AB型PBO新单体的合成及其树脂制备探索
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摘要
本文针对目前唯一由日本Toyobo公司生产的PBO纤维及树脂中存在的不足，在制得关键中间体4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)的基础上，设计其与对甲氧羰基苯甲酰氯(MBC)进行缩合反应获得苯并噁唑化合物5-硝基-6-羟基-2-(对甲氧羰基苯基)苯并噁唑(MHNB)后，通过加氢或水解、还原分别制得AB型PBO新单体：5-氨基-6-羟基-2-(对甲氧羰基苯基)苯并噁唑(MAB)、5-氨基-6-羟基-2-(对羧基苯基)苯并噁唑(ABA)及其磷酸盐(ABA·H_3PO_4)。其分子结构已经IR，~1H-NMR，~(13)C-NMR定性分析所确认，并对它们进行均缩聚合成PBO树脂的研究探索。
在所研究的路线中，以选择ANR·HCl与MBC缩环合成MHNB，然后将水解、还原两步反应集一锅内原位合成ABA的工艺是较为理想的方法，纯度98.2％，总收率75.96％；同时详细研究了制备MHNB的缩环合反应机理，运用机理指导合成的方法，确定PPA的用量是此反应中最关键的因素，其较佳用量PPA／ANR·HCl为5：1，并在120℃和150℃下分别反应2h和3h，得到MHNB纯度93.53％，收率89.9％。
在对玻璃聚合反应器进行有效改进的基础上，研究DAR·2HCl-TPA，DAR／TPA等共缩聚反应，分别获得了特性粘数为7.03，0.99 dl／g的PBO树脂；重点研究了以ABA及ABA·H_3PO_4制备PBO树脂的过程，得到经IR定性准确分子量达15000以上的PBO树脂，相应的特性粘数为9.18dl／g。同时研究了较准确测定特性粘数的方法，其中“一点法”则可以作为测定PBO树脂特性粘数简便有效的方法，相对于准确的“外推法”其误差在～13％之内。
本文从改善PBO树脂抗压缩性能及粘结性能等方面考虑，设计了带有羟基改性基团的AB型新单体2-(2，5-二羟基对羧基苯基)-5-氨基-6-羟基苯并噁唑(DHABA)合成路线，并成功制备了其前体物质2-(2，5-二羟基对羧基苯基)-5-硝基-6-羟基苯并噁唑(DHNBA)及过程中所需的共缩聚新单体2，5-二羟基对苯二甲酸(2，5-DHTA)，为进一步提高PBO的性能提供物质来源。同时采用DAR·2HCl与2，5-DHTA进行共缩聚制得特性粘数为2.53dl/g的改性PBO树脂。
New AB-type monomers are contrived in order to increase the performance of PBO resin and novel methods for preparing these monomers: Methyl 4-(5-amino-6-hydroxybenzoxazol-2-yl)benzoate (MAB), 4-(5 -amino-6-hydroxybenzoxazol-2-yl)-benzoic acid (ABA) and its phosphate are also described in this paper. The results are as follows:By condensation-cyclization reaction starting from 4-amino-6-nitroresorcinol hydrochloride (ANR-HCl) and methoxycarbonyl benzoyl chloride (MBC), 2-(4-meth-oxycarbonylphenyl)- 6-hydroxy-5-nitrobenzoxazole (MHNB) is prepared with the better yield of 89.9% and the HPLC purity of 93.53%. We explored the mechanism of this reaction and found that the dosage of PPA is a key factor.The MAB monomer is prepared from MHNB by catalytic hydrogenation with the yield of 87.49% and the HPLC purity of 98.99%. The total yield form ANR-HCl is 78.65%. At the same time, the ABA monomer is synthesized from MHNB via one pot method after hydrolyzation and hydrogenation reaction with the yield of 75.96% based on ANR-HCl and the HPLC purity of 98.2%. The chemical structure of MHNB and AB-type monomers are all identified by FT-IR, ~1H-NMR and ~(13)C-NMR.Further exploring polymeric experiments are carried out with the improvement of equipment designed. The PBO resin is prepared from different monomers, such as 4,6-diaminoresorciol dihydrochloride-terephthalic acid (DAR·2HCl-TPA), DAR/TPA, which has intrinstic viscosity of 7.03, 0.99dl/g in methansulfonic acid at 30℃respectively. Much attention is attached to the studies on PBO resin prepartion with ABA monomer and its phosphate, we have got the highest intrinstic viscosity (9.18 dl/g) and molecular weight (15000) PBO resin in glassware. These results show that the ABA monomer and its phosphate have the best polymeric capacity for preparing PBO resin.
We also explored other new AB type monomer dihydroxy-ABA(DHABA) in order to improving adhesive ability and resisting compression performance of PBO resin. The key material of 2,5-dihydroxyterephthalic acid (2,5-DHTA) is prepared from 1,4-benzendiol with the purity more than 99.5%, and other new substances, such as 2-(2,5-dihydroxy-4-carboxyphenyl)-5-nitro-6-hydroxybenzoxazole (DHNBA) are synthesized from 2,5-DHTA and all confirmed by ~(13)C-NMR. We have got PBO resin with -OH group from DAR.2HCl and 2,5-DHTA, whose the intrinstic viscosity is 2.53dl/g.
在所研究的路线中，以选择ANR·HCl与MBC缩环合成MHNB，然后将水解、还原两步反应集一锅内原位合成ABA的工艺是较为理想的方法，纯度98.2％，总收率75.96％；同时详细研究了制备MHNB的缩环合反应机理，运用机理指导合成的方法，确定PPA的用量是此反应中最关键的因素，其较佳用量PPA／ANR·HCl为5：1，并在120℃和150℃下分别反应2h和3h，得到MHNB纯度93.53％，收率89.9％。
在对玻璃聚合反应器进行有效改进的基础上，研究DAR·2HCl-TPA，DAR／TPA等共缩聚反应，分别获得了特性粘数为7.03，0.99 dl／g的PBO树脂；重点研究了以ABA及ABA·H_3PO_4制备PBO树脂的过程，得到经IR定性准确分子量达15000以上的PBO树脂，相应的特性粘数为9.18dl／g。同时研究了较准确测定特性粘数的方法，其中“一点法”则可以作为测定PBO树脂特性粘数简便有效的方法，相对于准确的“外推法”其误差在～13％之内。
本文从改善PBO树脂抗压缩性能及粘结性能等方面考虑，设计了带有羟基改性基团的AB型新单体2-(2，5-二羟基对羧基苯基)-5-氨基-6-羟基苯并噁唑(DHABA)合成路线，并成功制备了其前体物质2-(2，5-二羟基对羧基苯基)-5-硝基-6-羟基苯并噁唑(DHNBA)及过程中所需的共缩聚新单体2，5-二羟基对苯二甲酸(2，5-DHTA)，为进一步提高PBO的性能提供物质来源。同时采用DAR·2HCl与2，5-DHTA进行共缩聚制得特性粘数为2.53dl/g的改性PBO树脂。
New AB-type monomers are contrived in order to increase the performance of PBO resin and novel methods for preparing these monomers: Methyl 4-(5-amino-6-hydroxybenzoxazol-2-yl)benzoate (MAB), 4-(5 -amino-6-hydroxybenzoxazol-2-yl)-benzoic acid (ABA) and its phosphate are also described in this paper. The results are as follows:By condensation-cyclization reaction starting from 4-amino-6-nitroresorcinol hydrochloride (ANR-HCl) and methoxycarbonyl benzoyl chloride (MBC), 2-(4-meth-oxycarbonylphenyl)- 6-hydroxy-5-nitrobenzoxazole (MHNB) is prepared with the better yield of 89.9% and the HPLC purity of 93.53%. We explored the mechanism of this reaction and found that the dosage of PPA is a key factor.The MAB monomer is prepared from MHNB by catalytic hydrogenation with the yield of 87.49% and the HPLC purity of 98.99%. The total yield form ANR-HCl is 78.65%. At the same time, the ABA monomer is synthesized from MHNB via one pot method after hydrolyzation and hydrogenation reaction with the yield of 75.96% based on ANR-HCl and the HPLC purity of 98.2%. The chemical structure of MHNB and AB-type monomers are all identified by FT-IR, ~1H-NMR and ~(13)C-NMR.Further exploring polymeric experiments are carried out with the improvement of equipment designed. The PBO resin is prepared from different monomers, such as 4,6-diaminoresorciol dihydrochloride-terephthalic acid (DAR·2HCl-TPA), DAR/TPA, which has intrinstic viscosity of 7.03, 0.99dl/g in methansulfonic acid at 30℃respectively. Much attention is attached to the studies on PBO resin prepartion with ABA monomer and its phosphate, we have got the highest intrinstic viscosity (9.18 dl/g) and molecular weight (15000) PBO resin in glassware. These results show that the ABA monomer and its phosphate have the best polymeric capacity for preparing PBO resin.
We also explored other new AB type monomer dihydroxy-ABA(DHABA) in order to improving adhesive ability and resisting compression performance of PBO resin. The key material of 2,5-dihydroxyterephthalic acid (2,5-DHTA) is prepared from 1,4-benzendiol with the purity more than 99.5%, and other new substances, such as 2-(2,5-dihydroxy-4-carboxyphenyl)-5-nitro-6-hydroxybenzoxazole (DHNBA) are synthesized from 2,5-DHTA and all confirmed by ~(13)C-NMR. We have got PBO resin with -OH group from DAR.2HCl and 2,5-DHTA, whose the intrinstic viscosity is 2.53dl/g.
引文
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