This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characteri...This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.展开更多
A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide...A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide（PI） films with different side chain contents was synthesized from biphenyltetracarboxylicdianhydride（BPDA）,4,4＇-oxydianiline（ODA） and C6BBC4,and their thermal properties,optical transparency and liquid crystal alignment property,and so on,were investigated by thermogravimetric analysis（TGA）,differential scanning calorimetry（DSC）,crystal rotation method,polarizing microscopy and UV-Vis spectra.With the content of side chained diamine increasing from 0 to 100%,the η inh of poly（amide acid）（PAA） decreased rapidly from 3.0 to 0.51,the glass transition temperature（T g） of polyimides（PIs） decreased from 274 ℃ to 203 ℃ and the Vis-light transmittance of alignment films substantially increased.As for the alignment properties,the pretilt angle of PI alignment films without rubbing could reach 90° when the content of C6BBC4 was 60% or more.At the same time,the alignment stability could meet the industrial requirements.It was considered that the alkoxy spacer,the biphenyl unit and the alkoxy tail may all play important roles in achieving a large pretilt angle even up to 90°,and the introduction of only the alkoxy spacer or alkoxy tail can also improve the pretilt angle,but not by much.展开更多
基金We are grateful to the National Natural Science Foundation of China for financial support(project No.20274026)
文摘This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.
基金Supported by the National Natural Science Foundation of China(Nos.50773044,50973073)
文摘A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide（PI） films with different side chain contents was synthesized from biphenyltetracarboxylicdianhydride（BPDA）,4,4＇-oxydianiline（ODA） and C6BBC4,and their thermal properties,optical transparency and liquid crystal alignment property,and so on,were investigated by thermogravimetric analysis（TGA）,differential scanning calorimetry（DSC）,crystal rotation method,polarizing microscopy and UV-Vis spectra.With the content of side chained diamine increasing from 0 to 100%,the η inh of poly（amide acid）（PAA） decreased rapidly from 3.0 to 0.51,the glass transition temperature（T g） of polyimides（PIs） decreased from 274 ℃ to 203 ℃ and the Vis-light transmittance of alignment films substantially increased.As for the alignment properties,the pretilt angle of PI alignment films without rubbing could reach 90° when the content of C6BBC4 was 60% or more.At the same time,the alignment stability could meet the industrial requirements.It was considered that the alkoxy spacer,the biphenyl unit and the alkoxy tail may all play important roles in achieving a large pretilt angle even up to 90°,and the introduction of only the alkoxy spacer or alkoxy tail can also improve the pretilt angle,but not by much.
