CN1923833A - Diamine containing N-aminophthalimide structure unit, polyimide with the same as diamine and preparation method thereof - Google Patents
Diamine containing N-aminophthalimide structure unit, polyimide with the same as diamine and preparation method thereof Download PDFInfo
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- CN1923833A CN1923833A CN 200610017198 CN200610017198A CN1923833A CN 1923833 A CN1923833 A CN 1923833A CN 200610017198 CN200610017198 CN 200610017198 CN 200610017198 A CN200610017198 A CN 200610017198A CN 1923833 A CN1923833 A CN 1923833A
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- diamine
- aminophthalimide
- structural unit
- structural formula
- polyimide
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 50
- 239000004642 Polyimide Substances 0.000 title claims abstract description 33
- 229920001721 polyimide Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KSILMCDYDAKOJD-UHFFFAOYSA-N 2-aminoisoindole-1,3-dione Chemical group C1=CC=C2C(=O)N(N)C(=O)C2=C1 KSILMCDYDAKOJD-UHFFFAOYSA-N 0.000 title claims abstract 14
- -1 optical devices Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 16
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 150000003949 imides Chemical group 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 8
- 125000005543 phthalimide group Chemical class 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims 3
- 125000002751 aliphatic alkane group Chemical group 0.000 claims 2
- 125000006393 methylpyrimidinyl group Chemical group 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 229930003836 cresol Natural products 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 125000005462 imide group Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 47
- GQBONCZDJQXPLV-UHFFFAOYSA-N 4-aminoisoindole-1,3-dione Chemical compound NC1=CC=CC2=C1C(=O)NC2=O GQBONCZDJQXPLV-UHFFFAOYSA-N 0.000 description 43
- 238000001816 cooling Methods 0.000 description 33
- 238000001914 filtration Methods 0.000 description 33
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 24
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 24
- 238000004062 sedimentation Methods 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 150000001896 cresols Chemical class 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- MFUPLJQNEXUUDW-UHFFFAOYSA-N 2-phenylisoindole-1,3-dione Chemical class O=C1C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 MFUPLJQNEXUUDW-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- APOAEMIYHVGWEZ-UHFFFAOYSA-N 4-chloroisoindole-1,3-dione Chemical compound ClC1=CC=CC2=C1C(=O)NC2=O APOAEMIYHVGWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Indole Compounds (AREA)
Abstract
本发明涉及含N－氨基酞酰亚胺结构单元的二胺及以其为二胺的聚酰亚胺和制备方法。以含邻位取代的酰亚胺结构的化合物为原料，合成了一系列五元环的含N－氨基酞酰亚胺结构单元的二胺，并以这类二胺作为单体，同芳香二酐聚合的到了一系列的聚酰亚胺。本发明的方法，可以得到系列的高性能聚酰亚胺，这类聚酰亚胺具有高的玻璃化温度，良好的溶解性，以及优异的光学性能。需要重点指出的是有些聚合物可以得到无色的薄膜。这类聚合物可能广泛用于工程塑料，电子和微电子材料，光学器件，以及气体分离膜等领域。The invention relates to diamine containing N-aminophthalimide structural unit, polyimide using it as diamine and a preparation method. A series of five-membered ring diamines containing N-aminophthalimide structural units were synthesized from compounds containing ortho-substituted imide structures. Anhydrides are polymerized into a series of polyimides. The method of the invention can obtain a series of high-performance polyimides, which have high glass transition temperature, good solubility, and excellent optical properties. It is important to point out that some polymers give colorless films. Such polymers may be widely used in engineering plastics, electronic and microelectronic materials, optical devices, and gas separation membranes.
Description
Technical field
The present invention relates to contain the diamines of the amino phthalimide structural unit of N-and be the polyimide and the preparation method of diamines with it.
Background technology
Hydrazine is the simplest diamines, but because it is not quantitative generation imide with the reaction of dianhydride, so be that the polyimide of diamines combines very difficult with the hydrazine.As far back as the sixties in last century, Dine-hart has just synthesized N, N-diamino pyromellitic acid double imide and N, N-diaminostilbene, 4,5,8-naphthalenetetracarbacidic acidic double imide (J Polym Sci, Part A-1 1968,6,2755-2764), still because the monomer reaction activity is low and resulting polymkeric substance solubleness in reaction medium is very little, so do not obtain the high-molecular weight polyimide.Last century the nineties, Canadian Hay etc. utilize to introduce soft segment or with the mode of other diamines, (U.S.Patent 5 to have obtained high-molecular weight and with the hydrazine be the polyimide of diamines, 459,227 (1995), U.S.Patent 5,420,234 (1995) .U.S.Patent 5,359,092 (1994)).But, the N that Hay etc. adopted, the diamines of N-diamino diimine structure all is a six-ring, has therefore limited the application of this base polymer.
Summary of the invention
The present invention is a raw material with the compound of the imide structure that contains the ortho position and replace, has synthesized the diamines of the amino phthalimide structural units of a series of pentacyclic N-of containing, and with this class diamines as monomer, arrived a series of polyimide with the aromatic dianhydride polymeric.
One of purpose of the present invention provides the diamines of the amino phthalimide structural unit of a kind of N-of containing.
Two of purpose of the present invention provides the diamines of the amino phthalimide structural unit of a kind of N-of containing and is the polyimide of diamines with it.
It is the preparation method of the polyimide of diamines that three of purpose of the present invention provides a kind of reaching with it with the diamines that contains the amino phthalimide structural unit of N-.
The diamines that contains the amino phthalimide structural unit of N-of the present invention, its structural formula is:
R wherein
4For :-O-,-S-,-CO-,-SO
2-,-SO-.
R
5For shown in the following structural formula substituent any one:
Its structural formula of polyimide provided by the invention is:
Ar wherein
1For shown in the following structural formula substituent any one:
Ar
1In R
4For :-O-,-S-,-CO-,-SO
2-,-any one of SO-.
R
5For shown in the following structural formula substituent any one:
Ar in the formula
2For shown in the following structural formula substituent any one:
Formula Ar
2In R
6For-O-,-S-,-CO-,-C (CF
3)
2-and following structural formula shown in substituent any one.
The diamines of the amino phthalimide structural unit of the N-of containing of the present invention and be that preparation method's the step and the condition of the polyimide of diamines is with it:
1) contains the preparation of the diamines of the amino phthalimide structural unit of N-
The compound that will contain the phthalimide structure of ortho position replacement is dissolved in the polar solvent, wherein, imide ring is 1 with the mol ratio of hydrazine: 0.8-2, the compound that contains the phthalimide structure that the ortho position replaces is 1 with the weight ratio of solvent: 3-10, reacted 0.5-12 hour down at 50-200 ℃, preparation contains the diamines of the amino phthalimide structural unit of N-.
2). with the diamines that contains the amino phthalimide structural unit of N-is the preparation of the polyimide of diamines
The equal normal dianhydride of diamines that contains the amino phthalimide structural unit of N-with the step 1) gained, and adding catalyzer, this catalyzer is 1 with the mol ratio that contains the amino phthalimide structural unit of N-diamines: 100-2: 1, is 1 with dianhydride and the diamine monomer quality sum (g) that contains the amino phthalimide structural unit of N-with the ratio of polymerization solvent volume (ml): 2-20, under the nitrogen protection condition, 80-120 ℃ of reaction 1-4 hour, 180-220 ℃ of reaction 12-48 hour, the diamines that obtains to contain the amino phthalimide structural unit of N-was the polyimide of diamines again;
(1) the described compound that contains the phthalimide structure of ortho position replacement is:
A. the phthalimide that replaces of ortho position, its structural formula is:
R
1For: fluorine, chlorine, bromine, iodine, amino, phenyl, phenoxy group, benzene sulfydryl, aminophenyl, amino-benzene oxygen or amino-benzene sulfydryl.
R
2For: hydrogen, fluorine, chlorine, bromine, iodine, amino, phenyl, phenoxy group, benzene sulfydryl, aminophenyl, amino-benzene oxygen or amino-benzene sulfydryl.
R
3For: hydrogen, phenyl, aminomethyl phenyl, pyrimidyl, methylpyrimidine base or C
1-C
9Aliphatics alkane substituting group.
B. two phthalimides of replacing of ortho position, its structural formula is:
R
3For: hydrogen, phenyl, aminomethyl phenyl, pyrimidyl, methylpyrimidine base or C
1-C
9Aliphatics alkane substituting group.
R
4For :-O-,-S-,-CO-,-SO
2-,-any one of SO-.
R
5For shown in the following structural formula substituent any one:
(2) expression formula of described hydrazine is: H
2N-NH
2
(3) described polar solvent is: methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, tetrahydrofuran (THF), dioxane, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide or tetramethylene sulfone.
(4) the described diamines that contains the amino phthalimide structural unit of N-, its structural formula is:
R wherein
4, R
5The middle R of b in the substituting group of representative and (1)
4, R
5Identical.
(5) described aromatic dianhydride, its structural formula is:
R wherein
6For-O-,-S-,-CO-,-C (CF
3)
2-and following structural formula shown in substituent any one:
(6) described catalyzer is: phenylformic acid, P-hydroxybenzoic acid, quinoline or isoquinoline 99.9.
(7) described polymerization solvent is: phenol, ortho-cresol, meta-cresol, p-cresol, cresols, P-Chlorophenol, oil of mirbane, benzene nitrile or α-Lv Dainai.
Beneficial effect of the present invention is:
By method of the present invention, can obtain a series of high-performance polyimide, this quasi-polyimide has high second-order transition temperature, good solubility, and excellent optical property.Need emphasis to be pointed out that some polymkeric substance can obtain colourless film.This base polymer may be widely used in engineering plastics, electronics and microelectronic material, optics, and field such as gas separation membrane.
Embodiment 1:
With 0.10 mole (44.44g) 3,3 '-two (N-phenyl phthalimides), 12.50g hydrazine hydrate (80%) joins in the single port bottle of 1000ml, add 450ml DMAc, in 60 ℃ of reactions 12 hours, cooling, with the gained sedimentation and filtration, it is inferior to give a baby a bath on the third day after its birth with the ammoniacal liquor of 0.25mol/L, and N is used in oven dry, the dinethylformamide recrystallization, get 3,3 '-two (the amino phthalimide of N-) 22.55g, yield 70%.
Embodiment 2:
With 0.10 mole of (28.43g) 3-(4-amino-benzene sulfydryl)-N methyl phthalimide, 6.25g hydrazine hydrate (80%) joins in the single port bottle of 500ml, add 95ml DMF, 100 ℃ the reaction 6 hours, the cooling, with the gained mixture to going in the 500ml water, filter, it is inferior to give a baby a bath on the third day after its birth with the ammoniacal liquor of 0.25mol/L, gets 3-(4-amino-benzene sulfydryl)-N methyl phthalimide) 17.11g, yield 60%.
Embodiment 3:
With 0.10 mole of (18.16g) 3-chloro phthalimide, 6.25g hydrazine hydrate (80%) joins in the single port bottle of 250ml, adds 90ml ethanol, refluxed 0.5 hour, cooling is with the gained sedimentation and filtration, oven dry gets the amino phthalimide 9.83g of 3-chloro-N-, yield 50%.
Embodiment: 4
With the amino phthalimide of 0.10 mole of (25.77g) 3-chloro-N-, 5g hydrazine hydrate (80%) joins in the single port bottle of 250ml, adds 75ml methyl alcohol, 50 ℃ of reactions 10 hours, with the gained sedimentation and filtration, oven dry, get 3-chloro-N-aminoacyl imines 7.86g, yield 40%.
Embodiment 5:
With 0.10 mole of (46.04g) oxygen ether-3,3 '-two (N-phenyl phthalimides), 12.50g hydrazine hydrate (80%) joined in the single port bottle of 250ml, adds the 90ml N-Methyl pyrrolidone, 200 ℃ of reactions 0.5 hour, cooling, with the gained sedimentation and filtration, oven dry gets oxygen ether-3,3 '-two (the amino phthalimide of N-) 27.06g, yield 80%.
Embodiment 6:
With 0.10 mole of (47.65g) thioether-3,3 '-two (N-phenyl phthalimides), 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 300ml dimethyl formamide, 150 ℃ of reactions 1 hour, cooling, with the gained sedimentation and filtration, oven dry gets thioether-3,3 '-two (the amino phthalimide of N-) 26.58g, yield 75%.
Embodiment 7:
With 0.10 mole of (47.24g) carbonyl-3,3 '-two (N-phenyl phthalimides), 12.50g hydrazine hydrate (80%) joins in the single port bottle of 500ml, adds the 250ml dioxane, 70 ℃ of reactions 12 hours, cooling, with the gained sedimentation and filtration, oven dry, get carbonyl-3,3 '-two (the amino phthalimides of N-), 22.77g, yield 65%.
Embodiment 8:
With 0.10 mole of (50.81g) sulfuryl-3,3 '-two (N-phenyl phthalimides), 15g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 200ml propyl alcohol, 60 ℃ of reactions 18 hours, cooling, with the gained sedimentation and filtration, oven dry gets sulfuryl-3,3 '-two (the amino phthalimide of N-) 19.32g, yield 50%.
Embodiment 9:
With 0.10 mole of (49.21g) sulfoxide-3,3 '-two (N-phenyl phthalimides), 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 200ml Virahol, 60 ℃ of reactions 18 hours, cooling, with the gained sedimentation and filtration, oven dry gets sulfoxide-3,3 '-two (the amino phthalimide of N-) 26.66g, yield 72%.
Embodiment 10:
With 0.10 mole of (55.25g) 1,4-benzene-two [3-oxygen-(N-phenyl phthalimide)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 1000ml, adds 600ml acetone, 60 ℃ of reactions 18 hours, cooling, with the gained sedimentation and filtration, oven dry gets 1,4-benzene-two [3-oxygen-(the amino phthalimide of N-)] 32.71g, yield 76%.
Embodiment 11:
With 0.10 mole of (55.25g) 1,3-benzene-two [3-oxygen-(N-phenyl phthalimide)] 12.50g hydrazine hydrate (80%) joins in the single port bottle of 1000ml, add the 400ml tetrahydrofuran (THF), 50 ℃ of reactions 12 hours, cooling was with the gained sedimentation and filtration, oven dry, get 1,3-benzene-two [3-oxygen-(the amino phthalimide of N-)] 29.44g, yield 68%.
Embodiment 12:
With 0.10 mole of (55.25g) 1,2-benzene-two [(3-oxygen-(N-phenyl phthalimide))] 12.50g hydrazine hydrate (80%) joins in the single port bottle of 1000ml, add the 400ml tetrahydrofuran (THF), 50 ℃ of reactions 10 hours, cooling was with the gained sedimentation and filtration, oven dry, get 1,2-benzene-two [3-oxygen-(the amino phthalimide of N-)] 35.33g, yield 82%.
Embodiment 13:
With 0.10 mole of (62.86g) biphenyl-4,4 ' two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 200ml dimethyl sulfoxide (DMSO), 120 ℃ of reactions 3 hours, cooling, with the gained sedimentation and filtration, oven dry gets biphenyl-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 32.41g, yield 64%.
Embodiment 14:
With 0.10 mole of (64.46g) phenyl ether-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 200ml hexamethylphosphoramide, 100 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets phenyl ether-4,4 ' two [3-oxygen-(the amino phthalimide of N-)] 29.26g, yield 56%.
Embodiment 15:
With 0.10 mole of (66.07g) diphenyl sulfide-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 200ml hexamethylphosphoramide, 100 ℃ of reactions 12 hours, cooling, with the gained sedimentation and filtration, oven dry gets diphenyl sulfide-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 39.85g, yield 74%.
Embodiment 16:
With 0.10 mole of (64.66g) ditane-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 300ml tetramethylene sulfone, 120 ℃ of reactions 4 hours, cooling, with the gained sedimentation and filtration, oven dry gets ditane-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 30.19g, yield 58%.
Embodiment 17:
With 0.10 mole of (54.66g) 2,2 '-diphenyl propane-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joins in the single port bottle of 500ml, add the 100ml N,N-DIMETHYLACETAMIDE, in 120 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets 2,2 ' diphenyl propane-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 43.88g, yield 80%.
Embodiment 18:
With 0.10 mole of (65.66g) benzophenone-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 150ml N,N-DIMETHYLACETAMIDE, 120 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets benzophenone-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 40.09g, yield 75%.
Embodiment 19:
With 0.10 mole of (69.27g) sulfobenzide-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 250ml N,N-DIMETHYLACETAMIDE, 120 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets sulfobenzide-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 37.65g, yield 66%.
Embodiment 20:
With 0.10 mole of (76.07g) phenolphthalein-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 300ml N,N-DIMETHYLACETAMIDE, 120 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets phenolphthalein-4,4 '-two [3-oxygen-(the amino phthalimide of N-)] 44.06g, yield 69%.
Embodiment 21:
With 0.10 mole of (79.28g) fluorenes-9,9 '-two [3-(4-phenoxy group)-N-phenyl phthalimide], 12.50g hydrazine hydrate (80%) joined in the single port bottle of 500ml, adds the 350ml N,N-DIMETHYLACETAMIDE, 110 ℃ of reactions 6 hours, cooling, with the gained sedimentation and filtration, oven dry gets fluorenes-9,9 '-two [the amino phthalimide of 3-(4-phenoxy group)-N-] 48.96g, yield 73%.
Embodiment 22:
With 0.10 mole (36.81g) 1,2,3,4-connects two (N-phenyl) imides of benzene, and 12.50g hydrazine hydrate (80%) joins in the single port bottle of 500ml, adds the 100ml N,N-DIMETHYLACETAMIDE, 110 ℃ of reactions 6 hours, cooling was with the gained sedimentation and filtration, oven dry, get 1,2,3,4-connects two (N-amino) the imide 17.97g of benzene, yield 73%.
Embodiment 23:
With 0.10 mole (37.44g) 1,2,3, two (N-phenyl) imides of 4-cis hexanaphthene, 12.50g hydrazine hydrate (80%) joins in the single port bottle of 500ml, adds the 100ml N,N-DIMETHYLACETAMIDE, 110 ℃ of reactions 6 hours, cooling was with the gained sedimentation and filtration, oven dry, get 1,2,3, two (N-amino) the imide 17.91g of 4-cis hexanaphthene, yield 71%.
Embodiment 24:
With 0.10 mole (37.44g) 1,2,3, two (N-phenyl) imides of 4-trans cyclohexane, 12.50g hydrazine hydrate (80%) joins in the single port bottle of 500ml, adds the 100ml N,N-DIMETHYLACETAMIDE, 130 ℃ of reactions 6 hours, cooling was with the gained sedimentation and filtration, oven dry, get 1,2,3, two (N-amino) the imide 11.64g of 4-trans cyclohexane, yield 46%.
The polyreaction example:
Embodiment 25:
With 0.01 mole of (3.22g) 3,3 '-two (the amino phthalimides of N-), 0.01 mole of (4.02g) 4,4 ' triphen two ether dianhydride, 0.02 mole (2.44g) phenylformic acid, join in the there-necked flask that contains 14 milliliters of P-Chlorophenol, under nitrogen atmosphere and mechanical agitation condition, 80 ℃ of reactions 4 hours, be warming up to 200 ℃ then and also continue reaction 24 hours, cooling is poured reactant in the 150ml ethanol then, stirs 10min, filter, get product, with 30ml alcohol reflux 2h, filtering drying, get the 6.89g polyimide powder, productive rate 97%, logarithmic viscosity number 0.4dl/g (cresols is a solvent, 30 ℃).The polymkeric substance of gained can be paved into water white film.
Embodiment 26:
With 0.01 mole of (3.38g) oxygen ether-3,3 '-two (the amino phthalimides of N-), 0.01 mole (2.94g) 4,4 ' biphenyl dianhydride, 0.002 mole of (0.26g) isoquinoline 99.9, join in the there-necked flask that contains 130 milliliters of meta-cresols, under nitrogen atmosphere and mechanical agitation condition,, be warming up to 180 ℃ then and also continue reaction 48 hours 120 ℃ of reactions 1 hour, cooling, then reactant is poured in the 750ml ethanol, stirred 10min, filter, with 30ml alcohol reflux 2h, filtering drying gets the 5.98g polyimide powder, productive rate 95%, logarithmic viscosity number 0.35dl/g (cresols is a solvent, 30 ℃).
Embodiment 27:
With 0.01 mole of (3.54g) thioether-3,3 '-two (the amino phthalimides of N-), 0.01 mole (2.18g) pyromellitic acid dianhydride, 0.10 mole (1.29g) isoquinoline 99.9 joins in the there-necked flask that contains 100 milliliters of phenol, under nitrogen atmosphere and mechanical agitation condition, 120 ℃ of reactions 1 hour, be warming up to 220 ℃ then and also continue reaction 24 hours, cooling is poured reactant in the 500ml ethanol then, stir 10min, filter, with 30ml alcohol reflux 2h, filtering drying, get the 5.38g polyimide powder, productive rate 93%, logarithmic viscosity number 0.22dl/g (cresols is a solvent, 30 ℃).
Embodiment 28:
With 0.01 mole of (3.50g) carbonyl-3,3 '-two (the amino phthalimides of N-), 0.01 mole (3.22g) 4,4 '-benzophenone dianhydride, 0.002 mole of (1.29g) quinoline, join in the there-necked flask that contains 100 milliliters of meta-cresols, under nitrogen atmosphere and mechanical agitation condition,, be warming up to 190 ℃ then and also continue reaction 36 hours 100 ℃ of reactions 1 hour, cooling, then reactant is poured in the 400ml ethanol, stirred 10min, filter, with 30ml ethanol cocurrent flow 2h, filtering drying gets the 6.37g polyimide powder, productive rate 97%, logarithmic viscosity number 0.30dl/g (cresols is a solvent, 30 ℃).
Embodiment 29:
With 0.01 mole of (4.30g) 1,4-benzene-two [3-oxygen-(the amino phthalimide of N-)], 0.01 mole (3.10g) 4,4 '-phenyl ether dianhydride, 0.10 mole of (1.38g) P-hydroxybenzoic acid, join in the there-necked flask that contains 150 milliliters of ortho-cresols, under nitrogen atmosphere and mechanical agitation condition,, be warming up to 190 ℃ then and also continue reaction 36 hours 100 ℃ of reactions 1 hour, cooling, then reactant is poured in the 600ml ethanol, stirred 10min, filter, with 30ml alcohol reflux 2h, filtering drying gets the 7.06g polyimide powder, productive rate 95%, logarithmic viscosity number 0.42dl/g (cresols is a solvent, 30 ℃).
Embodiment 30:
With 0.01 mole of (5.48g) 2,2 '-diphenyl propane-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 0.01 mole of (5.20g) 4,4 '-the dihydroxyphenyl propane diaether dianhydride, 0.10 mole (1.38g) P-hydroxybenzoic acid joins in the there-necked flask that contains 100 milliliters of p-cresol, under nitrogen atmosphere and mechanical agitation condition, 100 ℃ of reactions 1 hour, be warming up to 190 ℃ then and also continue reaction 36 hours, cooling is poured reactant in the 400ml ethanol then, stir 10min, filter, with 30ml alcohol reflux 2h, filtering drying, get the 10.32g polyimide powder, productive rate 99%, logarithmic viscosity number 0.48dl/g (cresols is a solvent, 30 ℃).
Embodiment 31:
With 0.01 mole of (5.48g) 2,2 '-diphenyl propane-4,4 '-two [3-oxygen-(N-phenyl phthalimides)], 0.01 mole of (5.20g) 3,3 '-the dihydroxyphenyl propane diaether dianhydride, 0.10 mole (1.38g) P-hydroxybenzoic acid joins in the there-necked flask that contains 100 milliliters of benzene nitriles, under nitrogen atmosphere and mechanical agitation condition, 100 ℃ of reactions 1 hour, be warming up to 190 ℃ then and also continue reaction 36 hours, cooling is poured reactant in the 400ml ethanol then, stir 10min, filter, with 30ml alcohol reflux 2h, filtering drying, get the 10.32g polyimide powder, productive rate 99%, logarithmic viscosity number 0.49dl/g (cresols is a solvent, 30 ℃).
Embodiment 32:
With 0.01 mole of (6.71g) fluorenes-9,9 '-two [3-(4-phenoxy group)-N-phenyl phthalimide], 0.01 mole (3.26g) 4,4 '-thioether dianhydride, 0.10 mole of (1.38g) P-hydroxybenzoic acid, join in the there-necked flask that contains 100 milliliters of oil of mirbane, under nitrogen atmosphere and mechanical agitation condition,, be warming up to 190 ℃ then and also continue reaction 36 hours 100 ℃ of reactions 1 hour, cooling, then reactant is poured in the 400ml ethanol, stirred 10min, filter, with 30ml alcohol reflux 2h, filtering drying gets the 9.64g polyimide powder, productive rate 92%, logarithmic viscosity number 0.40dl/g (cresols is a solvent, 30 ℃).
Embodiment 33:
With 0.01 mole of (3.22g) 3,3 '-two (the amino phthalimides of N-), 0.01 mole (4.44g) 6F dianhydride, 0.10 mole (1.38g) P-hydroxybenzoic acid joins in the there-necked flask that contains 60 milliliters of cresolss, under nitrogen atmosphere and mechanical agitation condition, 100 ℃ of reactions 1 hour, be warming up to 190 ℃ then and also continue reaction 36 hours, cooling is poured reactant in the 300ml ethanol then, stir 10min, filter, with 30ml alcohol reflux 2h, filtering drying, get the 7.32g polyimide powder, productive rate 95%, logarithmic viscosity number 0.35dl/g (cresols is a solvent, 30 ℃).Resulting polymers can be paved into water white film.
Embodiment 34:
With 0.01 mole of (3.22g) 3,3 '-two (the amino phthalimides of N-), 0.01 mole (5.20g) 4,4 '-dihydroxyphenyl propane diaether dianhydride, 0.10 mole of (1.38g) P-hydroxybenzoic acid, join in the there-necked flask that contains 60 milliliters of cresolss, under nitrogen atmosphere and mechanical agitation condition,, be warming up to 190 ℃ then and also continue reaction 36 hours 100 ℃ of reactions 1 hour, cooling, then reactant is poured in the 300ml ethanol, stirred 10min, filter, with 30ml alcohol reflux 2h, filtering drying gets the 7.90g polyimide powder, productive rate 95%, logarithmic viscosity number 0.36dl/g (cresols is a solvent, 30 ℃).Resulting polymers can be paved into water white film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516541A (en) * | 2011-11-22 | 2012-06-27 | 中国航空工业集团公司北京航空材料研究院 | Polyimide containing phenolic hydroxy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516541A (en) * | 2011-11-22 | 2012-06-27 | 中国航空工业集团公司北京航空材料研究院 | Polyimide containing phenolic hydroxy |
| CN102516541B (en) * | 2011-11-22 | 2013-08-07 | 中国航空工业集团公司北京航空材料研究院 | Polyimide containing phenolic hydroxy |
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