CN101675084B - 高官能度胺化合物及其应用 - Google Patents
高官能度胺化合物及其应用 Download PDFInfo
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- CN101675084B CN101675084B CN2008800084048A CN200880008404A CN101675084B CN 101675084 B CN101675084 B CN 101675084B CN 2008800084048 A CN2008800084048 A CN 2008800084048A CN 200880008404 A CN200880008404 A CN 200880008404A CN 101675084 B CN101675084 B CN 101675084B
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- polyvalent alcohol
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- -1 amine compounds Chemical class 0.000 title claims description 69
- 150000001412 amines Chemical class 0.000 claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920005862 polyol Polymers 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims 1
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 7
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- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
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- 239000009261 D 400 Substances 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 1
- QUOBVYPFBJUOAJ-UHFFFAOYSA-N 1-isocyanato-2,4-dimethylbenzene Chemical compound CC1=CC=C(N=C=O)C(C)=C1 QUOBVYPFBJUOAJ-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- FIJSKXFJFGTBRV-UHFFFAOYSA-N 2-[[2-[[2-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1CC1=CC=CC=C1OCC1CO1 FIJSKXFJFGTBRV-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- HBKJFLIDOJLQOG-UHFFFAOYSA-N 4-(cyclohexylmethyl)-1,1-dimethylcyclohexane Chemical compound CC1(C)CCC(CC2CCCCC2)CC1 HBKJFLIDOJLQOG-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- PQAHUUKIZZSYTK-UHFFFAOYSA-N 5-isocyanato-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1(CC(=CC=C1)C)N=C=O PQAHUUKIZZSYTK-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
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- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000000806 elastomer Substances 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
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Abstract
在另一个例示性的具体实施方案中，胺官能固化剂的胺氢官能度(AHF)至少为7，胺-氢当量(AHEW)至少为约50。
Description
技术领域
本发明公开主要与作为固化剂的胺化合物有关。
背景技术
与生产环氧树脂有关的通常使用的制造工艺包括，纤维缠绕成型、拉挤成型、注塑成型、树脂传递模塑(RTM)、真空辅助RTM(VARTM)和湿法层叠成型或真空袋技术。
聚氧化亚烷基胺(有时称作为聚醚胺)，是环氧体系中有效的固化剂，用来提高柔韧性及延长在纤维增强型复合材料制造过程中的工作时间。这里的“工作时间”是指从环氧树脂的活性成分初次相互混合到混合物不再适合加工所需的时间。工作时间内，树脂或含树脂的物质都处于可浇注、柔性、柔韧或其他适合模压的状态。
诸如基于二醇和三元醇的那些的，以及包括例如
品牌的胺类商业产品的低官能度的聚醚胺已被用作环氧固化剂。当用于聚合标准的液态环氧树脂(比如主要含有双酚A的二缩水甘油醚的环氧树脂)时，增加这些低官能度胺的分子量会产生较低玻璃化转变温度(Tg)。增加低官能度聚醚胺的分子量也会导致凝胶期过长，相关问题还有例如在固化过程中如果表面暴露在空气中，胺会与二氧化碳和水发生反应。由于暴露而产生的油性表面现象通常被称为“胺致发白(amine blushing)”。
另一方面，由于反应基浓度较高，高官能度低分子量的胺会缩短凝胶期并具有较高的放热温度。通常，较高的放热温度会限制能成型部件的横断面厚度，因为较厚部分中会发生热降解。这种热降解可能表现为炭化或者会产生不良力学特性。
发明概述
胺组分在一具体的实施方案中如下所示：
其中，平均来说，0.0≤w+x+y+z≤25，每个R可独立选自包含氢、甲基、乙基、丙基和丁基的组。
在另一个例示性具体实施方案中，胺官能固化剂的胺氢官能度(AHF)至少为7，胺氢当量(AHEW)至少为约50。
在另一个例示性具体实施方案中，胺官能固化剂的胺氢官能度(AHF)至少为5，胺氢当量(AHEW)至少约115，且不高于约400。
在另一个例示性具体实施方案中，胺官能固化剂的胺氢官能度(AHF)至少为5，分子量(MW)介于约700到约2900之间。
在另一个例示性具体实施方案中，胺官能固化剂的胺氢官能度(AHF)至少为5，平均分子量(AMW)满足如下不等式：AMW≥2000-222·AHF且AMW≤500·AHF。
在另一个例示性具体实施方案中，胺官能固化剂的胺氢官能度至少为7，分子量(MW)介于约700与约5600之间。
在另一个例示性具体实施方案中，制备固化环氧树脂的方法包括提供根据任一上述胺官能固化剂或胺组分的胺组分，提供多官能环氧树脂，并将多官能环氧树脂与多胺化合物彼此接触。
在另一个例示性具体实施方案中，制备聚脲的方法包括提供有机多异氰酸酯，提供根据上述任一胺组分或胺官能固化剂的胺组分，并让该有机多异氰酸酯与多胺组分接触。
发明详述
在一个例示性具体实施方案中，公布的内容涉及基于具有至少4个羟基的多元醇或多羟基化合物的胺化合物，所述胺化合物可用作制备聚脲的环氧固化剂或共同反应物。在特定实施方案中，胺化合物基于烷氧基化的季戊四醇或烷氧基化的双季戊四醇。以四官能多元醇为例，比如季戊四醇与乙烯、丙烯、丁烯氧化物的反应产物可被还原氨化以提供官能度至少为8的环氧固化剂。除了固化产物中的理想机械特性外，胺化合物还提供理想的反应性和加工特性。
在一个例示性具体实施方案中，胺化合物具有较高的胺氢官能度(AHF)。胺氢官能度(AHF)的定义是在胺化合物中连接到每个伯和仲胺氮原子上的氢原子的总数。具体地，胺化合物的每个伯胺为胺氢官能度(AHF)贡献了2，每个仲胺贡献了1，每个叔胺贡献了0。因此，如果一个胺化合物包含四个伯胺基，则胺氢官能度(AHF)数量为8。再例如，含三个伯胺基的胺化合物的胺氢官能度(AHF)达到6。还例如，含三个伯和一个仲胺基的胺化合物的胺氢官能度(AHF)为7，胺化合物的胺氢官能度(AHF)可以通过将一个或多个伯胺基向仲胺基转化而改变。
在一个特定的具体实施方案中，胺化合物的胺氢官能度(AHF)至少为5。更特别的，胺化合物的胺氢官能度(AHF)可以最少为6，例如至少7，或者甚至至少8。在一个例示性的具体实施方案中，胺氢官能度(AHF)不超过14，例如不超过13。
用胺氢当量(AHEW)可以进一步表征胺化合物。胺氢当量(AHEW)是指胺化合物的平均分子量除以胺氢官能度(AHF)。在一个例示性的具体实施方案中，胺氢当量(AHEW)可以至少达到约50、例如至少约70、至少约115，甚或至少约120。在进一步实例中，胺氢当量(AHEW)可以不超过约400。例如胺氢当量(AHEW)可以不超过约350、例如不超过约300、不超过约200，甚或不超过约150。特别是，胺化合物的胺氢当(AHEW)可以介于约50到约400、例如约115到约400，或者甚至约115到约150之间。特别是，胺化合物的官能度大于等于5，且AHEW至少为50。
进一步来说，胺化合物的平均分子量可以至少达到约600，例如至少约670、至少约700，或者甚至至少约800。胺化合物的平均分子量可以不超过5600。举例来说，平均分子量可以不超过约4800，例如可以不超过约2900、不超过约2000，或者甚至不超过约1500。特别是，平均分子量可介于约600到约5600、例如约700到约4800，或者甚至约800到约1500之间。
特别的，所需的平均分子量至少可以部分地与胺氢官能度(AHF)相关，以实现不同应用目的。在特定的具体实施方案中，理想的胺化合物的平均分子量(AMW)是胺氢官能度(AHF)的一个函数。举例来说，胺化合物的AMW的下限可以由下列等式限定：AMW≥2000-222·AHF且AMW≥0。另一个实例中，胺化合物的AMW的上限可由下列等式限定：AMW＜400·AHF。
要改变由多官能原料形成的胺的AHEW，可以通过控制氧化物(如环氧乙烷、环氧丙烷、或环氧丁烷)的添加来调节起始多元醇的分子量。通过环氧丁烷的反应来终止多元醇链会导致最后产物中具有更大的胺的位阻。同样的，从此类原料制备得到的胺的反应性大大低于用环氧丙烷终止多元醇原料末端所得到的胺的反应性。如用环氧乙烷来终止末端，会导致甚至更小的位阻，并且因此导致最终的胺的反应性更高。此外，由环氧乙烷封端的多元醇形成的胺的更大反应性，会导致在胺化过程中此类胺部分冷凝，如此也导致官能度比通常由原料实现的情况更高。在一个实施例中，用环氧乙烷部分封端起始的多元醇，可用作增加固化剂的平均分子官能度的措施，同时也会在选定数量的耦合反应完成时生成较低反应性的固化剂。
在一个特定的实施例中，由烷氧基化的多元醇化合物生成胺化合物，其中多元醇化合物至少含有约4个羟基。可以用作原料以生成胺化合物的多元醇的例子包括：赤藓醇、季戊四醇、双季戊四醇以及它们的烷氧基化物，它们单独或相互混合使用。或者，也可以使用高官能度的多元醇，比如：曼尼希多元醇、胺多元醇、蔗糖/乙二醇多元醇、蔗糖/甘油多元醇、蔗糖/胺多元醇、山梨糖多元醇或上述各种原料的任意组合。
多元醇可被烷氧基化以增加分子量，这样就可以控制最终的胺的胺氢当量(AHEW)。例如，多元醇或其烷氧基化物可以用环氧乙烷、环氧丙烷、环氧丁烷、或它们的任意组合来烷氧基化。尤其是，使用不同反应物种(species)进行的烷氧基化反应会在最终的胺化合物中提供所需特性。例如，先用环氧乙烷或环氧丙烷进行烷氧基化反应，然后用环氧丁烷进行烷氧基化反应，这可能产生会影响从这些多元醇制备的胺化合物反应性的位阻。在另一个实例中，连续地用环氧丙烷进行烷氧基化反应并然后用环氧乙烷进行烷氧基化反应，这可能增加最终的胺化合物的反应性。烷氧基化的条件可以包括，使醇引发剂与氧化物及催化剂接触，接触温度介于90-160℃，压力范围为40-100psi，并接触持续足够时间让氧化物发生反应。
烷氧基化的多元醇中的醇基团可能通过还原胺化反应被转化成胺。例如，多元醇可以在氢和过量氨存在的情况下被还原胺化。特别的工艺条件包括，使多元醇接触过量氨和氢以及合适的胺化催化剂，压力范围在1200至2500psi，温度范围180-240℃，并接触持续适宜的时间以获得胺的高转化率。
在一个特定的具体实施方案中，胺化合物基于烷氧基化的季戊四醇且具有以下通式(I)：
其中，平均来说，0.0≤w+x+y+z≤25.0，每个R可独立选自包含氢、甲基、乙基、丙基和丁基的组。
例如，w，x，y，z的总和可介于4.0到13.0，例如4.0到10.0之间。在一个特定的实施例中，w，x，y，z的总和可介于4.0到5.0之间。在另一个实例中，w，x，y，z的总和可介于8.0到9.0。
在一个特定的具体实施方案中，与胺基邻近的R基的选择会影响胺的反应性。比如，乙基、丙基或丁基会产生位阻从而导致降低的反应性。相反，用氢代替R会提高反应性。
通式(I)的胺化合物可以有至少一个伯胺，例如至少两个、至少三个或甚至四个伯胺。或者，也可以将一个或多个胺转化成仲胺。
通式(I)的胺化合物的平均分子量至少为约600，例如至少为约800。进一步而言，胺化合物的胺氢当量(AHEW)至少为50、例如至少约70，或者甚至至少约115。
除了使用上述多胺外，上述的胺可以相互组合、与现有技术的胺或者它们的任意组合相组合，以形成胺组分。用于组合的胺包括，例如：N-氨乙基哌嗪(AEP)；二亚乙基三胺(DETA)；三亚乙基四胺(TETA)；四亚乙基五胺(TEPA)；2-甲基五亚甲基二胺(
A-DuPont)；1，3-戊烷二胺(从Invista North America S.A.R.L公司以
品牌获得，DYTEK是Invista North America S.A.R.L公司的注册商标)；三甲基六亚甲基二胺(2，2，4-和2，4，4-异构体的1∶1混合物，以
品牌获得，VESTAMIN是EvonikIndustries AG的注册商标)；聚酰胺固化剂；聚酰胺基胺固化剂；曼尼希碱型固化剂；二(氨甲基)环己胺(1，3-BAC)；异佛尔酮二胺(IPDA)；薄荷烷二胺；二(对-氨基环己胺)甲烷(PACM)；2，2′-二甲基二(对-氨基环己胺)甲烷(DMDC)；二甲基二环己基甲烷)；1，2-二氨基环己烷；1，4-二氨基环己烷；间-二甲苯二胺(m-XDA)；降莰烷二胺(NBDA)；间-苯二胺(m-PDA)；二氨基二苯砜(DDS或DADS)；亚甲基二苯胺(MDA)；
D-230胺(Hunt sman)；D-400胺(Hunt sman)；T-403胺(Hunt sman)；二乙基甲苯二胺(DETDA)，或其任何组合。
此处提供的胺、胺的组合及工艺特别有益于提供具有理想的固化时间及工艺特性(如低粘度)的环氧体系。
胺化合物可以与环氧树脂反应形成固化的环氧树脂。合适的多官能环氧树脂包括至少有两个环氧端基的那些及包括以下物质：
其中n可以介于0至约4之间；DGEBF(双酚F的二缩水甘油醚)，其具有下列结构：
例如Huntsman的
GY 285epoxy；和三官能及更高官能的环氧树脂，例如Huntsman的
742epoxy：
环氧官能的线性酚醛树脂，如D.E.N.
438环氧树脂、
EPN1180环氧树脂、D.E.N.431环氧树脂，也适用于该工艺中。D.E.N.是Dow Chemical公司的注册商标，ARALDITE是Huntsman公司的注册商标。所有分子结构中含有2个以上环氧基的材料均适用，包括但不局限于上述材料，将这类材料便利地统称为“多官能环氧树脂”。
在另一个具体实施方案中，胺可与有机多异氰酸酯反应以生成聚脲。这些多异氰酸酯包括标准的异氰酸酯组成，如MDI基的半预聚物，如Huntsman公司提供的
9480、
9484及
9495的那些。液化的MDI，如
可用作为全部或部分的异氰酸酯。例示性的异氰酸酯可以包括如美国专利4,748,192中所述的脂族异氰酸酯。相应的，它们通常包括脂肪族二异氰酸酯，特别包括三聚化或缩二脲形式的脂肪族二异氰酸酯，如六亚甲基二异氰酸酯，或四烷基二甲苯二异氰酸酯的双官能单体，如四甲基二甲苯二异氰酸酯。环己烷二异氰酸酯也被视为首选的脂肪族异氰酸酯。其他有用的脂族多异氰酸酯在美国专利4,705,814中有陈述，在此将其完全引用以供参考。它们包括脂族二异氰酸酯，例如在亚烃基自由基中具有4到12个碳原子的亚烷基二异氰酸酯，如1，12-十二烷二异氰酸酯和1，4-四亚甲基二异氰酸酯。同时提及脂环族二异氰酸酯，如1，3和1，4-环己烷二异氰酸酯以及这些异构体的任意混合，1-异氰酸根合-3，3，5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯)；4，4′-，2，2′-和2，4′-二环己基甲烷二异氰酸酯以及相应的异构体的混合物等。各种各样的芳族多异氰酸酯都可被用来生成泡沫聚脲弹性体。典型的芳族多异氰酸酯包括对苯二异氰酸酯，聚亚甲基聚苯基异氰酸酯，2，6-甲苯二异氰酸酯，联茴香胺二异氰酸酯，二甲代亚苯基二异氰酸酯，萘-1，4-二异氰酸酯，二(4-异氰酸根合苯基)甲烷，二(3-甲基-3-异氰酸根合苯基)甲烷，二(3-甲基-4-异氰酸根合苯基)甲烷和4，4′-二苯基丙烷二异氰酸酯。使用的其他芳族多异氰酸酯是亚甲基桥联的聚苯基多异氰酸酯混合物，其官能度介于约2到约4之间。后者的这些异氰酸酯化合物通常是由对相应的亚甲基桥联的聚苯基多胺进行光气化制备的，这些亚甲基桥联的聚苯基多胺通常是在存在氢氯酸和/或其他酸性催化剂的情况下，由甲醛和芳族伯胺(如苯胺)反应生成。有关制备多胺和尤其制备相应的亚甲基桥联的聚苯基多异氰酸酯的工艺在美国专利2,683,730、2,950,263、3,012,008、3,344,162和3,362,979中都有提及，将它们全部内容引用在此以供参考。通常情况下，亚甲基桥联的聚苯基多异氰酸酯混合物含有约20重量％-约100重量％的亚甲基二苯基二异氰酸酯异构体，其余的是有更高的官能度和分子量的聚亚甲基聚苯基二异氰酸酯。它们中比较典型的是含有约20重量％-约100重量％的二苯基二异氰酸酯异构体的聚苯基多异氰酸酯混合物，其中约20重量％-约95重量％是4，4′-异构体，其余的是有较高分子量和官能度(平均官能度介于约2.1到约3.5之间)的聚亚甲基聚苯基多异氰酸酯。这些异氰酸酯混合物是市场上能买到的已知原料，且能够通过在美国专利3,362,979中提及的方法制备。优选的芳族多异氰酸酯是亚甲基双(4-苯基异氰酸酯)或“MDI”。纯MDI、MDI的半预聚合物、改性的纯MDI等都可用于制备聚脲。由于纯MDI是固态的，因此通常不方便使用，此处使用基于MDI或亚甲基双(4-苯基异氰酸酯)的液体产品。美国专利3,394,164中描述了液态MDI产品，将其引入以供参考。更通常来说，脲酮亚胺改性的纯MDI也包括其中。该产品是通过在催化剂的存在下加热经过蒸馏的纯的MDI制备的。液态产品是纯MDI与改性MDI的混合物。术语“异氰酸酯”还包括含有异氰酸酯的半预聚物或具有活泼氢的多异氰酸酯的材料。“有机二异氰酸酯”可以包含上述异氰酸酯。
特别的，胺化合物，胺组分及其方法的具体实施方式提供了较理想的技术优势。对于含有伯胺的、AHEW较高的环氧固化剂而言，通常会导致在最终生成的给定的化学计量量的环氧树脂制剂中胺基(及环氧基)浓度较低。这在环氧涂层制剂方面是一个性能上的优势，因为环氧涂层表面较低浓度的胺基可导致更少地从空气中吸附污染物，如二氧化碳或湿气。通过减少在空气暴露中的二氧化碳的量及减少对水分的吸收，可以从胺固化的环氧涂层制剂表面减少或消除被称为“胺致发白”的有害现象。如果制剂的凝胶时间延长，则仅仅是较高的AHEW也许不会减少形成胺致发白的倾向。这被认为是由于在胺与环氧化物反应前，空气与易变化的含胺制剂之间有一个较长的接触时间所致。然而，在相同化合物中同时拥有高AHEW和高官能度会促进系统的较早凝胶，这样就将其固定并限制了可能发生的发白的数量。因此，基于官能度高于4的多元醇胺化的固化剂，尤其是基于季戊四醇衍生物的那些，在用于形成网络聚合物时可以提供独特优势。
特别地，胺化合物的使用会限制可固化的环氧制剂中胺基的浓度，而在较低的反应程度下则促进系统凝胶反应。这有利于降低具有较厚部分的模制件的放热温度，并减少在固化过程中在暴露于空气的表面上与胺致发白形成有关联的各种问题发生的可能性(包括降低光致泛黄(photo-yellowing))。特别的，使得在相对较低转化率下产生凝胶时间并且反应放热温和的足够低的端基反应性，容许了能在更大范围内配制。
43种常与环氧树脂配合使用的脂族胺化合物中只有6种的平均官能度大于4。最高官能度(6)的非加合固化剂曾是聚亚烷基醚胺类(即全部来自Huntsman公司的
T-403胺，和
T-3000胺，及
T-5000胺)。仅有的目前具有官能度大于6的物质的固化剂是一种高粘度的胺环氧树脂加合物(下文进一步说明)和四亚乙基五胺(TEPA)，其AHEW相对较低为约30并且由于将高官能度与低AHEW结合，其反应性很高。
与高官能度、低AHEW的脂族胺体系相比，基于诸如季戊四醇、双季戊四醇等的多官能原料的烷氧基化物的且有着足够分子量的高官能度的胺(并因此也是AHEW)具有优势，即它们可提供温和甚至缓慢的反应性和很长的工作时间，尽管它们有着高官能度。在环氧树脂配制这一方面，使用既有高官能度又有高AHEW特征的胺的其他优势在于，对于标准的液体环氧树脂，如具有环氧当量(EEW)为约180至200的双酚A的二缩水甘油醚，它们的混合比率和粘度比率更匹配，从而更容易混合以及在混合前可以更均匀地使填料分布在双部件系统的两个部件之间。
然而，具有高官能度及高AHEW的胺类固化剂的另一个优势是，尽管这种具有相对较高的AHEW的胺可能预计会在已固化产品中产生较低的玻璃化转变温度(Tg)，但是高官能度会增加交联，从而提高固化聚合物的Tg。
上述胺化合物通常具有较高的胺氢官能度(通常大于等于6)且AHEW值也较高，目前可获得的环氧固化剂中除了环氧树脂胺加合物之外没有具备上述条件者。环氧树脂胺加合物是由显著化学计量过量的胺与环氧树脂反应从而使得配混物保持不凝胶而得到的胺配混物。尽管环氧树脂胺加合物通过配制被广泛用作为减少胺致发白问题的手段，但它的使用还是有一些弊端。环氧树脂胺加合物在用作同时获得高官能度和高AHEW的手段时的弊端是：
1)这种加合物含有大量羟基，其大大增加了它们的粘度并降低了混入环氧树脂配制剂及后续对其脱气的容易性。
2)为了避免合成中由于加合物分子的连接而产生过高的分子量，使用用来随之降低加合混合物的AHEW的过量胺，或通过额外使用处理步骤将其从混合物中提出。
3)最终聚合物中的胺浓度并没有减少，这意味着可能发生了类似于低AHEW材料的吸收大气中水分和二氧化碳的现象。
4)加合反应是额外的合成步骤，所以使过程更复杂，也增加了产品的成本。
在特定的具体实施方案中，胺组分不包含环氧树脂胺加合物。
实施例：
制备基于季戊四醇烷氧基化物的两种不同的胺化合物并将其用来聚合基于双酚A的标准液体环氧树脂，其具有的环氧当量约为184。该胺化反应采用标准方法进行。
实施例1-环氧树脂固化，使用基于用8.5摩尔的环氧丙烷烷氧基化的季戊四醇的胺
根据对这类胺的湿实验室分析(web lab analysis)，胺的AHEW约为85.9克每胺-氢当量。有关环氧固化的胺的AHF为8。
通过混合89.11份实施例1的产物和190.89份环氧树脂-液体双酚A基的环氧树脂(环氧当量为184)，以及在玻璃模具中在80℃的温度下烘焙3小时并随后在125下烘焙2小时来进行浇铸，从而形成一个标称厚度为八分之一英寸的未填充铸件。用DSC(差示扫描量热计)在加热速率为20℃/分钟下测量时，该聚合物的Tg是98.6℃。机械测试显示挠曲强度为20,600psi，抗拉强度为10,200psi，而拉伸模量为446,000psi。
实施例2-环氧树脂固化，使用用8.5摩尔德环氧丙烷并随后用5摩尔环氧丁烷烷氧基化的基于季戊四醇的胺
根据对这类胺的湿实验室分析，胺的AHEW约为126克每胺-氢当量。有关环氧固化的胺的AHF为8。
通过按照1∶1的化学计量量混合106.76份这种胺和173.24份环氧树脂-液体双酚A基的环氧树脂(环氧当量为184)，以及在110℃的温度下烘焙2小时并随后在125℃下烘焙2小时来进行浇铸，从而形成一个标称厚度为八分之一英寸的未填充铸件。用DSC(差示扫描量热计)在加热速率为20℃/分钟下测量时，该聚合物的玻璃化转变温度(Tg)是64℃。
与此相反，当按照56份的1∶1的化学计量水平使用JEFFAMINE
D-400胺(这种胺的AHEW为115，AHF为4)来固化100份环氧树脂-液体双酚A基的环氧树脂(环氧当量184)时，得到的Tg为56℃，即使胺的AHEW略低。
机械测试显示，基于季戊四醇的胺当用于聚合标准的基于双酚A的液体环氧树脂时，得到的产品具有挠曲强度17,900psi，抗拉强度为7200psi，拉伸模量为467,000psi。
Claims (16)
1.具有如下结构的胺组分用作环氧体系中固化剂的用途：
其中，平均来说，4.0≤w+x+y+z≤13.0，每个R独立地选自包含氢、甲基、乙基、丙基和丁基的组；所述固化剂具有的胺氢官能度为至少5，胺-氢当量为至少50。
2.如权利要求1中所述的用途，其中平均来说，4.0≤w+x+y+z ≤5.0。
3.如权利要求1中所述的用途，其中平均来说，8.0≤w+x+y+z≤9.0。
4.如权利要求1中所述的用途，其中的胺官能固化剂由烷氧基化的多元醇化合物形成。
5.如权利要求4中所述的用途，其中所述的烷氧基化的多元醇化合物有至少4个羟基。
6.如权利要求4中所述的用途，其中烷氧基化的多元醇化合物具有选自于以下化合物的多元醇：赤藓醇、季戊四醇、双季戊四醇以及它们的组合。
7.如权利要求4中所述的用途，其中所述的烷氧基化的多元醇化合物具有至少含4个羟基的多元醇。
8.如权利要求4中所述的用途，其中所述烷氧基化的多元醇化合物具有选自于以下化合物的多元醇：曼尼希多元醇、胺多元醇、蔗糖/乙二醇多元醇、蔗糖/甘油多元醇、蔗糖/胺多元醇、山梨醇多元醇及其组合。
9.如权利要求1中所述的用途，其中胺-氢当量是至少70且不大于400。
10.如权利要求1中所述的用途，其中胺-氢当量是至少115且不大于150。
11.如权利要求1中所述的用途，其中胺氢官能度是至少7。
12.如权利要求1中所述的用途，其中胺氢官能度是至少8。
13.如权利要求1中所述的用途，其中所述的胺官能固化剂包含至少3个伯胺基。
14.如权利要求1中所述的用途，其中胺官能固化剂含有至少4个伯胺基。
15.如权利要求1中所述的用途，其中胺官能固化剂的分子量为至少600。
16.如权利要求1中所述的用途，其中胺官能固化剂的分子量为至少800且不大于1500。
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- 2008-03-14 EP EP08743878.4A patent/EP2125920B1/en active Active
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| Publication number | Publication date |
|---|---|
| EP2125920A1 (en) | 2009-12-02 |
| CA2679711A1 (en) | 2008-09-18 |
| US8178726B2 (en) | 2012-05-15 |
| WO2008112952A1 (en) | 2008-09-18 |
| CA2679711C (en) | 2018-05-01 |
| US20120184778A1 (en) | 2012-07-19 |
| US20100069672A1 (en) | 2010-03-18 |
| US8471065B2 (en) | 2013-06-25 |
| EP2125920A4 (en) | 2013-04-03 |
| JP5491872B2 (ja) | 2014-05-14 |
| CN101675084A (zh) | 2010-03-17 |
| JP2010521563A (ja) | 2010-06-24 |
| AU2008224980B2 (en) | 2012-11-08 |
| AU2008224980A1 (en) | 2008-09-18 |
| EP2125920B1 (en) | 2014-12-31 |
| MX2009009502A (es) | 2009-09-18 |
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