CN1034339C - 新型热致液晶聚酯酰亚胺的合成 - Google Patents
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Abstract
本发明属于新型热致液晶高分子聚酯酰亚胺的合成。
本发明以对羟基苯甲酸、含酰亚胺键二元酸及各种芳香族二元酚为单体,在催化剂三氧化二锑、醋酸锌、醋酸锰,以及三氧化二锑/醋酸锌、三氧化二锑/醋酸锰作用下,采用直接熔融缩聚/固相缩聚法合成新型液晶高分子聚醋酰亚胺,通过对单体配比进行调整合成出不同玻璃化转变及熔融温度的系列热致液晶高分子聚酯酰亚胺。
Description
本发明属于新型热致液晶高分子聚酯酰亚胺的合成。
热致液晶高分子材料自八十年代中期工业化以来,作为一种具有性能优异的材料日益受到人们的重视。德国的Kricheldorf,H.R.1987年首次报道了热致液晶聚酯酰亚胺的合成研究,从而开发了一种新型热致液晶高分子。该类液晶高分子既含酯键又含酰亚胺键,综合了聚酯及聚酰亚胺的优异性能,有望成为一类耐热工程塑料,液晶又赋予它一些特殊的性能,如:优异的热性能、机械性能、较低的线膨胀系数、较高的自取向性能等。
日本公开特许公报80-91818以对羟基苯甲酸、对苯二酚、对苯二甲酸、碳原子数为4-8的N,N′-烷撑-α,ω-双-偏苯三酸酰亚胺(I)制备了聚酯酰亚胺,由于玻璃化转变温度较低,主要用于纤维和压片。
Babe,S.G.采用碳原子数为2-6的N,N′-烷撑-α,ω-双-偏苯三酸酰亚胺(I)与联苯双酚酯制得了热致液晶聚酯酰亚胺(Makromol.Chem.21,65-77,1972.),由于有许多缺点而应用价值不大。在专利DE3516427A1中,德国的Kricheldorf,H.R.采用碳原子为8-16的N,N′烷撑-α,ω-双-偏苯三酸酰亚胺(I)与联苯二酚(II)由酯交换法、甲硅烷基化法制得了聚酯酰亚胺。
其中X为1-7碳原子烷撑,5-12碳原子的环烷撑,O,S,SO,SO2,CO,以及它们的中心烷基化衍生物。Dike,H.R.由对羟基苯甲酸及含酰亚胺键羟基酸(III)采用酯交换法合成了高热稳定性的聚酯酰亚胺,他选用的催化剂范围较广:路易斯酸,氢卤酸,氧化物,氢化物,卤化物,酚盐,无机盐,有机盐,碱土金属的复盐或混盐等。
在专利EP0293713中,Kricheldorf,H.R.综合了专利DE-OS2025971及DE-OS3516427由对羟基苯甲酸及单元IV、V采用直接熔融缩聚法和酯交换法合成了聚酯酰亚胺。
n为3-2的整数,
HO-Ar-OH (V)
其中单体V为1,4-苯撑或4,4′-联苯撑或它们的混合物。
本发明的目的是以对羟基苯甲酸、含酰亚胺键二元酸及各种芳香族二元酚为单体,在催化剂三氧化二锑、醋酸锌、醋酸锰,以及三氧化二锑/醋酸锌、三氧化二锑/醋酸锰作用下,采用直接熔融缩聚/固相缩聚法合成新型聚酯酰亚胺液晶高分子,通过对单体配比进行调整合成出不同玻璃化转变及熔融温度的系列热致液晶高分子。
1.本发明采用的单体及结构为:
其中Y为O,S,SO2,CO,C(CH3)2,及其烷基取代衍生物;
对羟基苯甲酸的用量为20-80mol%,二元酸与二元酚的单体配比(mol)为0.98∶1-1.02∶1;
2、本发明中采用的催化剂有:三氧化二锑、醋酸锌、醋酸锰;以及三氧化二锑/醋酸锌(2.5∶1-1∶2.5)、三氧化二锑/醋酸锰(2.5∶1-1∶2.5)复合催化剂,投入量占单体投入总量的0.01-0.2wt%;
在上述催化体系、单体及配比下,以醋酸酐为反应介质,氮气保护下,于200-250℃下预聚2-4h。之后,迅速升温至290-320℃,高温聚合2-4h,然后密封反应体系,维持真空度在133-665Pa之间,熔态下继续聚合反应2-8h,得到韧性好,可拉成纤维的棕褐色产物,收率为90-98%;
所得液晶聚合物纤维,置于190-250℃下,维持真空度在133-250Pa之间进行固相后聚合,可明显提高纤维的力学强度和聚合物的分子量。
聚酯酰亚胺液晶高分子在三氟乙酸/二氯甲烷(体积比25/2)的混合溶剂中,采用乌氏粘度计25℃下测得粘度范围0.45-0.65。
由本发明中的液晶高分子对高性能树脂PES-C、PEK-C、PI、PES、PEEK等进行改性,其中液晶材料含量为2.0-30wt%,所制得的原位复合材料在不降低基体树脂的综合物理力学性能的基础上,可明显地降低树脂的熔体粘度、加工压力和加工温度,从而改善了基体树脂的熔体加工性能。
聚芳醚酮PEK-C50,PEK-C63分别为注射级和模压级的高性能树脂,将本发明中的热致液晶聚酯酰亚胺与聚芳醚酮通过熔融共混(液晶含量为10wt%),可明显降低基体树脂的熔体加工粘度,加工温度和加工压力,基体树脂及其共混物的综合力学性能见表1。
实施例1
在装有机械搅拌器、冷凝器、水分离器、有氮气出入口的2L的三口瓶中,投入对羟基苯甲酸41.5g(0.30mol),4,4′羟二苯酮75.0g(0.35mol),酰亚胺二酸(n=6)162.6g(0.35mol),以及醋酸酐250ml,醋酸锰0.03g,三氧化二锑0.04g,将反应瓶置于铝加热套中,在氮气保护下,温度升高到250℃左右使体系保持回流状态2h,然后蒸除醋酸、水及过量的醋酸酐,迅速升温到300℃,保温2h,除去水分离器,关闭氮气,在此温度下减压抽空至665Pa,保持2h,在熔融态下取出产物,得产物252g,产率:91%,玻璃化转变温度Tg:92℃,熔融温度Tm:227℃,特性粘度:0.23。熔融样品在偏光显微镜下可观察到双折射现象,具有向列型液晶特性的织构。
实施例2
实验方法同实施例1,加入对羟基苯甲酸69.1g(0.5mol)4,4′二羟基二苯酮53.6g(0.25mol),含酰亚胺键二元酸(n=6)116.1g(0.25mol),醋酸酐250ml,醋酸锌0.05g,三氧化二锑0.06g,得产物210g,产率:95%,玻璃化转变温度Tg:89℃,熔融温度Tm:215℃,特性粘度:0.60%。所得棕褐色产物很容易直接拉成较韧的丝,其力学性能与所拉成的丝的直径成反比,也就是愈细的丝取向程度愈高,力学性能愈好。
表2.聚酯酰亚胺丝的力学性能与其直径的关系*
*括号内为经固相缩聚后结果实施例3实验方法同实施例1,投入单体对羟基苯甲酸96.7g(0.7mol),酰亚胺二元酸(n=6)69.7g(0.15mol),4,4′-二羟基二苯酮32.1g(0.15mol),以及醋酸酐250ml,醋酸锌0.07g,得产物172g,产率:96%,玻璃化转变温度Tg:75℃熔融温度Tm:207℃,特性粘度:0.45。样品在偏光显微镜下观察到双折射现象,具有向列型液晶特性。
d(mm) | 拉伸强度(MPa) | 断裂伸长(%) | 拉伸模量(MPa) |
1.580.700.650.50 | 130.6(153.6)144.2(194.3)150.7(215.6)164.1(260.8) | 19.7(15.3)12.4(9.6)7.1(5.4)6.7(4.3) | 2032(2983)3291(4279)3291(4721)3887(5227) |
实施例4
实验方法同实施例1,投入单体对羟基苯甲酸69.1g(0.5mol),含酰亚胺键二元酸(n=6)116.1g(0.25mol),1,4-萘二酚40g(0.25mol),以及醋酸酐250ml,醋酸锌0.04g,三氧化二锑0.04g,所得产物具有明显的向列型液晶特征,并且有很强的韧性,共得产物192g,产率:93%,玻璃化转变温度Tg:104℃,熔融温度Tm:267℃,特性粘度:0.29。
实施例5
实验方法同实施例1,投入单体对羟基苯甲酸69.1g(0.5mol),酰亚胺二元酸(n=8)123.1g(0.25mol),对苯二酚27.5g(0.25mol),以及醋酸酐250ml,三氧化二锑0.08g,所得产物具有明显的向列型液晶特征,共得产物190g,产率:95%,
实施例6
实验方法同实施例1,单体对羟基苯甲酸96.7g(0.7mol),酰亚胺二元酸(n=4)65.5g(0.15mol),间苯二酚16.5g(0.15mol),以及醋酸酐250ml,醋酸锰0.08g,所得产物具有明显的向列型液晶特征,得产物152g,产率:95%,表1.LCP/PER-C共混物与基体树脂力学性能的比较
性能 PEK-C50/LCP PEK-C63/LCP PEK-C50 PEK-C63拉伸强度(MPa) 108 110 105 102拉伸模量(GPa) 2.49 3.77 1.76 2.43断裂伸长度(%) 9.13 7.28 39.9 6.1弯曲强度(MPa) 172 169 166 132弯曲模量(GPa) 1.92 2.71 3.10 2.74
冲击强度无缺口(KJ/m2) 170.6 214.8 147 -缺口(J/m) 32.2 32.2 70 46玻璃化转变(℃) 206 219
Claims (1)
1.一种新型热致液晶高分子聚酯酰亚胺的合成方法,其特征在于采用直接熔融缩聚/固相缩聚法合成,合成步骤如下:
①本发明采用的单体及结构为:
A.对羟基苯甲酸:
B.含柔性链段酰亚胺键二元酸单体:其中n为4-12的整数;
C.芳香族二元酚:
其中Y为O,S,SO2,CO,C(CH3)2,及其烷基取代衍生物:
其中对羟基苯甲酸的用量为20-80mol%,二元酸与二元酚的单体配比(mol)为0.98∶1-1.02∶1;
②本发明中采用的催化剂有:三氧化二锑、醋酸锌、醋酸锰;以及三氧化二锑/醋酸锌(2.5∶1-1∶2.5)、三氧化二锑/醋酸锰(2.5∶1-1∶2.5)复合催化剂,投入量占单体投入总量的0.01-0.2wt%;
③在上述催化体系、单体及配比下,以醋酸酐为反应介质,氮气保护下,于200-250℃下预聚2-4h,之后,迅速升温至290-320℃,高温聚合2-4h,然后密封反应体系,维持真空度在133-665Pa之间,熔态下继续聚合反应2-8h,得到韧性好,可拉成纤维的棕褐色产物,收率为90-98%;
④所得液晶聚合物纤维,置于190-250℃下,维持真空度在133-250Pa之间进行固相后聚合4-8h,获得高力学强度和高分子量液晶聚合物。
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CN94116639A CN1034339C (zh) | 1994-10-20 | 1994-10-20 | 新型热致液晶聚酯酰亚胺的合成 |
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CN94116639A CN1034339C (zh) | 1994-10-20 | 1994-10-20 | 新型热致液晶聚酯酰亚胺的合成 |
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AU2003235407A1 (en) * | 2002-06-12 | 2003-12-31 | Mitsubishi Chemical Corporation | Process for producing polyester resin |
CN101508897B (zh) * | 2009-03-11 | 2011-11-09 | 中山大学 | 新型可纺性热致液晶聚酯酰亚胺及其合成方法和应用 |
CN101560294B (zh) * | 2009-05-19 | 2011-11-09 | 中山大学 | 一种相容性热致液晶聚合物及其制备方法和应用 |
CN106810695B (zh) * | 2017-01-12 | 2019-09-06 | 苏州大学 | 一种芳香族聚酯酰亚胺及其制备方法 |
CN109825082A (zh) * | 2019-02-10 | 2019-05-31 | 成都其其小数科技有限公司 | 一种聚酯酰亚胺/双马来酰亚胺树脂复合材料及制备方法 |
Citations (4)
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---|---|---|---|---|
DE3516427A1 (de) * | 1985-05-08 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | Thermotrope aromatische polyesterimide mit hoher waermeformbestaendigkeit, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von formkoerpern, filamenten, fasern und folien |
EP0293713A1 (de) * | 1987-06-02 | 1988-12-07 | Bayer Ag | Thermotrope Polyesterimide mit ausgezeichneter Verarbeitbarkeit, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien |
US4988792A (en) * | 1990-01-19 | 1991-01-29 | General Electric Company | Liquid crystalline polyesteretherimide from a bisimidodiphenol |
US5173562A (en) * | 1990-10-29 | 1992-12-22 | Chisso America Inc. | Liquid crystal polymer composition containing bisphenol A in combination with 4,4'-thiodiphenol |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3516427A1 (de) * | 1985-05-08 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | Thermotrope aromatische polyesterimide mit hoher waermeformbestaendigkeit, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von formkoerpern, filamenten, fasern und folien |
EP0293713A1 (de) * | 1987-06-02 | 1988-12-07 | Bayer Ag | Thermotrope Polyesterimide mit ausgezeichneter Verarbeitbarkeit, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien |
US4988792A (en) * | 1990-01-19 | 1991-01-29 | General Electric Company | Liquid crystalline polyesteretherimide from a bisimidodiphenol |
US5173562A (en) * | 1990-10-29 | 1992-12-22 | Chisso America Inc. | Liquid crystal polymer composition containing bisphenol A in combination with 4,4'-thiodiphenol |
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