CN1035511C - Polyimide with sulfonate segment in main chain - Google Patents
Polyimide with sulfonate segment in main chain Download PDFInfo
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- CN1035511C CN1035511C CN93111577A CN93111577A CN1035511C CN 1035511 C CN1035511 C CN 1035511C CN 93111577 A CN93111577 A CN 93111577A CN 93111577 A CN93111577 A CN 93111577A CN 1035511 C CN1035511 C CN 1035511C
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- Prior art keywords
- polyimide
- main chain
- group
- tetravalence
- sulfonate
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Abstract
The present invention discloses a polyimide, the main chain of which comprises a sulphonate (-SO3-M-SO3-) chain joint, wherein M in the -SO3-M-SO3- chain joint is a divalent metallic element, such as Ba, Ca , Mg, etc., and the introduction of bivalent metal makes the polyimide have the characteristics of better solubility, good heat resistance and specific absorption spectrum. The polyimide is widely used as engineering plastics, composite heat-resisting materials, functional materials, paints, films, catalysts, stealth materials, etc.
Description
The present invention relates to a kind of superpolymer, contain sulfonate (SO in particularly a kind of main chain
3-M-O
3S-) polyimide of chain link.
Polyimide is a kind of important macromolecular material.It has excellent comprehensive performances, its heat-resisting and radiation resistance is best in the macromolecular material of present suitability for industrialized production, have outstanding dielectric properties, mechanical property, radiation resistance, firing resistance, wear resisting property under the high temperature, the product size good stability, organic solvent-resistant, and low-temperature performance is good.But the problem that prior art is deposited is: existing imide is insoluble not molten, thereby processing difficulties, and the cost height contains sulfonate (SO on the main chain
3-M-SO
3-) polyimide of chain link (wherein M is a metal) do not appear in the newspapers as yet both at home and abroad to.Japanese document J.Polym.Sci., Polym.Chem., 29,83-91 (1991).Author HIDEAKI MATSODA has reported for work and has contained polyureas and the Polyurethane urea of COOMOOC in a kind of main chain, and wherein M is a metal, but does not belong to same class with theme of the present invention.
The object of the present invention is to provide a kind of soluble, easy processing, cost low, have better resistance toheat, special absorption spectrum feature and a polyimide of certain function.
Technical solution of the present invention is: contain sulfonate (SO in a kind of main chain
3-M-O
3S-) polyimide of chain link, its structural formula is:
Wherein M can form or have H for all
2N-Ar-SO
3-M-O
3S-Ar-NH
2The divalent metal element of structure; X is the tetravalence aromatic group, tetravalence is alicyclic and aliphatic group or tetravalence heterocyclic group; Y is that divalence is an organic group; Ar is the divalence aromatic group.Metallic-SO
3-M-SO
3The introducing of-chain link is to pass through H
2N-Ar-SO
3-M-O
3S-Ar-NH
2Realize with the participation of diamines and dianhydride reaction.
The present invention compared with prior art, its remarkable advantage is:
1. have special absorption spectrum feature, can make special purposes such as stealth material;
2. solubility is good, and good processing properties is arranged;
3. in polyimide, introduce after the metal, increased the functional of material, can do uses such as catalyzer;
4. the resistance toheat of material improves a lot than current material.
Below by embodiment the present invention is further described.Embodiment 1: contain in the main chain-SO
3-Ba-SO
3-polyimide, its structural formula is:
Reaction formula is
Preparation process is: add quantitative diamines ASA (Ba) and MDA[ASA (Ba) molar percentage in total diamines and change between 0~100% in reaction flask], dissolve with polar solvent such as DMF, (mol ratio of dianhydride and diamines is 1.020: 1 to add dianhydride (PMDA) powder under 10~25 ℃ of stirrings one by one on a small quantity, solid content remains on 25% in the reaction, the molecular weight maximum that obtain this moment), behind the reaction 4h, with gained polyamic acid (PAA) solution hectare on sheet glass, wipe off, remove desolvate PAA (Ba) film, this film through 300 ℃ of high-temperature vacuum dehydration 2h, promptly gets PI (Ba) film again.So just made on the main chain and contained-SO
3-Ba-O
3The polyimide of S.
Experiment records physical and chemical parameter and is: 1.PI (Ba) IR wave number (cm
-1)
Imide structure-SO
2-O-structure 10% 1,775 1,725 720 1,190 1,050 645 50% 1,780 1,725 720 1,190 1,050 645 100% 1,780 1,720 720 1,190 1,050 645
2.PI (Ba) solid-state nuclear magnetic resonance carbon spectrum data (ppm)
1., 2., 3., 4., 5., 6. represent C in I formula, the II formula
1~6The position.
C
1C
2C
3C
4C
5C
6PIBa (10%) (formula I, 165.4 142.8 136.9 131.8 117.1 42.3 PIBa (50%) (formula I down together), 165.4 143.2 138.1 130.9 117.4 42.3 PIBa (100%) (formula II, down together) 165.4 142.7 136.8 131.0 117.8 129.2 down together)
3.PAA (Ba) viscosities il
Inh(d1/g) (among the DMF, 25 ℃, down together)
10% 0.75
50% 0.51
100% 0.30
4.PI thermostability (Ba) (still air, 10 ℃/min of temperature rise rate, down together)
T
d(℃) T
p(℃)
10% 512.4 602.1
50% 480.0 530.8
100% 472.3 508.7
T
d: temperature of initial decomposition among the TG
T
p: heat release peak-to-peak temperature among the DTA
Purposes: PI (Ba) can be used as engineering plastics, heat-resisting composite, and coating, film etc., PI (Ba) film is brighter more than PI film.Embodiment 2: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Ca, and corresponding physical and chemical parameter is: PI (Ca) IR wave number (cm
-1)
Imide structure-SO
2-O-structure 10% 1,775 1,715 720 1,175 1,020 64550% 1,775 1,720 720 1,175 1,020 630100% 1,775 1,720 720 1,175 1,020 645
2.PI (Ca) solid-state nuclear magnetic resonance carbon spectrum data (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 142.0 137.3 130.0 119.0 42.3
50% 165.4 143.0 136.7 130.5 121.1 42.3
100% 165.8 145.1 137.6 133.1 116.4 127.8
3.PAA (Ca) viscosity
10% 0.78
50% 0.52
100% 0.31
4.PI thermostability (Ca)
T
d(℃) T
p(℃)
10% 536.5 574.1
50% 480.2 540.9
100% 470.1 498.6 embodiment 3: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Sr, and corresponding physical and chemical parameter is:
1.PI (Sr) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1175 1720 720 1190 1050 645
50% 1780 1720 720 1180 1050 645
100% 1780 1720 720 1180 1050 645
2.PI (Sr) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 141.6 137.8 130.1 116.4 41.8
50% 165.4 143.5 137.8 129.4 116.4 41.8
100% 164.9 143.5 138.3 133.1 116.4 127.8
3.PAA (Ca) viscosity
10% 0.67
50% 0.38
100% 0.22
4.PI thermostability (Sr)
T
d(℃) T
p(℃)
10% 517.9 590.6
50% 490.2 580.2
100% 467.8 500.1 embodiment 4: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Zn, and corresponding physical and chemical parameter is:
1.PI (Zn) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1775 1720 720 1195 1040 645
50% 1775 1720 720 1195 1040 645
100% 1780 1720 720 1195 1040 645
2.PI (Zn) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 143.0 137.8 129.4 116.9 41.8
50% 165.4 143.0 137.8 129.3 116.8 41.8
100% 166.0 145.1 137.8 133.7 116.9 127.3
3.PAA (Zn) viscosity
10% 0.83
50% 0.58
100% 0.32
4.PI thermostability (Zn)
T
d(℃) T
p(℃)
10% 492.0 530.2
50% 460.7 500.7
100% 450.9 498.2 embodiment 5: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Cu, and corresponding physical and chemical parameter is:
1.PI (Cu) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1770 1715 720 1175 1035 645
50% 1775 1720 720 1180 1035 645
100% 1775 1720 720 1175 1035 645
2.PI (Cu) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 142.9 136.8 129.4 117.1 42.8
50% 165.4 143.2 138.4 130.2 116.3 42.1
100% 164.8 143.7 139.1 133.7 116.5 127.8
3.PAA (Cu) surmise
10% 0.62
50% 0.39
100% 0.26 embodiment 6: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Pb, and corresponding physical and chemical parameter is:
1.PI (Pb) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1775 1710 720 1175 1035 645
50% 1775 1720 720 1175 1035 645
100% 1780 1725 720 1190 1050 645
2.PI (Pb) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 143.1 137.6 130.0 116.4 42.8
50% 165.4 143.5 137.8 129.4 116.4 41.8
100% 164.9 143.5 138.3 133.1 116.4 127.9
3.PAA (Pb) viscosity
10% 0.72
50% 0.45
100% 0.25
4.PI thermostability (Pb)
T
d(℃) T
p(℃)
10% 468.3 536.0
50% 467.0 492.2
100% 461.4 484.8 embodiment 7: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Co, and corresponding physical and chemical parameter is:
1.PI (Co) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1750 1715 720 1175 1040 650
50% 1775 1720 720 1175 1035 650
100% 1780 1720 720 1175 1040 645
2.PI (Co) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 143.0 137.8 129.4 116.9 41.8
50% 165.4 142.7 137.6 129.6 117.1 41.9
100% 166.1 145.2 137.6 132.7 116.8 127.3
3.PAA (Co) viscosity
10% 0.47
50% 0.30
100% 0.23
4.PI thermostability (Co)
T
d(℃) T
p(℃)
10% 484.4 522.3
50% 460.7 498.6
100% 455.6 478.9 embodiment 8: other is with embodiment 1, and its difference is that the metal Ba in the main chain is changed to Ni, and corresponding physical and chemical parameter is:
1.PI (Ni) IR wave number (cm
-1)
Imide structure-SO
2-O-structure
10% 1775 1715 720 1175 1020 645
50% 1780 1715 720 1180 1035 650
100% 1775 1720 720 1180 1035 650
2.PI (Ni) solid carbon spectrum (ppm)
C
1 C
2 C
3 C
4 C
5 C
6
10% 165.4 143.0 137.8 130.0 117.4 42.3
50% 165.4 143.0 137.8 130.0 117.4 42.3
100% 164.7 142.9 137.6 131.2 117.8 128.1
3.PAA (Ni) viscosity
10% 0.53
50% 0.40
100% 0.24
4.PI thermostability (Ni)
T
d(℃) T
p(℃)
10% 484.4 522.3
50% 467.2 500.6
100% 453.7 489.8
Claims (5)
Wherein M is a divalent metal element; X is the tetravalence aromatic group, tetravalence is alicyclic and aliphatic group, tetravalence heterocyclic group; Y is a divalent organic group; Ar is the divalence aromatic group.
2. polyimide according to claim 1 is characterized in that M is divalent metal Mg, Ca, Sr, Ba, Zn, Pb, Cu, Co, Ni.
3. polyimide according to claim 1 and 2 is characterized in that X is:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN93111577A CN1035511C (en) | 1993-07-10 | 1993-07-10 | Polyimide with sulfonate segment in main chain |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN93111577A CN1035511C (en) | 1993-07-10 | 1993-07-10 | Polyimide with sulfonate segment in main chain |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1097430A CN1097430A (en) | 1995-01-18 |
CN1035511C true CN1035511C (en) | 1997-07-30 |
Family
ID=4989346
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CN93111577A Expired - Fee Related CN1035511C (en) | 1993-07-10 | 1993-07-10 | Polyimide with sulfonate segment in main chain |
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CN (1) | CN1035511C (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100682861B1 (en) * | 2004-02-17 | 2007-02-15 | 삼성에스디아이 주식회사 | Polyimide comprising sulfonic acid group at the terminal of side chain, method for preparing the same and polymer electrolyte and fuel cell using the same |
KR102529151B1 (en) * | 2016-01-27 | 2023-05-08 | 삼성전자주식회사 | Composition for preparing article including polyimide or poly(amide-imide) copolymer, article obtained therefrom, and display device including same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56104941A (en) * | 1980-01-25 | 1981-08-21 | Mitsui Toatsu Chem Inc | Polysulfonamide ester and preparation therefor |
US4588805A (en) * | 1984-09-06 | 1986-05-13 | General Electric Company | Sulfonate-terminated polyimides and polyamic acids and method for their preparation |
JPS6463952A (en) * | 1987-09-03 | 1989-03-09 | Nippon Telegraph & Telephone | Photosensitive polyimide |
US5214123A (en) * | 1992-02-25 | 1993-05-25 | Eastman Kodak Company | Preparation of aromatic poly(imide-amide)s from CO, primary diamine and di(trifluoro methane sulfonate) containing phthalimide group |
-
1993
- 1993-07-10 CN CN93111577A patent/CN1035511C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56104941A (en) * | 1980-01-25 | 1981-08-21 | Mitsui Toatsu Chem Inc | Polysulfonamide ester and preparation therefor |
US4588805A (en) * | 1984-09-06 | 1986-05-13 | General Electric Company | Sulfonate-terminated polyimides and polyamic acids and method for their preparation |
JPS6463952A (en) * | 1987-09-03 | 1989-03-09 | Nippon Telegraph & Telephone | Photosensitive polyimide |
US5214123A (en) * | 1992-02-25 | 1993-05-25 | Eastman Kodak Company | Preparation of aromatic poly(imide-amide)s from CO, primary diamine and di(trifluoro methane sulfonate) containing phthalimide group |
Non-Patent Citations (1)
Title |
---|
J POLYM SCI,POLYM.CHEM.29,83-91(1991),HIDEAKI MATSODA * |
Also Published As
Publication number | Publication date |
---|---|
CN1097430A (en) | 1995-01-18 |
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