CN1269874C - Novel copolypolyimide and its preparation process - Google Patents

Novel copolypolyimide and its preparation process Download PDF

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CN1269874C
CN1269874C CN 200510011871 CN200510011871A CN1269874C CN 1269874 C CN1269874 C CN 1269874C CN 200510011871 CN200510011871 CN 200510011871 CN 200510011871 A CN200510011871 A CN 200510011871A CN 1269874 C CN1269874 C CN 1269874C
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polyimide
multiblock
dianhydride
preparation
acid anhydride
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CN1693338A (en
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詹茂盛
鲁云华
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Beihang University
Beijing University of Aeronautics and Astronautics
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Beihang University
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Abstract

The present invention relates to copolyimides (CPI) with multiple block sections and a preparation method thereof. The CPI is synthesized from more than one dianhydride and more than one diamine. The present invention uses biphenyl tetracid dianhydride (symmetrical isomers and asymmetrical isomers) and/or tetracarboxylic dianhydride as fixed dianhydride to carry out multiple copolymerization with other kinds of dianhydride and diamine in a strong polar solvent, and the proportion of a rigid section and a soft section can be arbitrarily adjusted. The synthesized copolymerization polyamic acid can be prepared into a thin film by hot imidization or be prepared into powder by chemical imidization. The glass transition temperature of the copolymerization polyimide is from 200 to 400 DEG C, and the processing performance of the copolymerization polyimide is good.

Description

A kind of novel copolypolyimide and preparation method thereof
Technical field
The present invention relates to a kind of novel copolypolyimide and preparation method thereof.
Background technology
(copolyimides is a kind of multiblock polyimide (Multi-blockcopolyimides) CPI) to novel copolypolyimide of the present invention, and belonging to is polyimide (polyimides, PI) certain species in the family.And PI is the big veriety that over-all properties is best in the macromolecular material, temperature tolerance is the highest.
In this big veriety of polyimide, most typical representative is by pyromellitic dianhydride and 4,4 '-diaminodiphenyl oxide synthetic line style PI, and the main chain rigidity of this class PI is big, the temperature classification height, the mechanical property under the high low temperature is all good.Though this PI is a linear structure, because the rigid structure of main chain makes it not molten, insoluble, processing has brought difficulty to goods.Not only technical difficulty is big for the working method of employing powder metallurgy, and cost is higher.
In order to improve the shortcoming of traditional polyimide, people have developed the PI of another kind of type.Polyimide by a kind of diamines and the preparation of a kind of dianhydride monomer is the homopolymerization polyimide, and the polyimide that is prepared by more than one diamines and more than one dianhydrides is a copolyimide.The copolymerization structure deteriorate the structural and regularity of molecular chain, reduced crystallinity, help the raising of processibility.If in main chain, introduce the kindliness that groups such as ehter bond, ketonic bond, structure of bisphenol A change main chain again, can further improve the processing characteristics of PI.The polyetherimide (calling PEI in the following text) (US 3847867, and US 3983093) of U.S. GE company invention is a basic raw material with the dihydroxyphenyl propane dianhydride, and the PEI that obtains has thermoplasticity preferably, the method moulding of available conventional plastic working.But its temperature classification reduces greatly, and Tg is at 180~240 ℃, and use temperature is lower than 180 ℃.This country's application number is that 01132395.7 invention is to utilize pyromellitic dianhydride, 1, and two (3,4-dicarboxylic acid phenoxy group) benzene dianhydrides of 4-and phenyl ether dianhydride prepare the terpolymer polyimide, and obtain powder by chemical imidization.Though the copolyimide powder that makes has high glass transition, processing temperature is higher, and needs bigger pressure, still has difficulties for production application.
Copolyimide can be divided into terpolymer, quarternary copolymerized or multi-component copolymer polyimide according to the monomeric species of participating in reaction.Copolyimide is according to the difference of reaction process, also can be divided into alternately, block and random.(1) alternately or block copolymerization: at first, dianhydride is joined in the solution of diamines with mol ratio such as non-, form acid anhydride base or the end capped prepolymer of amido; And then another kind of dianhydride or diamines joined in the above-mentioned solution, no longer increase up to the viscosity of solution, make to react completely.(2) random copolymerization: the dianhydride of equivalent is joined in the mixing solutions of diamines, and till the viscosity of solution no longer increased, reaction obtained the random copolymerization polyimide.
Utilizing existing commercial dianhydride and diamine monomer to carry out modification by copolymerization research is a kind of approach of the simplest, most convenient with the preparation new type polyimide.Because the preparation of copolyimide can be carried out Molecular Structure Design to the PI performance demands according to practical application, so copolyimide can be used as composite resin matrix, film, coating, tackiness agent etc.
Summary of the invention
The present invention carries out copolyreaction by more than one diamines and more than one dianhydrides, is devoted to prepare the multiblock polyimide, makes it have good processibility and thermotolerance.
The feature chemical structural formula of multiblock polyimide:
Figure C20051001187100081
In the formula: x 1, x 2, y 1, y 2, m and n represent the polymerization degree, x 1/ x 2=100/0~0/100, be preferably 50/50~10/90, y 1/ y 2=100/0~0/100, be preferably 50/50~10/90, m/n=100/0~0/100 is preferably 50/50~10/90.
Figure C20051001187100101
Employed end-capping reagent can be single acid anhydride or monoamine, and also end-blocking is not selected according to actual needs.Single acid anhydride:
Monoamine:
The typical synthetic method of copolyimide:
1. earlier a kind of aromatic diamine is dissolved in the N,N-dimethylacetamide (DMAc);
2. under agitation act on, add a kind of aromatic series dianhydride of certain proportioning, temperature of reaction is 0~25 ℃, and the reaction times is 4~6 hours, obtains amino or the end capped oligomer solution of acid anhydride base;
3. and then in succession the dianhydride and the diamines that add other kinds fully reacted 6~8 hours, obtained the multipolymer of block structure;
4. add a certain amount of end-capping reagent again, supply solvent, make solids content at 5~30% copolyamide acid solution;
5. adopt chemical imide or hot imide legal system to get the powder or the film of copolyimide.
Described aromatic series dianhydride is a symmetry and asymmetric, for biphenyl dianhydride (3,3 ', 4,4 '-BPDA or 2,3,3 ', 4 '-BPDA) and pyromellitic dianhydride (PMDA).
Described aromatic diamine is a symmetry and asymmetric, is selected from: diaminodiphenyl oxide (3,4 '-ODA, 4,4 '-ODA and 3,3 '-ODA), adjacent,, in the Ursol D one or more.
The mol ratio of described biphenyl tetracarboxylic acid anhydrides and pyromellitic dianhydride is 100/0~0/100, is preferably 50/50~10/90; The mol ratio of described aromatic diamine and aromatic series dianhydride is 0.95~1.05, is preferably 0.98~1.02, when aromatic diamine is excessive, obtains amino-terminated oligopolymer, when the aromatic series dianhydride is excessive, obtains the end capped oligopolymer of acid anhydride base.When needing the oligopolymer of certain molecular weight, can calculate according to formula (1), thereby determine the ratio of aromatic series dianhydride and diamines, thereby obtain the oligopolymer of given molecular weight.
x n = n a , o + n b , o + n b , o ′ n a , o + n b , o + n b , o ′ - 2 n a , o p a = 1 + r 1 + r - 2 rpa - - - ( 1 )
In the formula, n A, 0And n B, 0The amount of substance of representing diamines and dianhydride respectively, n B, 0The amount of substance of expression end-capping reagent, r = n a , o n b , o + n b , o ′ .
Described other dianhydrides are selected from: 3,3 ', 4,4 '-benzophenone dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether dianhydride (ODPA), dihydroxyphenyl propane dianhydride (BSAA), 1, two (3, the 4-dicarboxylic acid phenoxy group) benzene dianhydrides (HQDEA), 2 of 4-, one or more of two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides (6FDA) of 2-.
Described other diamines are selected from: benzophenone diamines (DABP), dihydroxyphenyl propane diamines (BAPP), 1, two (4-amino-benzene oxygen) benzene (1 of 3-, 3,4-APB), 1, two (4-amino-benzene oxygen) benzene (1 of 4-, 4,4-APB), 2, one or more in two [4 (3-amino-benzene oxygen) phenyl] HFC-236fa (BDAF) of 2-.
The mol ratio of aromatic dianhydride of the present invention and aromatic diamines is different, can change and change according to the design molecular weight, can obtain molecular weight greater than 10000 polyimide.The method of mol ratio that designs dianhydride and diamines according to change of molecular weight is referring to above-mentioned formula (1).
The rigid chain segment of copolyimide of the present invention and soft segment length can be regulated as required.
The end-capping reagent that the present invention uses is single acid anhydride or monoamine, decides on the end group of the copolyamide acid that obtains, when end group is the acid anhydride base, carries out end-blocking with monoamine; When end group is amido, carry out end-blocking with single acid anhydride.
The solvent that the present invention uses is N,N-dimethylacetamide (DMAc).
The synthetic of copolyamide acid of the present invention carries out under 0~25 ℃, and solid content is 5~30%.The solid content height, viscosity is big; Solid content is low, and solvent is big.
The viscosity of copolyamide acid solution of the present invention is 150~5000cps.
In order to control molecular weight distribution and to improve thermotolerance, can adopt single acid anhydride or monoamine to do end-capping reagent.
The present invention can adopt chemical imidization method to make polyimide powder, also can adopt the hot-imide method to obtain Kapton.
The chemical equation that is transformed into polyimide by the polyamic acid imidization is as follows:
The typical heat imidization technology that the present invention adopts is: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 2hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.According to the difference of polyimide molecule structure, needed final imide temperature difference is generally between 200~400 ℃.
The chemical imidization process that the present invention adopts is: slowly add the acetic anhydride and the triethylamine (acetic anhydride and triethylamine are equimolar amounts) of 4 times of diamines molar weights while stirring in the copolyamide acid solution, behind the aaerosol solution to be formed, repeatedly wash with ethanol again.Obtain not the toner of imidization fully through suction filtration, it at 200~300 ℃ of further back imidizations, is obtained the copolyimide powder.
Pyromellitic dianhydride (PMDA) and symmetry and asymmetric biphenyl dianhydride (BPDA) are two kinds of stronger dianhydride monomers of rigidity, polyimide based on their preparations all has better heat-resisting and mechanical property, can regulate the molecular rigidity of polyimide according to actual needs by the rigidity cosegment that they are formed, keep its better heat-resisting and mechanical property.And, can improve the processibility of polyimide by the flexible cosegment that other flexible monomers based on thermoplastic polyimide (especially fluorochemical monomer) are formed.By compliant section is carried out molecular designing, can better improve processibility and keep its thermotolerance again.This copolyimide combines processibility and the good mechanical performance of high-temperature stability and the plasticity-PI of PI.Its outstanding feature is can be by regulating the composition and the ratio of rigid section and compliant section, and the structure of design PI obtains the different multiblock polyimide series of products of temperature resistant grade, mechanical property and processibility.
Embodiment
Embodiment 1
About BPDA and the preparation of ODPA with the polyimide of 10 to 90 molar ratio copolymerization, i.e. x 1/ x 2=100/0, y 1/ y 2=100/0, m/n=10/90.
In being equipped with three neck reaction flasks of agitator, with 5.000g3, in the DMAc solvent of 4 '-ODA (0.025mol) dissolving and 25ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 6.8398gODPA (0.022mol) then, wash with 50mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.7208gBPDA (0.0024mol) again, wash with 25mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.1398g (0.0009mol) Tetra hydro Phthalic anhydride (PA) end-blocking again, completion 14.3mlDMAc solvent, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is the presoma of this novel copolypolyimide, and gross weight is 127g, and solid content is 10wt%.The theoretical molecular Mn=25k of institute's synthesis of polyimides.
Can finish by the transformation of polyamic acid by chemical imidization method to polyimide.The triethylamine that in this solution, adds 10.21g (0.1mol) acetic anhydride and 10.12g (0.1mol), the light yellow resin powder that imidization obtains after stirring, washing, suction filtration, 200 ℃, its Tg is 250 ℃.
Embodiment 2
About BPDA and the preparation of ODPA with the polyimide of 10 to 90 molar ratio copolymerization, i.e. x 1/ x 2=100/0, y 1/ y 2=100/0, m/n=10/90.
In being equipped with three neck reaction flasks of agitator, with 5.000g3, in the DMAc solvent of 4 '-ODA (0.0250mol) dissolving and 15ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 6.8398gODPA (0.0220mol) then, wash with 15mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.7208gBPDA (0.0024mol) again, wash with 15mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.1398g (0.0009mol) end-capping reagent PA again, completion 9.92mlDMAc solvent, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 63.502g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthesis of polyimides.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by the hot-imide method.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is 251 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 1.
Table 13,4 '-ODA/BPDA//ODPA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
100/0 100/0 80/20 1425 270
100/0 100/0 50/50 979.7 262
100/0 100/0 40/60 900 259
100/0 100/0 20/80 756 255
Embodiment 3
About BPDA and the preparation of BTDA with the polyimide of 10 to 90 molar ratio copolymerization, i.e. x 1/ x 2=100/0, y 1/ y 2=100/0, m/n=10/90.
In being equipped with three neck reaction flasks of agitator, with 1.000g3, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 1.4203gBTDA (0.0044mol) then, wash with 5mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.1441gBPDA (0.0005mol) again, wash with 3mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.0286g (0.0002mol) end-capping reagent PA again, completion solvent 1.5mlDMAc, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 16.75g, and solid content is 20wt%.The theoretical molecular Mn=30k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain pale brown look transparent film, and the Tg of this film is 280 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 2.
Table 23,4 '-ODA/BPDA//BTDA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
100/0 100/0 80/20 1302 285
100/0 100/0 50/50 642.1 282
100/0 100/0 40/60 628.6 280
100/0 100/0 20/80 438.1 279
Embodiment 4
About BPDA and the preparation of BSAA with the polyimide of 20 to 80 molar ratio copolymerization, i.e. x 1/ x 2=100/0, y 1/ y 2=100/0, m/n=20/80.
In being equipped with three neck reaction flasks of agitator, with 1.000g3, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 2.026gBSAA (0.0039mol) then, wash with 5mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.286gBPDA (0.001mol) again, wash with 3mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.038g (0.0003mol) end-capping reagent PA again, completion solvent 1.5mlDMAc, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 16.75g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is 222 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 3.
Table 33,4 '-ODA/BPDA//BSAA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
100/0 100/0 80/20 587.2 245
100/0 100/0 50/50 504.3 237
100/0 100/0 40/60 288.6 230
100/0 100/0 20/80 238.9 222
Embodiment 5
About BPDA and the preparation of 6FDA with the polyimide of 50 to 50 molar ratio copolymerization, i.e. x 1/ x 2=100/0, y 1/ y 2=100/0, m/n=50/50.
In being equipped with three neck reaction flasks of agitator, with 1.000g4, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 1.0857g6FDA (0.0024mol) then, wash with 3mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.7191gBPDA (0.0024mol) again, wash with 2mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.0314g (0.00023mol) end-capping reagent PA again, completion solvent 2.7mlDMAc, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 14.18g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is at 320 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 4.
Table 44, the performance of 4 '-ODA/BPDA//6FDA/PA system is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
100/0 100/0 80/20 576.5 289
100/0 100/0 60/40 486.1 307
100/0 100/0 40/60 325.2 329
100/0 100/0 20/80 215.7 335
Embodiment 6
About BSAA and the preparation of PMDA with the polyimide of 80 to 20 molar ratio copolymerization, i.e. x 1/ x 2=0/100, y 1/ y 2=100/0, m/n=80/20.
In being equipped with three neck reaction flasks of agitator, with 1.000g3, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 2.028gBSAA (0.0039mol) then, wash with 3mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.212gPMDA (0.001mol) again, wash with 3mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.037g (0.00025mol) end-capping reagent PA again, completion solvent 3.17mlDMAc, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 16.385g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is more than 300 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 5.
Table 53,4 '-ODA/BSAA//PMDA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
0/100 0/100 80/20 336.2 269
0/100 0/100 50/50 296.8 254
0/100 0/100 40/60 227.9 247
0/100 0/100 20/80 189.6 238
Embodiment 7
About PMDA and the preparation of 6FDA with the polyimide of 80 to 20 molar ratio copolymerization, i.e. x 1/ x 2=0/100, y 1/ y 2=100/0, m/n=80/20.
In being equipped with three neck reaction flasks of agitator, with 1.000g4, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 0.436g6FDA (0.001mol) then, wash with 2mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.857gPMDA (0.004mol) again, wash with 2mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, add 0.025g (0.0002mol) end-capping reagent PA again, completion solvent 1.02mlDMAc, the total time of reaction is 8~10 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 11.59g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is 390 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 6.
Table 64,4 '-ODA/PMDA//6FDA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
0/100 100/0 90/10 681.3 403
0/100 100/0 50/50 426.2 375
0/100 100/0 40/60 354.9 369
0/100 100/0 20/80 296.7 356
Embodiment 8
About x 1=BPDA, x 2=PMDA and y 1=6FDA, y 2=ODPA, m and n are with the preparation of the polyimide of 50 to 50 molar ratio copolymerization, i.e. x 1/ x 2=90/10, y 1/ y 2=10/90, m/n=50/50.
In being equipped with three neck reaction flasks of agitator, with 1.000g3, in the DMAc solvent of 4 '-ODA (0.005mol) dissolving and 5ml, stirring makes solution becomes get clear, does not have visible solid particulate.In this solution, slowly add 0.649gBPDA (0.0022mol) then, wash with 2mlDMAc, stirring makes it to dissolve fully after about 2~3 hours and adds 0.053gPMDA (0.00024mol) again, wash with 2mlDMAc, after treating that two kinds of dianhydrides and ODA react for a long time, in this solution, successively add 0.109g6FDA (0.00024mol) and 0.684gODPA (0.00022mol) again, treat to add again after soltion viscosity no longer increases 0.028g (0.0002mol) end-capping reagent PA, completion solvent 1.91mlDMAc, the total time of reaction is 10~15 hours.Resulting transparent thick liquid polyamic acid is this novel copolymerized imido presoma, and gross weight is 12.615g, and solid content is 20wt%.The theoretical molecular Mn=25k of institute's synthetic polyimide.
This polyamic acid can be finished by the transformation of polyamic acid to polyimide by hot-imide.Method by hot-imide can obtain faint yellow transparent film, and the Tg of this film is 271 ℃.
The performance variation that changes the copolyimide that causes owing to the ratio of m and n sees Table 7.
Table 73,4 '-ODA/PMDA//BPDA//6FDA//ODPA/PA system performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
90/10 10/90 80/20 696.8 305.4
90/10 10/90 60/40 512.6 278.9
90/10 10/90 40/60 325.9 264.3
90/10 10/90 20/80 151.1 251.9
In addition, we have also done the copolyimide that different copolymer is formed, following embodiment:
Embodiment 9:
1,3-PDA//2,3,3 ', 4 ' BPDA//PMDA//6FDA//4,4 '-HQDPA/APA system (Mn=30000) performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
80/20 20/80 50/50 627.9 325.6
70/30 30/70 50/50 496.9 315.4
60/40 40/60 50/50 305.1 309.1
20/80 80/20 50/50 171.4 303.9
Embodiment 10:
1,3-APB//PMDA//BPDA//4,4 '-TDPA//BTDA/ aniline system (Mn=40000) performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
20/80 50/50 80/20 809.8 310.6
40/60 50/50 60/40 698.3 305.2
60/40 50/50 40/60 421.3 298.7
80/20 50/50 20/80 289.7 293.6
Embodiment 11:
1,4-PDA//1,4-APB//BPDA//4,4 '-TDPA//BTDA/PEPA system (Mn=15000) performance is enumerated
x 1/x 2 y 1/y 2 m/n Viscosity/cps Tg/℃
50/50 20/80 80/20 579.6 310.6
50/50 40/60 60/40 495.2 305.2
50/50 60/40 40/60 322.5 298.7
50/50 80/20 20/80 198.1 293.6

Claims (14)

1. multiblock polyimide, it is characterized in that: the imido chemical structural formula of described multiblock is as follows:
Figure C2005100118710002C1
In the formula: x 1, x 2, y 1, y 2, m and n represent the polymerization degree, x 1/ x 2=50/50~10/90, y 1/ y 2=50/50~10/90, m/n=50/50~10/90;
In the formula:
Figure C2005100118710002C2
-R-= -O-
Figure C2005100118710003C3
-S-
-R′-= -O-
-S-
2. multiblock polyimide as claimed in claim 1, it is characterized in that :-Ar-is selected from: With -R-and-R '-be selected from :-O-,
Figure C2005100118710003C8
With
Figure C2005100118710003C9
3. one kind as each described multiblock polyimide in the claim 1~2, it is characterized in that: described multiblock polyimide end-capping reagent end-blocking.
4. multiblock polyimide as claimed in claim 3, it is characterized in that: described end-capping reagent is single acid anhydride or monoamine.
5. multiblock polyimide as claimed in claim 4, it is characterized in that: described single acid anhydride is selected from:
Described monoamine is selected from:
6. the preparation method of a multiblock polyimide as claimed in claim 1, it is characterized in that: described method comprises the steps:
1. earlier a kind of aromatic diamine is dissolved in the N,N-dimethylacetamide;
2. under agitation act on, add a kind of aromatic series dianhydride of certain proportioning, temperature of reaction is about 0~25 ℃, and the reaction times is 4~6 hours, obtains amino or the end capped oligomer solution of acid anhydride base;
3. and then in succession the dianhydride and the diamines that add other kinds fully reacted 6~8 hours, obtained the multipolymer of block structure;
4. adopt chemical imide or hot imide legal system to get the powder or the film of copolyimide.
7. the preparation method of a multiblock polyimide as claimed in claim 6, it is characterized in that: described aromatic series dianhydride is biphenyl dianhydride and pyromellitic acid anhydride.
8. the preparation method of a multiblock polyimide as claimed in claim 6, it is characterized in that: described aromatic diamine is selected from: one or more of diaminodiphenyl oxide, dihydroxyphenyl propane diamines.
9. the preparation method of a multiblock polyimide as claimed in claim 6, it is characterized in that: described other dianhydrides are selected from: 3,3 ', 4,4 '-benzophenone dianhydride, 3,3 ', 4,4 '-phenyl ether dianhydride, dihydroxyphenyl propane dianhydride, 1,4-two (3,4-dicarboxylic acid phenoxy group) benzene dianhydride, 2, one or more of two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-.
10. the preparation method of a multiblock polyimide as claimed in claim 6, it is characterized in that: described other diamines are selected from: the benzophenone diamines,, neighbour, Ursol D, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 2 of 4-, one or more in two [4 (3-amino-benzene oxygen) phenyl] HFC-236fa of 2-.
11. the preparation method of a multiblock polyimide as claimed in claim 6 is characterized in that: described method comprises the steps: that also 3. obtaining adding in the multipolymer of block structure a certain amount of end-capping reagent in step carries out end-blocking.
12. the preparation method of a multiblock polyimide as claimed in claim 11 is characterized in that: described end-capping reagent is single acid anhydride or monoamine.
13. the preparation method of a multiblock polyimide as claimed in claim 11 is characterized in that: described single acid anhydride is selected from:
Described monoamine is selected from:
Figure C2005100118710006C1
14. the preparation method of a multiblock polyimide as claimed in claim 6 is characterized in that: described final imidization temperature is 200~400 ℃, and the imidization time is 0.1~2 hour.
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