CN108137780B - 聚酰胺亚胺的制备 - Google Patents
聚酰胺亚胺的制备 Download PDFInfo
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- CN108137780B CN108137780B CN201680054744.9A CN201680054744A CN108137780B CN 108137780 B CN108137780 B CN 108137780B CN 201680054744 A CN201680054744 A CN 201680054744A CN 108137780 B CN108137780 B CN 108137780B
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- CN
- China
- Prior art keywords
- diisocyanate
- composition
- component
- solvent
- phenylene diisocyanate
- Prior art date
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- 239000004962 Polyamide-imide Substances 0.000 title claims description 17
- 229920002312 polyamide-imide Polymers 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011877 solvent mixture Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000008199 coating composition Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 239000002981 blocking agent Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 claims description 4
- OIEHLJRTPUHJJY-UHFFFAOYSA-N 4,8-dioxabicyclo[3.2.1]octane Chemical class O1C2CCC1OCC2 OIEHLJRTPUHJJY-UHFFFAOYSA-N 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- NZLNKKUMUPWQMW-UHFFFAOYSA-N 1,3,5-triethyl-2,4-diisocyanatobenzene Chemical compound CCC1=CC(CC)=C(N=C=O)C(CC)=C1N=C=O NZLNKKUMUPWQMW-UHFFFAOYSA-N 0.000 claims description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- YJCCKJOGVKKKIH-UHFFFAOYSA-N 1,3-diethyl-2,4-diisocyanato-5-methylbenzene Chemical compound CCC1=CC(C)=C(N=C=O)C(CC)=C1N=C=O YJCCKJOGVKKKIH-UHFFFAOYSA-N 0.000 claims description 2
- BQHPNDYUVBBCQF-UHFFFAOYSA-N 1,3-diisocyanato-5-methylbenzene Chemical compound CC1=CC(N=C=O)=CC(N=C=O)=C1 BQHPNDYUVBBCQF-UHFFFAOYSA-N 0.000 claims description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 2
- LGLNTUFPPXPHKF-UHFFFAOYSA-N 1,4-diisocyanato-2,3,5,6-tetramethylbenzene Chemical compound CC1=C(C)C(N=C=O)=C(C)C(C)=C1N=C=O LGLNTUFPPXPHKF-UHFFFAOYSA-N 0.000 claims description 2
- DKBHJZFJCDOGOY-UHFFFAOYSA-N 1,4-diisocyanato-2-methylbenzene Chemical compound CC1=CC(N=C=O)=CC=C1N=C=O DKBHJZFJCDOGOY-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- PEZADNNPJUXPTA-UHFFFAOYSA-N 1,5-bis(isocyanatomethyl)-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(CN=C=O)C=C1CN=C=O PEZADNNPJUXPTA-UHFFFAOYSA-N 0.000 claims description 2
- PCXYTFRAVPVHBV-UHFFFAOYSA-N 1,5-diethyl-2,4-diisocyanato-3-methylbenzene Chemical compound CCC1=CC(CC)=C(N=C=O)C(C)=C1N=C=O PCXYTFRAVPVHBV-UHFFFAOYSA-N 0.000 claims description 2
- XKTWBSJOROQZOC-UHFFFAOYSA-N 1-chloro-2,4-diethyl-3,5-diisocyanato-6-methylbenzene Chemical compound CCC1=C(Cl)C(C)=C(N=C=O)C(CC)=C1N=C=O XKTWBSJOROQZOC-UHFFFAOYSA-N 0.000 claims description 2
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 claims description 2
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- VXQILLTWRZPRQF-UHFFFAOYSA-N 2,4-diisocyanato-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1N=C=O VXQILLTWRZPRQF-UHFFFAOYSA-N 0.000 claims description 2
- WHIRALQRTSITMI-UHFFFAOYSA-N 6,8-dioxabicyclo[3.2.1]octan-4-one Chemical compound O=C1CCC2COC1O2 WHIRALQRTSITMI-UHFFFAOYSA-N 0.000 claims description 2
- DYXJGWLSYLPWMO-UHFFFAOYSA-N 6,8-dioxabicyclo[3.2.1]octane Chemical compound C1CCC2COC1O2 DYXJGWLSYLPWMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 claims description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- -1 aromatic tricarboxylic acid Chemical class 0.000 abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
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- 229910000831 Steel Inorganic materials 0.000 description 3
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- WHIRALQRTSITMI-UJURSFKZSA-N (1s,5r)-6,8-dioxabicyclo[3.2.1]octan-4-one Chemical compound O1[C@@]2([H])OC[C@]1([H])CCC2=O WHIRALQRTSITMI-UJURSFKZSA-N 0.000 description 2
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Abstract
一种液体组合物，包含(a)基于溶剂量包含至少50wt％二氧双环烷烃衍生物的溶剂或溶剂混合物、(b)芳族三羧酸酸酐和(c)芳族二异氰酸酯，该液体组合物可用作金属表面的涂料组合物。
Description
本发明涉及一种包含特定溶剂或溶剂混合物、芳族酸酸酐和芳族二异氰酸酯的液体组合物、由该组合物制备的聚酰胺亚胺以及该聚酰胺亚胺用作金属表面涂层材料的用途。
早就已知在极性非质子溶剂如N-甲基吡咯烷酮(NMP)中由三羧酸单酸酐和二异氰酸酯制备聚酰胺亚胺(PAI)。但最近已经将NMP重新归类为再生产和开发的毒物并且列为对呼吸道有特定有机毒性。
另外，在许多情况下在NMP中由PAI制备的涂层的固化时间可能太长和对于一些应用来说溶剂耐受性可能太低。
因此，需要热稳定且耐受溶剂的PAI涂层，其可以在基本不使用有害溶剂混合物的情况下快速制备。
已经令人惊讶地发现，应用二氧双环烷烃衍生物作为溶剂在很大程度上解决了上述问题。
因此，本发明涉及一种液体组合物，其包含(a)基于溶剂量包含至少50wt％二氧双环烷烃衍生物的溶剂或溶剂混合物、(b)芳族三羧酸酸酐和(c)芳族二异氰酸酯。
衍生自二氧双环烷烃的液体化合物相对于PAI具有出色的溶剂性能。这些溶剂可以由可再生资源如木材或其它含纤维素的产品生产和通常是生物可降解的。
合适的二氧双环烷烃衍生物为二氧双环[3.2.1]辛烷、二氧双环[2.2.2]辛烷、二氧双环[3.3.2]癸烷、二氧双环[4.2.2]癸烷、二氧双环[4.3.1]癸烷、二氧双环[5.2.1]癸烷、二氧双环[3.3.3]十一烷、二氧双环[4.3.2]十一烷、二氧双环[4.4.1]十一烷和二氧双环[5.3.1]十一烷以及它们的液体衍生物，特别是它们的酮衍生物。
优选地，组分(a)的溶剂是2,8-二氧双环[3.2.1]辛烷或6,8-二氧双环[3.2.1]辛烷的衍生物。
这些化合物为天然产物，如zaragozic酸A或sordidin，或者可以按照已知方法制备。合适的2,8-二氧双环[3.2.1]辛烷衍生物例如在J.Am.Chem.Soc.117，8106-8125(1995)中有述。
合适溶剂的例子有2,8-二氧双环[3.2.1]辛烷、2,8-二氧双环[3.2.1]辛-4-酮、2,8-二氧双环[3.2.1]辛-4-硫酮、4-亚甲基-2,8-二氧双环[3.2.1]辛烷、1-甲基-2,8-二氧双环[3.2.1]辛-7-酮、1,4,4-三甲基-2,8-二氧双环[3.2.1]辛-7-酮、1,3,5-三甲基-2,8-二氧双环[3.2.1]辛-7-酮、1-甲基-4-苯基-2,8-二氧双环[3.2.1]辛-7-酮、1-甲基-4-苯基-2,8-二氧双环[3.2.1]辛-7-基乙酸酯、6,8-二氧双环[3.2.1]辛烷、6,8-二氧双环[3.2.1]辛-4-硫酮和6,8-二氧双环[3.2.1]辛-4-酮。
作为组分(a)特别优选的是6,8-二氧双环[3.2.1]辛-4-酮。
二氢左旋葡萄糖酮(6,8-二氧双环[3.2.1]辛-4-酮)为由可再生纤维素制备的双极性非质子溶剂和已经针对可能的突变进行测试，结果没有发现突变。
同时，6,8-二氧双环[3.2.1]辛-4-酮可以商标CyreneTM商购(由Circa Group提供)。
已经令人惊讶地发现，应用二氧双环烷烃衍生物代替常规极性非质子溶剂如NMP作为羧酸酸酐和二异氰酸酯缩聚的溶剂不仅促进迅速固化，而且提供了具有增强的溶剂耐受性的涂层。
在所述组合物中应用的溶剂混合物可以包含至多50wt％的其它极性非质子溶剂，例如丙酮、环己酮、四甲基脲、硝基甲烷、亚硫酸亚乙酯、N,N-二甲基乙酰胺(DMAC)、N,N-二甲基甲酰胺(DMF)、N,N′-二甲基亚乙基脲、3-甲基
唑烷-2-酮、乙腈、二甲基亚砜(DMSO)，N,N′-二甲基亚丙基脲(DMPU)、N-甲基-ε-己内酰胺、二甲基砜、S,S-二甲基磺亚酰胺、四乙基磺酰胺、环丁砜、碳酸亚乙酯、二氧六环、二氧戊环、甲基膦酸二(二甲基酰胺)、碳酸亚丙酯、六甲基磷酸三酰胺(HMPT)、ε-己内酯、δ-戊内酯、γ-戊内酯、柠檬烯、5-(二甲基氨基)-2-甲基-5-氧戊酸甲基酯、戊二酸、2-甲基-1,5-二甲基酯、3-甲氧基丙酰基-N,N-二甲基酰胺和3-丁氧基丙酰基-N,N-二甲基酰胺。
在优选的实施方案中，本发明的组合物包含含有90-100wt％二氧双环烷烃衍生物的溶剂或溶剂混合物作为组分(a)。
重要的是所应用溶剂的水含量尽可能低。
当溶剂水含量<0.1wt％时反应平稳进行。
特别优选的是组合物包含纯二氧双环烷烃衍生物、特别是纯6,8-二氧双环[3.2.1]辛-4-酮作为组分(a)。
用于制备聚酰胺亚胺的合适起始产品即组分(b)和(c)是公知的，它们可以商购获得或者可以根据已知方法合成。
作为组分(b)的芳族三羧酸酸酐的例子有偏苯三酸酸酐(TMA)、连苯三酸酸酐、甲基偏苯三酸酸酐、4′-羧基二苯基-3,4-二羧酸酸酐、1,2,3-苯三羧酸酸酐、3,4,6-和1,3,8-萘三羧酸酸酐、1,2,7-蒽三羧酸酸酐和它们的组合。
偏苯三酸酸酐是特别优选的。
适合的作为组分(c)的二异氰酸酯为例如2,4-甲苯二异氰酸酯、2,5-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、3,5-甲苯二异氰酸酯、1-甲氧基-2,4-亚苯基二异氰酸酯、1,3,5-三乙基-2,4-亚苯基二异氰酸酯、1-甲基-3,5-二乙基-6-氯-2,4-亚苯基二异氰酸酯、p-苯二甲基二异氰酸酯、m-苯二甲基二异氰酸酯、苯甲酮-4,4′-二异氰酸酯、1,4-萘二异氰酸酯、1,5-萘二异氰酸酯、4,4-二异氰酸酯基二苯基甲烷、4,4-二异氰酸酯基-3,3′-二甲基二苯基甲烷、2,2′-二异氰酸酯基-4,4′-二甲基二苯基甲烷、4-甲氧基-1,3-亚苯基二异氰酸酯、4,4-二异氰酸酯基-3,3′-二氯二苯基甲烷，4,4-二异氰酸酯基二苯基醚、2,4-二异氰酸酯基二苯基醚、1,3-亚苯基二异氰酸酯、3,3′-二甲氧基-4,4′-二亚苯基二异氰酸酯、3,3′-二乙氧基-4,4′-二亚苯基二异氰酸酯、4-氯-1,3-亚苯基二异氰酸酯、4,4′-二亚苯基二异氰酸酯、3,3′-二甲基-4,4′-二亚苯基二异氰酸酯、1-甲基-3,5-二乙基-2,4-亚苯基二异氰酸酯、4-异丙基-1,3-亚苯基二异氰酸酯、四甲基对苯二异氰酸酯、3,3′-二甲苯-4,4′-二异氰酸酯、1-甲基—3,5-二乙基-2,6-亚苯基二异氰酸酯、2,2-二(4-异氰酸酯基苯基)丙烷和4,6-二甲基-1,3-苯二甲基二异氰酸酯以及它们的组合。
优选地，组分(c)为4,4′-二异氰酸酯基二苯基甲烷。
组分(b)和(c)适宜地以大约等摩尔量应用。在本文中大约等摩尔量指每1摩尔二异氰酸酯应用0.7-1.3mol、优选0.8-1.2mol、特别是0.9-1.1mol三羧酸。
组分(a)、(b)和(c)的相对量可以在宽范围内变化。在优选的实施方案中，基于整个组合物计，组分(a)的量为60-95wt％，更优选为70-90wt％，和特别是75-85wt％，组分(b)+(c)的总量为5-40wt％，更优选为10-30wt％，和特别是15-25wt％。
组分(b)和(c)相继溶解在作为组分(a)的溶剂或溶剂混合物中，如果需要在高温下进行，例如在50-150℃下，优选为60-100℃。随后，反应在高温下在搅拌下进行，优选为110-180℃，更优选为120-160℃。在缩聚反应过程中，随时确定溶液粘度。对于涂料应用，建议粘度为2000-6000mPa·s，优选为3000-5000mPa·s(按照ISO 3219在25℃应用具有锥6的CAP 2000粘度计(Brookfield)确定)。当达到所需粘度时，可以通过添加异氰酸酯封阻剂猝灭反应。
合适的异氰酸酯封阻剂例如在WO 2011/051412中有述。典型的异氰酸酯封阻剂包括：醇如酚和多元醇；胺；酰胺如内酰胺；带有不稳定亚甲基部分的活性亚甲基化合物如丙二酸酯；含氮的杂芳基化合物如吡唑；肟；酮肟如二烷基酮肟；和羟肟酸酯。合适的异氰酸酯封阻剂的例子有二乙基丙二酸酯、3,5-二甲基吡唑、甲基乙基酮肟和优选为ε-己内酰胺。
如果需要，本发明的液体组合物可以包含通常的添加剂，如稳定剂、增链剂、填料、补强剂、颜料、染料、增塑剂、增粘剂、橡胶、促进剂、稀释剂或它们的任意混合物。
因此，本发明还涉及制备芳族聚酰胺亚胺溶液的方法，特征在于将权利要求1的组合物加热到50-230℃，直到溶液粘度为3000-5000mPa·s，和通过添加异氰酸酯封阻剂使聚合反应猝灭。
本发明的进一步实施方案是通过上述方法制备的聚酰胺亚胺。
在溶液形式中，如此获得的PAI非常适合制备纤维、绝缘漆、粘合剂和特别是涂覆膜。
可以通过本领域技术人员已知的方法如喷涂、浸涂、刷涂、涂漆、辊涂等以所需的厚度将PAI溶液固化剂施涂到一个或多个基材表面上。在施涂后，涂层在环境条件下和/或通过施加热量固化。所述基材可以为但不限于水泥、金属、混凝土、砖、水泥板或石膏灰胶纸夹板。
优选地，通过上述方法获得的芳族聚酰胺亚胺溶液用作金属表面的涂料组合物，具体用于铝和钢表面。
因此，本发明还涉及在基材上形成固化涂层的方法，包括向基材上施涂按照上述方法制备的芳族聚酰胺亚胺溶液以形成涂层，和使所述涂层经受固化条件。
可以使所施用的涂层固化足以使涂层硬化的任何时间段，例如1分钟至约10天。高温通常加速固化反应，例如2h/80℃+1h/120℃+2h/220℃通常就足够了。由本发明的组合物获得的涂层可以通过加热至温度>200℃而在很短时间内固化。通常，在230℃下在3分钟内实现完全固化。
固化涂层的特征在于良好的热稳定性和溶剂耐受性，特别是相对于NMP的溶剂耐受性。
因此，在又一个实施方案中，提供一种按照上述方法涂覆的制品或基材。
通过如下非限定性实施例描述本发明。
实施例
性能测量和所用原料列表：
除非另有说明，溶液粘度在25℃应用带有锥6的CAP 2000粘度计(Brookfield)(ISO 3219)测量。
在实施例中应用的溶剂为商购产品。CYRENETM为6,8-二氧双环[3.2.1]辛-4-酮(二氢左旋葡萄糖酮，由Cerca Group提供)。4,4′-二异氰酸酯基二苯基甲烷(MDI)和偏苯三酸酸酐(TMA)同样为纯度>95％的可商购产品。
实施例A1
将79.8g Cyrene加入配备有KPG-搅拌器(桨叶)、热电偶、气密性搅拌管、温度控制设施、回流冷凝器和氮入口的玻璃反应器中。8.41g(0.0438mol)偏苯三酸酸酐(TMA)在155rpm的搅拌下加入。加热混合物，其中TMA在65℃下溶解。在89℃的内部温度下，加入10.97g(0.0438mol)4,4′-二异氰酸酯基二苯基甲烷(MDI)。在85℃下MDI开始溶解。烧瓶内的内部温度升至145℃并保持1小时。在136℃下观察到不同的气体逸出。在145℃下确定反应粘度。在145℃下反应5小时后，粘度为3540mPa·s(锥6，500rpm.CAP 2000，Brookfield)。烧瓶内容物冷却至100℃的内部温度，和加入0.83gε-己内酰胺。黑液在100℃下保持另外3小时。之后将溶液冷却至室温。
收率：83.65g，η25℃＝3345mPa·s，锥6，500rpm(CAP 2000，Brookfield)。
实施例A2和A3及对比例C1
如以上实施例A1中所述，由TMA和MDI制备聚酰胺亚胺的溶液，其中应用Cyrene和环丁砜的混合物(实施例A2)、Cyrene和N-甲基吡咯烷酮(NMP)的混合物(实施例A3)以及纯NMP(对比例C2)。
溶剂耐受性测试
A.在负载下对NMP的耐受性
将实施例A1-A3和C1中制备的溶液施涂到铝板上和使所述涂层在烘箱中固化(3min/230℃)。随后，涂覆后板材在室温(RT)下在负载(分别为2kg/3h或2kg/6h)下浸在NMP中。涂层外观通过视觉评价。
B.对NMP的耐受性-24h测试
将实施例A1-A3和C1中制备的溶液施涂到钢板上和使所述涂层在烘箱中固化(2h/80℃，1h/120℃，2h/220℃)。随后，涂覆后板材在RT下浸在NMP中24h。涂层外观通过视觉评价分级如下：+＝通过；/＝临界；-＝未通过。
测试结果在下表1中给出。
表1：组合物A1、A2、A3和C1的组分量以重量份给出
测试结果讨论
本发明的组合物A1、A2和A3提供的固化产品完全符合用于铝和钢表面的耐热涂层的要求。令人惊讶地，由本发明组合物在金属板上制备的薄膜可以在230℃下在3分钟内固化，和固化涂层在RT下在NMP中以及在负载下在NMP中均保持稳定。另一方面，由对比组合物C1获得的涂层在溶剂耐受性方面不合要求。
Claims (12)
1.一种液体组合物，包含(a)基于溶剂总量包含至少50wt％二氧双环烷烃衍生物的溶剂或溶剂混合物、(b)芳族三羧酸酸酐和(c)芳族二异氰酸酯，其中基于整个组合物计组分(a)的量为75-95wt％和组分(b)+(c)的总量为5-25wt％，和其中作为组分(c)的芳族二异氰酸酯选自2,4-甲苯二异氰酸酯、2,5-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、3,5-甲苯二异氰酸酯、1-甲氧基-2,4-亚苯基二异氰酸酯、1,3,5-三乙基-2,4-亚苯基二异氰酸酯、1-甲基-3,5-二乙基-6-氯-2,4-亚苯基二异氰酸酯、p-苯二甲基二异氰酸酯、m-苯二甲基二异氰酸酯、苯甲酮-4,4′-二异氰酸酯、1,4-萘二异氰酸酯、1,5-萘二异氰酸酯、4,4′-二异氰酸酯基二苯基甲烷、4,4-二异氰酸酯基-3,3′-二甲基二苯基甲烷、2,2′-二异氰酸酯基-4,4′-二甲基二苯基甲烷、4-甲氧基-1,3-亚苯基二异氰酸酯、4,4-二异氰酸酯基-3,3′-二氯二苯基甲烷，4,4-二异氰酸酯基二苯基醚、2,4-二异氰酸酯基二苯基醚、1,3-亚苯基二异氰酸酯、3,3′-二甲氧基-4,4′-二亚苯基二异氰酸酯、3,3′-二乙氧基-4,4′-二亚苯基二异氰酸酯、4-氯-1,3-亚苯基二异氰酸酯、4,4′-二亚苯基二异氰酸酯、1-甲基-3,5-二乙基-2,4-亚苯基二异氰酸酯、4-异丙基-1,3-亚苯基二异氰酸酯、四甲基对苯二异氰酸酯、1-甲基-3,5-二乙基-2,6-亚苯基二异氰酸酯、2,2-二(4-异氰酸酯基苯基)丙烷和4,6-二甲基-1,3-苯二甲基二异氰酸酯以及它们的组合。
2.权利要求1的组合物，其包含2,8-二氧双环[3.2.1]辛烷或6,8-二氧双环[3.2.1]辛烷的衍生物作为组分(a)。
3.权利要求1的组合物，其包含6,8-二氧双环[3.2.1]辛-4-酮作为组分(a)。
4.权利要求1的组合物，其包含含90-100wt％二氧双环烷烃衍生物的溶剂或溶剂混合物作为组分(a)。
5.权利要求1-4任一项的组合物，其包含偏苯三酸酸酐作为组分(b)。
6.权利要求1-4任一项的组合物，其包含4,4′-二异氰酸酯基二苯基甲烷作为组分(c)。
7.权利要求1-4任一项的组合物，其中基于整个组合物计组分(a)的量为85-90wt％和组分(b)+(c)的总量为10-15wt％。
8.一种制备芳族聚酰胺亚胺溶液的方法，特征在于将权利要求1-7任一项的组合物加热到50-230℃，直到溶液粘度为3000-5000mPa·s，和通过加入异氰酸酯封阻剂猝灭聚合反应。
9.通过权利要求8的方法制备的聚酰胺亚胺。
10.通过权利要求8的方法获得的芳族聚酰胺亚胺溶液用作金属表面涂料组合物的用途。
11.一种在基材上形成固化涂层的方法，包括向基材上施用通过权利要求8的方法制备的芳族聚酰胺亚胺溶液以形成涂层和随后使所述涂层置于固化条件下。
12.按照权利要求11的方法制备的固化涂层。
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| US3790530A (en) | 1971-11-03 | 1974-02-05 | Phelps Dodge Magnet Wire Corp | Method of making amide-imide resins,aromatic amides and aromatic polyamide resins |
| US3884880A (en) | 1973-09-21 | 1975-05-20 | Phelps Dodge Magnet Wire Corp | Modified amide-imide resins and method of making the same |
| JPS5836018B2 (ja) * | 1981-04-06 | 1983-08-06 | 日立化成工業株式会社 | 耐熱性樹脂の製造法 |
| JPS5880326A (ja) | 1981-11-06 | 1983-05-14 | Hitachi Chem Co Ltd | ポリアミドイミド樹脂の製造法 |
| DE3249544C2 (de) | 1981-11-06 | 1985-07-11 | Hitachi Chemical Co., Ltd., Tokio/Tokyo | Isolierter Draht |
| DE3544548A1 (de) | 1985-12-17 | 1987-06-19 | Beck & Co Ag Dr | Verfahren zur herstellung lagerstabiler polyamidimidlacke und deren verwendung |
| JPH085961B2 (ja) * | 1986-10-06 | 1996-01-24 | 三菱化学株式会社 | 水素の分離方法 |
| FR2629088B1 (fr) | 1988-03-24 | 1990-12-14 | Rhone Poulenc Chimie | Polyamide-imides aromatiques fonctionnalises par des groupes maleimido, un procede pour leur preparation et leur emploi pour notamment preparer des polymeres reticules |
| DE69212281T2 (de) | 1991-11-22 | 1997-01-09 | Sumitomo Electric Industries | Isolierter Draht |
| US7267883B2 (en) * | 2002-09-25 | 2007-09-11 | Kaneka Corporation | Polyimide film and laminate having metal layer and same |
| CN101280107B (zh) * | 2008-05-13 | 2011-03-30 | 广东生益科技股份有限公司 | 一种聚酰亚胺树脂、使用其制作的挠性覆铜板及其制作方法 |
| EP2449057B1 (en) | 2009-07-01 | 2021-08-11 | Circa Group PTY Ltd | Method for converting lignocellulosic materials into useful chemicals |
| CA2779065A1 (en) | 2009-10-29 | 2011-05-05 | Sun Chemical B.V. | Polyamideimide adhesives for printed circuit boards |
| US9751986B2 (en) * | 2011-12-15 | 2017-09-05 | Fujifilm Hunt Chemicals Us, Inc. | Low toxicity solvent system for polyamideimide resins and solvent system manufacture |
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