A series of“hairy-rod”polyimides,BBPA(n),with multiple alkyl side chains was prepared from 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA)and 4,4'-biphenyldiamine substituted in the 2,2'-position...A series of“hairy-rod”polyimides,BBPA(n),with multiple alkyl side chains was prepared from 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA)and 4,4'-biphenyldiamine substituted in the 2,2'-positions with benzoate,whichwas substituted in the 3,4,5-positions with ether side chains of varying lengths.The number of the methylene units,n,inthese alkyl side chains were in even numbers ranging from 8 to 18.Combining techniques of one-dimensional(1D)and 2Dwide angle x-ray diffraction,1D small angle X-ray scattering,differential scanning calorimetry experiments,it was found thatthis series of“hairy-rod”polyimides possess a micro-phase separation between the backbones and side chains.This led to theformation of ordered structures in two different length scales,of which both are hexagonal packing:one is attributed to thealkyl side chains on the sub-nanometer scale,and another is for the whole polymer chains on the nanometer scale.Thedevelopment of the hexagonal structure on the sub-nanometer scale was critically dependent upon the lengths of the alkylside chains.Three relaxation processes were captured by dynamic mechanical analysis,i.e.,segmental motion of thebackbones,α,the melting of the side chain crystals,β_1,which exits only for the materials with longer side chains(n=18,16);and the subglass relaxation of side chains,β_2.The peak relaxation temperature of the α process decreased withincreasing the length of side chains,while the one of the β_2 process increased.The activation energy of the α relaxation wasrelatively independent on the length of side chain,whereas,β_2 process showed the increasing of activation energy withincreasing the length of side chains.展开更多
We report on generating uniaxial negative birefringent compensation films, made of specifically designedpolyimides. These polymers were synthesized via a polycondensation of dianhydride [such as 2, 2' -bis(3, 4-di...We report on generating uniaxial negative birefringent compensation films, made of specifically designedpolyimides. These polymers were synthesized via a polycondensation of dianhydride [such as 2, 2' -bis(3, 4-dicarboxyphenyl)hexafluoropropane dianhydride] and 2, 2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. The uniaxial negative birefringent (n_x =n_y > n_z) polyimide substrates are achieved using a solution-casting method in conventional solvents, which exhibit thedesirable optical phase retardation [(n_x - n_z)×d] values from 50 to 400 nm varying with the film thickness. In thesepolyimide films, the long chain rigid molecules adopt intrinsic planar orientaion. In detail, the majority of phenylene-imiderings and phenylenes preferentially adopt nearly planar conformations parallel to the film substrae. In addition, these filmsalso possess high transparency (or transmittance) and little color shift. The unique color dispersion curve indicates that thistype of materials is very suitable for the applications in LCDs due to an excellent mimic for the retardation color dispersioncurve with respect to LC molecules. Significantly low in-plane retardation (< 1 nm) allows this new technology based film toachieve sufficiently high contrast ratio while highly negative retardation dramatically suppresses the gray scale inversion toimprove the viewing angle performance in a variety of new mode LCDs.展开更多
基金This work was supported by the NSF(DMR-0203994).
文摘A series of“hairy-rod”polyimides,BBPA(n),with multiple alkyl side chains was prepared from 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA)and 4,4'-biphenyldiamine substituted in the 2,2'-positions with benzoate,whichwas substituted in the 3,4,5-positions with ether side chains of varying lengths.The number of the methylene units,n,inthese alkyl side chains were in even numbers ranging from 8 to 18.Combining techniques of one-dimensional(1D)and 2Dwide angle x-ray diffraction,1D small angle X-ray scattering,differential scanning calorimetry experiments,it was found thatthis series of“hairy-rod”polyimides possess a micro-phase separation between the backbones and side chains.This led to theformation of ordered structures in two different length scales,of which both are hexagonal packing:one is attributed to thealkyl side chains on the sub-nanometer scale,and another is for the whole polymer chains on the nanometer scale.Thedevelopment of the hexagonal structure on the sub-nanometer scale was critically dependent upon the lengths of the alkylside chains.Three relaxation processes were captured by dynamic mechanical analysis,i.e.,segmental motion of thebackbones,α,the melting of the side chain crystals,β_1,which exits only for the materials with longer side chains(n=18,16);and the subglass relaxation of side chains,β_2.The peak relaxation temperature of the α process decreased withincreasing the length of side chains,while the one of the β_2 process increased.The activation energy of the α relaxation wasrelatively independent on the length of side chain,whereas,β_2 process showed the increasing of activation energy withincreasing the length of side chains.
基金This work was supported by the NSF Science and Technology Center of Advanced Liquid Crystalline Optical Materials (ALCOM, DMR-91-57738) and Nitto Denko America as well as NSF DMR0203994.
文摘We report on generating uniaxial negative birefringent compensation films, made of specifically designedpolyimides. These polymers were synthesized via a polycondensation of dianhydride [such as 2, 2' -bis(3, 4-dicarboxyphenyl)hexafluoropropane dianhydride] and 2, 2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. The uniaxial negative birefringent (n_x =n_y > n_z) polyimide substrates are achieved using a solution-casting method in conventional solvents, which exhibit thedesirable optical phase retardation [(n_x - n_z)×d] values from 50 to 400 nm varying with the film thickness. In thesepolyimide films, the long chain rigid molecules adopt intrinsic planar orientaion. In detail, the majority of phenylene-imiderings and phenylenes preferentially adopt nearly planar conformations parallel to the film substrae. In addition, these filmsalso possess high transparency (or transmittance) and little color shift. The unique color dispersion curve indicates that thistype of materials is very suitable for the applications in LCDs due to an excellent mimic for the retardation color dispersioncurve with respect to LC molecules. Significantly low in-plane retardation (< 1 nm) allows this new technology based film toachieve sufficiently high contrast ratio while highly negative retardation dramatically suppresses the gray scale inversion toimprove the viewing angle performance in a variety of new mode LCDs.
