TWI461465B - 酸官能性聚醯胺醯亞胺 - Google Patents
酸官能性聚醯胺醯亞胺 Download PDFInfo
- Publication number
- TWI461465B TWI461465B TW095145274A TW95145274A TWI461465B TW I461465 B TWI461465 B TW I461465B TW 095145274 A TW095145274 A TW 095145274A TW 95145274 A TW95145274 A TW 95145274A TW I461465 B TWI461465 B TW I461465B
- Authority
- TW
- Taiwan
- Prior art keywords
- anhydride
- triamine
- acid
- diisocyanate
- amine
- Prior art date
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- 239000002253 acid Substances 0.000 title claims abstract description 8
- 239000004962 Polyamide-imide Substances 0.000 title abstract 3
- 229920002312 polyamide-imide Polymers 0.000 title abstract 3
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- -1 anhydride acid chloride Chemical class 0.000 claims description 23
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 23
- 150000008064 anhydrides Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000007859 condensation product Substances 0.000 claims description 6
- 239000004135 Bone phosphate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 150000002632 lipids Chemical class 0.000 claims 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 14
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- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 27
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 239000012467 final product Substances 0.000 description 12
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 6
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- 239000005056 polyisocyanate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 5
- 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 description 4
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- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 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
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Description
本發明係關於聚醯胺醯亞胺(PAI)基底塗料組合物；且更特定言之，係關於具有過量羧基官能性之該等塗料組合物。
吾人熟知呈清漆及瓷漆形式之樹脂塗料組合物，且其中為易於塗覆，將聚合物溶解於相容性溶劑中。聚醯胺醯亞胺組合物係描述於(例如)美國專利4,259,221中。
最適用之塗料組合物為基於聚醯胺醯亞胺之塗料組合物。聚醯胺醯亞胺塗料組合物形成可撓性且耐久性薄膜，且尤其適用作導線瓷漆、清漆、疊層用黏著劑、不黏塗料、油漆及其類似物。該等組合物以其長期高溫耐受性(220℃(430℉))而著名。另外，該等組合物亦適用於電絕緣應用(諸如用於磁線瓷漆)及作為用於炊具之不黏塗料。
迄今為止，聚醯胺醯亞胺係藉由使用相對昂貴之有機溶劑來製備而得，故造成使用醯胺醯亞胺塗料成為經濟上難實施的。由有機溶劑產生之高含量VOC'亦已成為一限制其使用之因素。
作為聚醯胺醯亞胺製備之一實例，一羧酸酐與有機第一胺一起反應以形成醯胺醯亞胺預聚物。隨後使此預聚物與聚異氰酸酯反應產生一相對高分子量之嵌段聚合物，其在溶液中提供聚醯胺醯亞胺所固有且吾人所欲之成膜及其他特性。
多種羧酸酐用於製造聚醯胺醯亞胺。該等羧酸酐包括但不限於偏苯三甲酸酐(TMA)；2,6,7－萘三羧酸酐；3,3',4－二苯基三羧酸酐；3,3',4－二苯甲酮三羧酸酐；1,3,4－環戊烷四羧酸酐；2,2',3－二苯基三羧酸酐；二苯基碸3,3',4－三羧酸酐；二苯基亞異丙基3,3',4－三羧酸酐；3,4,10－苝三羧酸酐；3,4－二羧基苯基3－羧基苯基醚酐；伸乙基三羧酸酐；1,2,5－萘三羧酸酐等。該等三羧酸物質之特徵在於下式：
其中R為三價有機基團。
適用於上述關係中之多元胺係在此項技術領域中為人所熟知，且可由下式表示：X－R"－(－NH2
)n
其中R"為有機基團，X為氫、胺基或包括彼等含有至少一個胺基之有機基團，且n具有2或2以上之值。多元胺亦可由下式表示：R'''－(－NH2
)n
其中R'''係選自由具有至少兩個碳原子之有機基團(經鹵化及未經鹵化均可)組成之群之成員，其包括但不限於，例如高達40個碳原子之烴基，且由至少兩個芳基殘基組成之基團，其中兩芳基殘基係經由選自由具有1至10個碳原子之伸烷基、－S－、－SO2
－、
及－O－等組成之群之成員的媒體彼此連接。在上式中，n再次具有至少2之值。
下列胺可單獨或以混合物形式使用：對二甲苯二胺雙(4－胺基－環己基)甲烷己二胺庚二胺辛二胺壬二胺癸二胺3－甲基－庚二胺4,4'－二甲基庚二胺2,11－二胺基－十二烷1,2－雙－(3－胺基－丙氧基)乙烷2,2－二甲基丙二胺3－甲氧基－己二胺2,5－二甲基己二胺2,5－二甲基庚二胺5－甲基壬二胺1,4－二胺基－環己烷1,12－二胺基－十八烷2,5－二胺基－1,3,4－噁二唑H2
N(CH2
)3
O(CH2
)2
O(CH2
)3
NH2
H2
N(CH2
)3
S(CH2
)3
NH2
H2
N(CH2
)3
N(CH3
)(CH2
)3
NH2
間苯二胺對苯二胺4,4'－二胺基－二苯基丙烷4,4'－二胺基－二苯基甲烷聯苯胺4,4'－二胺基－二苯硫4,4'－二胺基－二苯碸3,3'－二胺基－二苯碸4,4'－二胺基－二苯醚2,6－二胺基－吡啶雙(4－胺基－苯基)二乙基矽烷雙(4－胺基－苯基)二苯基矽烷雙(4－胺基－苯基)膦氧化物4,4'－二胺基二苯甲酮雙(4－胺基－苯基)－N－甲基胺雙(4－胺基丁基)四甲基二矽氧烷1,5－二胺基萘3,3'－二甲基－4,4'－二胺基－聯苯3,3'－二甲氧基聯苯胺2,4－雙(β－胺基－第三丁基)甲苯甲苯二胺雙(對－β－胺基－第三丁基－苯基)醚對雙(2－甲基－4－胺基－戊基)苯對雙(1,1－二甲基－5－胺基－戊基)苯間二甲苯二胺聚亞甲基聚苯胺。
任何聚異氰酸酯，亦即具有兩個或兩個以上異氰酸酯基之任何異氰酸酯，無論封端或未封端，均可用於製造聚醯胺醯亞胺。使用(例如)酚或醇作為封端組份之封端異氰酸酯亦可使用。一般而言，其提供更高分子量之最終物質且其在(例如)清漆中為有利的。另一方面，未封端之異氰酸酯提供更多可撓性最終材料。不管使用何種，應將盡可能多的封端物質蒸出，且自純反應觀點看，關於使用何種材料不存在優點。典型封端聚異氰酸酯為Mondur STM
(獲自Mobay Chemical Company)，其中使2,4－及2,6－甲苯二異氰酸酯與三甲基醇丙烷反應，且以三莫耳異氰酸酯、一莫耳三甲基醇丙烷及三莫耳酚之比例酯化來封端。另一封端聚異氰酸酯為Mondur SHTM
(獲自Mobay Chemical Company)，其中經混合之2,4－及2,6－甲苯二異氰酸酯之異氰酸酯基係以甲酚酯化來封端。可單獨或以混合物形式使用之聚異氰酸酯包括：四亞甲基二異氰酸酯六亞甲基二異氰酸酯1,4－伸苯基二異氰酸酯1,3－伸苯基二異氰酸酯1,4－伸環己基二異氰酸酯2,4－甲苯二異氰酸酯2,5－甲苯二異氰酸酯2,6－甲苯二異氰酸酯3,5－甲苯二異氰酸酯4－氯－1,3－伸苯基二異氰酸酯1－甲氧基－2,4－伸苯基二異氰酸酯1－甲基－3,5－二乙基－2,6－伸苯基二異氰酸酯1,3,5－三乙基－2,4－伸苯基二異氰酸酯1－甲基－3,5－二乙基－2,4－伸苯基二異氰酸酯1－甲基－3,5－二乙基－6－氯－2,4－伸苯基二異氰酸酯6－甲基－2,4－二乙基－5－硝基－1,3－伸苯基二異氰酸酯對二甲苯二異氰酸酯間二甲苯二異氰酸酯4,6－二甲基－1,3－二甲苯二異氰酸酯1,3－二甲基－4,6－雙－(b－異氰酸酯基乙基)－苯3－(a－異氰酸酯基乙基)－苯基異氰酸酯1－甲基－2,4－伸環己基二異氰酸酯4,4'－伸聯苯基二異氰酸酯3,3'－二甲基－4,4'－伸聯苯基二異氰酸酯3,3'－二甲氧基－4,4'－伸聯苯基二異氰酸酯3,3'－二乙氧基－4,4－伸聯苯基二異氰酸酯1,1－雙－(4－異氰酸酯基苯基)環己烷4,4'－二異氰酸酯基－二苯醚4,4'－二異氰酸酯基－二環己基甲烷4,4'－二異氰酸酯基－二苯基甲烷4,4'－二異氰酸酯基－3,3'－二甲基二苯基甲烷4,4'－二異氰酸酯基－3,3'－二氯二苯基甲烷4,4'－二異氰酸酯基－二苯基二甲基甲烷1,5－伸萘基二異氰酸酯1,4－伸萘基二異氰酸酯4,4',4"－三異氰酸酯基－三苯基甲烷2,4,4'－三異氰酸酯基－二苯醚2,4,6－三異氰酸酯基－1－甲基－3,5－二乙基苯鄰聯甲苯胺－4,4'－二異氰酸酯間聯甲苯胺－4,4'－二異氰酸酯二苯甲酮－4,4'－二異氰酸酯縮二脲三異氰酸酯聚亞甲基聚伸苯基異氰酸酯
一般而言，將輕微莫耳過量之羧酸酐及有機多元胺係在惰性氣氛下且以如上所述之溶劑自約200℃(392℉)加熱至約245℃(473℉)。此舉分離出任何形成之水，且形成含有預聚物之醯胺醯亞胺基。隨後添加聚異氰酸酯且混合物反應形成具有相對高分子量之嵌段醯胺－醯亞胺預聚物。隨後將此固化(如藉由加熱)以形成可撓性薄膜或塗層。或者，使羧酸酐及有機二胺以等莫耳比例反應以提供需要之可撓性薄膜或塗層、導線瓷漆、油漆、疊層黏著劑及其類似物。
第二種更常用之方法涉及使用等莫耳量之羧酸酐及二異氰酸酯。聚合物分子量依賴於CO2
氣體之析出。聚合物通常在諸如NMP或DMF之惰性溶劑中合成。
如(例如)美國專利第3,817,926號中所教示，高達75莫耳百分比之羧酸酐可由經取代或未經取代之脂族酸酐或二酸(諸如草酸、順丁烯二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸及十二烷二酸)以及尤其包括順丁烯二酸物質及反丁烯二酸物質之不飽和物質替代。該等酸係由下式表示：HOOC－R'－COOH
其中R'為二價飽和或不飽和脂族基團，或含有一碳碳雙鍵且具有約1至40個碳原子之基團。該等酸酐可由下式表示：
用於該等物質之常用有機溶劑包括甲酚或甲苯酚、酚、二甲苯、N－甲基吡咯啶酮、二甲基甲醯胺、二甲亞碸、二甲基乙醯胺及其類似物；其不僅會在固化過程中污染大氣，且在一些實例中有毒或可燃且可造成嚴重化學灼傷。
上述聚醯胺醯亞胺之製備方法僅為例示性的，且其他方法係教示於所引用之專利中，以及與此項技術有關之文獻中，包括(例如)New Linear Polymers,Lee等人，McGraw－Hill,1967。
基於上述，其會為非常需要的，且若更廉價溶劑可用於製造該等組合物，則聚醯胺醯亞胺塗料組合物之高溫特性會更完全商業化地實現。
本發明揭示一種製造含有相對廉價溶劑系統之聚醯胺醯亞胺塗料組合物之方法。該等系統不僅在經濟上更可行以用於調配塗料組合物，且當其在樹脂基底之固化過程中蒸發時亦不產生不合意濃度之污染物。除最小化製備聚醯胺醯亞胺塗料組合物中目前所使用之昂貴有機溶劑的使用之外，另一優點在於使用諸如水之不僅較廉價且對環境較完全之溶劑的能力。
依據本發明之方法之一態樣，該等聚醯胺醯亞胺基底塗料組合物具有過量羧基官能性。該等過量羧酸酯基係經由添加三胺及三當量之三酸酐或兩當量之三酸酐及一當量之胺反應性水助溶基之縮合產物而併入。該等游離羧酸酯基係以容許於通常與聚醯胺醯亞胺樹脂不相容之水(或替代性溶劑)中還原之第三胺中和。
以下詳細描述作為實例且並非作為限制來說明本發明。此描述極會使熟習此項技術者能夠進行且使用本發明，且描述本發明之若干實施例、修改、改變、替代物及用途，其包括目前吾人認為實施本發明之最佳模式。儘管可在不脫離本發明之範疇情況下在上述構造中作出各種改變，但希望將以上描述中所含有或附圖中所展示之所有物質理解為說明性的且並非限制意義。
首先使三胺與兩或三當量之三酸酐反應。該三胺可為脂族三胺、芳族三胺或兩者之混合物。三胺可包含兩個第一胺及一或多個第二胺。可接受之三胺之實例包括(但不限於)二伸乙基三胺(DETA)、二伸丙基三胺(DPTA)及4,4'－二胺基二苯基胺(DADPA)。該三酸酐亦可包括三酸，諸如可經脫水為偏苯三甲酸酐之偏苯三甲酸。另一取代可為諸如偏苯三甲酸氯化物之三酸酐酸氯化物。
三酸酐首先與三胺上之兩個第一胺反應。在該兩個第一胺與三酸酐反應之後，諸如偏苯三甲酸酐、鄰苯二甲酸酐或對酞醯氯之水助溶基係用於與第二胺反應。
反應方程式係展示如下：
其中R為任何經取代或未經取代之脂族或芳族基團；R'及R"為H、經取代或未經取代之烷基或芳基(包括1,2－二取代之芳環基)；且R'''為任何經取代或未經取代之脂族或芳族基團。
在涉及二異氰酸酯及三酸酐之典型PAI合成中，使用1：1莫耳比率之二異氰酸酯及三酸酐。以上所示之三胺/三酸酐加合物可以三酸酐與二異氰酸酯之典型1：1比率置換10－90莫耳分率之三酸酐。隨後將所得溶液加熱至介於80－200℃(176－392℉)之間的溫度以增加聚合物分子量及所得黏度。
實現相同聚合物之第二種方法為將上述單體酸基團之兩者轉變為酸氯化物。此可藉由諸如亞硫醯氯或磷醯氯之試劑來實現。在涉及二胺及三酸酐酸氯化物之典型PAI合成中，使用1：1莫耳比率之二胺與三酸酐酸氯化物。以上所示之所得單體可以三酸酐酸氯化物與二胺之典型1：1比率置換10－90莫耳分率之三酸酐酸氯化物。隨後將所得溶液在室溫下攪拌以增加聚合物分子量及所得黏度。
以下展示3莫耳TMA與三胺之間的反應。縮合產物隨後置換TMA與亞甲基苯基二異氰酸酯(MDI)之反應中之一部分TMA。隨後獲得生成之聚醯胺醯亞胺聚合物以及其他衍生物。
適用於於水中還原聚合物材料之胺或含有胺基之物質較佳為第三胺且尤其包括二甲基乙醇胺、三乙醇胺、苯基甲基乙醇胺、丁基二乙醇胺、苯基二乙醇胺、苯基乙基乙醇胺、甲基二乙醇胺及三乙胺。第二胺亦適用。本發明之塗料組合物係製造為寬範圍之固體含量以適應與塗佈簡易及能力一致之特定應用。通常，自實踐之觀點看，固體含量在以固體重量計約10－40%或甚至更高之範圍內。
向160.0 g冰醋酸中添加38.4 g(2當量)之偏苯三甲酸酐及10.3 g(1當量)之二伸乙基三胺。將所得混合物在氮氣層下攪拌且將批料加熱至110－120℃(230－248℉)之回流溫度。保持一(1)小時。將批料冷卻至室溫且使產物自溶液沉澱析出。濾出產物，以乙醇洗滌且將該產物於一烘箱中乾燥。最終產物為淺棕色粉末。藉由NMR及MS對該物質進行表徵以確定具有未反應之第二胺之雙醯亞胺加合物的結構。
向160.0 g冰醋酸中添加38.4 g(2當量)之偏苯三甲酸酐及13.1 g(1當量)之二伸丙基三胺。將混合物在氮氣層下攪拌。將批料加熱至110－120℃(230－248℉)之回流溫度且保持一(1)小時。將批料冷卻至室溫且使產物自溶液沉澱析出。濾出產物，以乙醇洗滌且將該產物於一烘箱中乾燥。最終產物為白色粉末。藉由NMR及MS對該物質進行表徵以確定具有未反應之第二胺之雙醯亞胺加合物的結構。
向1000.0 g冰醋酸中添加384.2 g(2當量)之偏苯三甲酸酐及297.3 g(1當量)之4,4'－二胺基二苯基胺硫酸鹽。將混合物在氮氣層下攪拌。將批料加熱至110－120℃(230－248℉)之回流溫度且保持三(3)小時。將批料冷卻至室溫且使產物自溶液沉澱析出。濾出產物，以甲醇洗滌，且將該產物於一烘箱中乾燥。最終產物為深藍色粉末。藉由NMR及MS對該物質進行表徵以確定具有未反應之第二胺之雙醯亞胺加合物的結構。
向673.0 g冰醋酸中添加387.8 g(3當量)之偏苯三甲酸酐及200.1 g(1當量)之4,4'－二胺基二苯基胺硫酸鹽。將混合物在氮氣層下攪拌。將批料加熱至110－120℃(230－248℉)之回流溫度且保持六(6)小時。將批料冷卻至室溫且使產物自溶液沉澱析出。濾出產物，以甲醇洗滌，且將該產物於一烘箱中乾燥。最終產物為深藍色粉末。藉由NMR及MS對該物質進行表徵以確定具有偏苯三甲酸酐之第二醯胺之雙醯亞胺加合物的結構。
向1323.0 g之N－甲基－2－吡咯定酮中添加324.8 g(3當量)之偏苯三甲酸酐及58.2 g(1當量)之二伸乙基三胺。將混合物在氮氣層下攪拌。隨後，加熱至190℃(374℉)且保持餾出物減量。冷卻至60℃(140℉)且向溶液中添加433.1 g偏苯三甲酸酐及704.9 g 4,4'－亞甲基雙(苯基異氰酸酯)。接著將所得溶液首先加熱至95℃(203℉)且保持一(1)小時，隨後加熱至110℃(230℉)且保持一(1)小時，且隨後加熱至120℃(248℉)且保持直至溶液具有R之處理中加登納－荷耳得黏度(Gardner-Holt viscosity)。以23.1 g之甲醇使批料中止反應且以1488.2 g之N－甲基－2－吡咯啶酮使其變稀。將批料冷卻至25℃(77℉)且添加126.0 g之二甲醇胺。最終產物為深棕色、黏性液體。以水將此最終產物還原100%。所得混合物為半凝膠狀溶液。產物亦可於諸如二醇醚EB及丙酮之溶劑中還原以形成透明、均質溶液。
使用一梅爾(Meyer)棒將所得聚合物溶液塗佈於一鋁面板上以達到約15－20微米之乾薄膜厚度。在260℃(500℉)下將塗層於一通風烘箱中固化三十(30)分鐘。獲得具有良好黏著力及塗佈品質之黃色薄膜。
亦將所得溶液塗覆於以30－40英呎/分鐘(fpm)之速度用聚酯底塗層預塗佈四遍之18 AWG銅導線上且於一具有400－500℃(752－932℉)之溫度範圍之烘箱中固化。絕緣內建為約3.1－3.3 mil，其具有厚度為0.7－0.8 mil之聚醯胺醯亞胺面漆。導線性質與不具有聚合物主鏈中固有之酸官能基之對照樣品相當。
向1812.0 g之N－甲基－2－吡咯啶酮中添加597.2 g(3當量)之偏苯三甲酸酐及106.9 g(1當量)之二伸乙基三胺。將混合物在氮氣層下攪拌，加熱至190℃(374℉)，且保持餾出物減量。將批料冷卻至60℃(140℉)且向溶液中添加298.6 g偏苯三甲酸酐及648.1 g 4,4'－亞甲基雙(苯基異氰酸酯)。接著將所得溶液首先加熱至95℃(203℉)且保持一(1)小時，隨後加熱至110℃(230℉)且保持一(1)小時，且隨後加熱至120℃(248℉)且保持直至溶液具有S之處理中加登納－荷耳得黏度。以21.2 g之甲醇使批料中止反應且以1368.2 g之N－甲基－2－吡咯啶酮使其變稀。最終產物為深棕色、黏性液體。將批料冷卻至25℃(77℉)且添加282.0 g二乙醇胺。最終產物為深棕色、黏性液體。以水將此最終產物還原100%。所得混合物為既不含微粒亦不含凝膠物質之流體溶液。
使用一梅爾棒將所得聚合物溶液塗佈於一鋁面板上以達到約15－20微米之乾薄膜厚度。在260℃(500℉)下將塗層於一通風烘箱中固化三十(30)分鐘。獲得具有良好黏著力及塗佈品質之黃色薄膜，其由DSC顯示253℃(487℉)之Tg。
向1812.0 g之N－甲基－2－吡咯啶酮中添加597.2 g(3當量)之偏苯三甲酸酐、307.9 g(1當量)之4,4'－二胺基二苯基胺硫酸鹽及200 g之碳酸鈉。將混合物在氮氣層下攪拌，加熱至190℃(374℉)，且保持餾出物減量。將該所得混合物冷卻至60℃(140℉)且向溶液中添加298.6 g之偏苯三甲酸酐及648.1 g之4,4'－亞甲基雙(苯基異氰酸酯)。接著將所得溶液首先加熱至95℃(203℉)且保持一(1)小時，隨後加熱至110℃(230℉)且保持一(1)小時，且隨後加熱至120℃(248℉)且保持直至溶液具有S之處理中加登納－荷耳得黏度。以21.2 g之甲醇使批料中止反應且以1368.2 g之N－甲基－2－吡咯啶酮使其變稀。最終產物為深棕色液體。現冷卻至25℃(77℉)且添加282.0 g二乙醇胺。以水將此最終產物還原100%。所得混合物為既不含微粒亦不含凝膠物質之流體溶液。
向1323.0 g之N－甲基－2－吡咯啶酮中添加539.7 g(1當量)之偏苯三甲酸酐及702.6 g(1當量)之4,4'－亞甲基雙(苯基異氰酸酯)。接著將所得溶液首先加熱至95℃(203℉)且保持一(1)小時，隨後加熱至110℃(230℉)且保持一(1)小時，且隨後加熱至120℃(248℉)且保持直至溶液具有R之處理中加登納－荷耳得黏度。以23.1 g之甲醇使批料中止反應，且隨後以1488.2 g之N－甲基－2－吡咯啶酮使其變稀。冷卻至25℃(77℉)且添加126.0 g二乙醇胺。最終產物為深棕色、黏性液體且不可以水還原。水添加導致聚合物自溶液沉澱，產生黃色固體。以二醇醚EB或丙酮還原亦產生具有微粒物質之混濁溶液。
鑒於上述，應瞭解已達成本發明之若干目標及優點且已獲得其他有利結果。
Claims (10)
- 一種製造聚醯胺醯亞胺(PAI)樹脂之方法，該方法包含：使三酸酐與二異氰酸酯反應，其中10-90莫耳%之該三酸酐係被三胺與兩當量之三酸酐及一當量之具有下式之化合物之縮合產物所置換 及/或其中R'及R"為H、經取代或未經取代之烷基或芳基(包括1,2-二取代之芳環基)；且R'''為任何經取代或未經取代之脂族或芳族基團，其中該三胺包含兩個第一胺基團及一個第二胺基團。
- 如請求項1之方法，其中該三酸酐及該二異氰酸酯係以約等莫耳量反應。
- 如請求項1之方法，其中該三胺係為包含兩個第一胺及至少一個第二胺之脂族或芳族三胺。
- 如請求項1之方法，其中該三胺與該三酸酐之該縮合產物係為二伸乙基三胺(DETA)、二伸丙基三胺(DPTA)及二胺基二苯基胺(DADPA)之一或多者與約3當量偏苯三甲酸酐(TMA)之反應產物。
- 一種製造聚醯胺醯亞胺樹脂之方法，該方法包含：使三酸酐酸氯化物與二胺反應，其中10-90莫耳%之該三酸酐酸氯化物係被三胺與兩當量之三酸酐及一當量之具有下式之化合物之縮合產物所置換 及/或其中R'及R"為H、經取代或未經取代之烷基或芳基(包括1,2-二取代之芳環基)；且R'''為任何經取代或未經取代之脂族或芳族基團，其中該三胺包含兩個第一胺基團及一個第二胺基團。
- 如請求項5之方法，其中該等三胺及三酸酐之酸性基團係轉變為酸氯化物。
- 如請求項6之方法，其中該三酸酐酸氯化物與二胺係以約等莫耳量反應。
- 如請求項6之方法，其中在該三腔與三酸酐之該縮合產物中，該三胺係與約三當量之該三酸酐反應。
- 如請求項5之方法，其中該三胺為包含兩個第一胺及至少一個第二胺之脂族或芳族三胺。
- 如請求項5之方法，其中該三胺與三酸酐之縮合產物係為二伸乙基三胺(DETA)、二伸丙基三腔(DPTA)及二胺基二苯基胺(DADPA)之一或多者與約3當量偏苯三甲酸酐(TMA)之反應產物。
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| US11/314,267 US20070142616A1 (en) | 2005-12-21 | 2005-12-21 | Acid functional polyamideimides |
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| US10406791B2 (en) | 2011-05-12 | 2019-09-10 | Elantas Pdg, Inc. | Composite insulating film |
| US10253211B2 (en) | 2011-05-12 | 2019-04-09 | Elantas Pdg, Inc. | Composite insulating film |
| WO2018159459A1 (ja) * | 2017-03-03 | 2018-09-07 | 日本ゼオン株式会社 | ジアリールアミン系化合物、老化防止剤、およびポリマー組成物 |
| JP6915433B2 (ja) * | 2017-08-01 | 2021-08-04 | 昭和電工マテリアルズ株式会社 | ポリアミドイミド樹脂液及びその製造方法 |
| CN116836515B (zh) * | 2023-05-25 | 2023-12-29 | 广东安拓普聚合物科技股份有限公司 | 一种耐老化装饰用pcr热固性板材及其制备方法 |
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| US4481339A (en) * | 1983-09-15 | 1984-11-06 | General Electric Company | Acid-extended copolyamideimides and method for their preparation |
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| US3260691A (en) * | 1963-05-20 | 1966-07-12 | Monsanto Co | Coating compositions prepared from condensation products of aromatic primary diamines and aromatic tricarboxylic compounds |
| US3471444A (en) * | 1966-02-23 | 1969-10-07 | Gen Electric | Polyamide-imides and precursors thereof |
| US3518219A (en) * | 1967-08-31 | 1970-06-30 | Monsanto Co | Novel polyimide forming mixtures |
| US3518230A (en) * | 1968-01-04 | 1970-06-30 | Schenectady Chemical | Imide modified amide imide wire enamel |
| US3766117A (en) * | 1970-03-12 | 1973-10-16 | Gen Electric | Method of making a dispersion from polyamide acid |
| US3804793A (en) * | 1970-10-23 | 1974-04-16 | Gen Electric | Making polyamide-acid aqueous dispersions for electrocoating |
| US3817926A (en) * | 1970-12-14 | 1974-06-18 | Gen Electric | Polyamide-imides |
| US3737478A (en) * | 1971-05-28 | 1973-06-05 | Gen Electric | Method for making polyamide acid salts and products derived therefrom |
| US3810858A (en) * | 1971-12-13 | 1974-05-14 | Gen Electric | Method for recovering polyamide acid values from deteriorated dispersions of polyamide acid |
| GB1419881A (en) * | 1972-03-06 | 1975-12-31 | Sumitomo Electric Industries | Electrically insulated wire |
| US3975345A (en) * | 1972-06-23 | 1976-08-17 | General Electric Company | Polyamideimides and method for making |
| US3847878A (en) * | 1973-04-09 | 1974-11-12 | Standard Oil Co | Process for preparation of polyamide-imides and shaped articles of same |
| JPS5128297B2 (zh) * | 1973-08-16 | 1976-08-18 | ||
| JPS5118463B2 (zh) * | 1974-05-01 | 1976-06-10 | ||
| US4014834A (en) * | 1975-02-04 | 1977-03-29 | E. I. Du Pont De Nemours And Company | Aqueous solutions of polyamide acids which can be precursors of polyimide polymers |
| JPS63283705A (ja) * | 1987-05-13 | 1988-11-21 | Agency Of Ind Science & Technol | ポリアミドイミド選択透過膜 |
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2005
- 2005-12-21 US US11/314,267 patent/US20070142616A1/en not_active Abandoned
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2006
- 2006-12-06 TW TW095145274A patent/TWI461465B/zh not_active IP Right Cessation
- 2006-12-20 AT AT06830751T patent/ATE543855T1/de active
- 2006-12-20 EP EP06830751A patent/EP1963400B1/en not_active Not-in-force
- 2006-12-20 WO PCT/EP2006/069990 patent/WO2007071717A2/en not_active Ceased
- 2006-12-20 ES ES06830751T patent/ES2378470T3/es active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259221A (en) * | 1976-12-20 | 1981-03-31 | General Electric Company | Water-soluble polyamideimides |
| US4252707A (en) * | 1977-01-04 | 1981-02-24 | Ruid John O | Polyamide-imide-acid binder with amine base |
| US4481339A (en) * | 1983-09-15 | 1984-11-06 | General Electric Company | Acid-extended copolyamideimides and method for their preparation |
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| Publication number | Publication date |
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| TW200740884A (en) | 2007-11-01 |
| WO2007071717A2 (en) | 2007-06-28 |
| EP1963400A2 (en) | 2008-09-03 |
| WO2007071717A3 (en) | 2007-08-30 |
| ES2378470T3 (es) | 2012-04-12 |
| US20070142616A1 (en) | 2007-06-21 |
| ATE543855T1 (de) | 2012-02-15 |
| EP1963400B1 (en) | 2012-02-01 |
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