在取代的芳基酰胺基多胺上的部分或全部一级胺基团可缓解发白现象以外，使酰胺基多胺与环氧官能团反应有着留下一个对环氧基团有反应活性的自由胺属氢的优点。尽管如此，让酰胺基多胺化合物上的一级胺与环氧官能团反应还留下了对环氧树脂更具反应活性的二级胺属氢。因此，获得了双重优点，即在室温下无外来催化剂的情况下保持足够的反应活性来固化体系的同时缓解了发白现象。与单官能性环氧化合物反应也形成了羟基，它也可用来与环氧组分反应。
单官能性环氧化合物是选自1,2-己烯化氧、1,2-庚烯化氧、异庚烯化氧、1,2-辛烯化氧、1,2-十二碳烯单氧化物、1,2-十五碳烯化氧、丁二烯单氧化物、异戊间二烯单氧化物、苯乙烯化氧、甲基缩水甘油醚、乙基缩水甘油醚、苯基缩水甘油醚醚、正丁基缩水甘油醚、甲苯基缩水甘油醚、异丙基缩水甘油醚、苯甲基缩水甘油醚、缩水甘油氧基丙基三甲氧基甲硅烷、辛基缩水甘油醚、壬基缩水甘油醚、癸基缩水甘油醚、十二碳烷基缩水甘油醚、C12、C14烷基单缩水甘油醚、对-第三丁基苯基缩水甘油醚以及邻-甲苯基缩水甘油醚所组成的群组之至少一者。
第一实施例
在氮气气氛下，混合100克聚乙二醇PEG6000与5.3克甲基六氢苯酐(MHHPA)，在120℃的温度下反应3小时，使其产生酯化反应，以得到105.3克的酯基乳化剂(A)。
混合105克酯基乳化剂(A)与258克南亚塑料生产环氧树脂NPEL-136以进行扩链反应，于120℃的温度反应1小时，再于140℃的温度反应2小时，得到一聚合物中间体(B)。
混合175克聚合物中间体(B)与过量二乙烯三胺(DETA)，在70℃的温度下反应4小时，去除多余的DETA，得到硬化剂(C)。
再加入55.6克的正丁基缩水甘油醚(BGE)进行封端反应，于70℃的温度下反应2小时候降温至60℃，并加入去离子水280克于200rpm恒速下搅拌1小时，得到硬化剂(D)。
前述反应的到的硬化剂(D)进一步以NMR以及FT-IR和光谱进行结构鉴定，如图2及图3所示。
实施例的有益效果
本发明的其中一有益效果在于，本发明所提供的硬化剂及其制备方法，其能通过本发明的步骤流程、以及特定比例的技术方案，以提供无须额外添加挥发性有机化合物的硬化剂制备方法，制备水兼容的不含溶剂的硬化剂，并提供具有良好性能的硬化产物。本发明所提供的硬化剂借由双官能性环氧树脂的结构使得其与环氧树脂具有较的兼容性。本发明的固化剂可以有效地固化水性环氧树脂，可以在室温环境下或在升温下被固化。水性环氧树脂举例而言可以是分子量为350-10,000的水性环氧树脂。
以上所公开的内容仅为本发明的优选可行实施例，并非因此局限本发明的权利要求书的保护范围，所以凡是运用本发明说明书及附图内容所做的等效技术变化，均包含于本发明的权利要求书的保护范围内。
Claims (11)
1.一种硬化剂的制备方法，其特征在于，所述硬化剂的制备方法包括：
酯化步骤：以1.1：1当量比混合一多元醇与一多元酸酐，进行一酯化反应以得到一酯基乳化剂(A)；
扩链步骤：以0.05：1当量比混合所述酯基乳化剂(A)与一双官能性环氧树脂进行扩链，得到一聚合物中间体(B)；以及
使所述聚合物中间体(B)与一多胺化合物以0.2：1当量比混合反应，以得到一硬化剂(C)：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基；R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18脂族、脂环族或芳族基团；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环。
2.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述多元醇具有以下化学式：
其中，m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基或羟甲基。
3.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述多元酸酐是选自由丁二酸酐、顺丁烯二酐、邻苯二甲酸酐、反-1,2-环己羧酸酐、四氢苯酐、甲基六氢苯酐以及所组成的群组之至少一者。
4.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述双官能性环氧树脂可选自由二羟基酚的二缩水甘油醚、支化或线型脂肪族缩水甘油醚、环氧酚醛树脂以及脂环族环氧树脂所组成的群组之至少一者。
5.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述多胺化合物是选自由间亚二甲苯基二胺、1,3-二(氨基甲基)环己烷、2-甲基-1,5-戊烷二胺、1,3-戊烷二胺、乙二胺、二亚乙基三胺、三亚乙基四胺、聚环氧丙烷二胺、2,2(4),4-三甲基1,6-己烷二胺、异佛尔酮二胺、2,4-甲苯二胺、1,6-己二胺、1,2-二氨基环己烷以及对二氨基二环己基甲烷所组成的群组之至少一者。
6.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述酯化步骤是在氮气气氛下进行反应，所述酯化步骤的反应温度是介于110至130℃，且反应时间是3小时。
7.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述扩链步骤包括：所述酯基乳化剂(A)与所述双官能性环氧树脂先于110至130℃的温度下反应1小时，再于130至150℃的温度下反应2小时。
8.根据权利要求1所述的硬化剂的制备方法，其特征在于，所述聚合物中间体(B)与所述多胺化合物反应是在70℃的温度下反应4小时。
9.根据权利要求4所述的硬化剂的制备方法，其特征在于，所述的硬化剂的制备方法还进一步包括：使所述硬化剂(C)与一单官能性环氧化合物进行封端反应，所得到的产物再与去离子水混合，以得到一封端硬化剂(D)：
其中，R1是经非反应活性氧、至多平均4个二级或三级氮原子取代或非经取代的C2至C18脂族、脂环族或芳族基团；m＝1-100、n＝1-15，X以及Y各自独立地选自H、甲基、乙基、羟甲基；R2和R3各自独立地选自H、经取代或未经取代的烷基、经取代或未经取代的芳基，或R2与R3彼此键结以形成经取代或未经取代的环；R0是经氧原子、氮原子、硫原子取代或未经取代C6至C30的烃基且具有至少一个芳香环，或C6至C17的脂族烃基。
10.根据权利要求9所述的硬化剂的制备方法，其特征在于，所述单官能性环氧化合物是选自1,2-己烯化氧、1,2-庚烯化氧、异庚烯化氧、1,2-辛烯化氧、1,2-十二碳烯单氧化物、1,2-十五碳烯化氧、丁二烯单氧化物、异戊间二烯单氧化物、苯乙烯化氧、甲基缩水甘油醚、乙基缩水甘油醚、苯基缩水甘油醚醚、正丁基缩水甘油醚、甲苯基缩水甘油醚、异丙基缩水甘油醚、苯甲基缩水甘油醚、缩水甘油氧基丙基三甲氧基甲硅烷、辛基缩水甘油醚、壬基缩水甘油醚、癸基缩水甘油醚、十二碳烷基缩水甘油醚、C12、C14烷基单缩水甘油醚、对-第三丁基苯基缩水甘油醚以及邻-甲苯基缩水甘油醚所组成的群组之至少一者。
11.一种硬化剂，其特征在于，所述的硬化剂是根据权利要求1所述的硬化剂的制备方法所制成。
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| CN105367755A (zh) * | 2015-12-01 | 2016-03-02 | 江苏丰彩新型建材有限公司 | 一种环氧固化剂、防腐清漆及其制备方法 |
| CN106317381A (zh) * | 2016-08-29 | 2017-01-11 | 佛山市高明同德化工有限公司 | 一种水性环氧固化剂及其制备方法 |
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| US20210122876A1 (en) | 2021-04-29 |
| US11702503B2 (en) | 2023-07-18 |
| TWI705082B (zh) | 2020-09-21 |
| TW202116853A (zh) | 2021-05-01 |
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