CN112194792B - High-strength low-thermal-expansion transparent polyimide and preparation method thereof - Google Patents

High-strength low-thermal-expansion transparent polyimide and preparation method thereof Download PDF

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CN112194792B
CN112194792B CN202010548005.3A CN202010548005A CN112194792B CN 112194792 B CN112194792 B CN 112194792B CN 202010548005 A CN202010548005 A CN 202010548005A CN 112194792 B CN112194792 B CN 112194792B
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dianhydride
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CN112194792A (en
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郭海泉
杨正慧
康传情
周云春
高连勋
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides high-strength low-thermal-expansion transparent polyimide and a preparation method thereof. The colorless transparent polyimide with high strength and low thermal expansion coefficient is based on that the polyimide molecular structure contains an amide structure, the prepared polyimide containing the amide structure can form intermolecular hydrogen bonds, and further forms a hydrogen bond cross-linked network, and the strong intermolecular interaction enables the transparent polyimide to show high modulus, high strength and low thermal expansion coefficient, and simultaneously retains the transparency of the polyimide. According to the present invention, a polyimide and a polyimide film containing the polyimide can be provided, and thus can be used in the field of transparent films requiring resistance to bending, such as cover materials for flexible displays, substrate materials, and the like.

Description

High-strength low-thermal-expansion transparent polyimide and preparation method thereof
Technical Field
The invention belongs to the technical field of flexible display, and particularly relates to high-strength low-thermal-expansion transparent polyimide and a preparation method thereof.
Background
Flexible display technology is an important development direction in the field of flat panel displays at present. Flexible, light and thin flexible display devices, such as flexible Organic Light Emitting Diode (OLED) displays, flexible solar cells, etc., have become essential elements of high-tech products in the field of consumer electronics. The flexible display device replaces glass materials with polymer film materials, and achieves thinning, light weight and flexibility of a display.
At present, colorless and transparent polyimide materials are needed for cover plate and substrate materials of flexible display. A wholly aromatic polyimide obtained by a polycondensation reaction of a generally used aromatic tetracarboxylic dianhydride and an aromatic diamine exhibits a deep amber color, and is difficult to apply to a field of high transparency. Further, since the wholly aromatic polyimide has a high thermal expansion coefficient, it is limited as an application requiring transparency and a low thermal expansion coefficient. Generally, in order to achieve high transparency, polyimide is generally produced using a fluorine-containing dianhydride monomer, an alicyclic tetracarboxylic dianhydride and a monomer diamine, but these transparent polyimides are generally low in modulus and strength, are not resistant to bending, and have a high thermal expansion coefficient, and therefore the current transparent polyimides are not satisfactory in the field of application of flexible displays. In flexible display applications, the flexible material needs to have high heat resistance, high modulus, high strength, and bending resistance as well as transparency. In addition, the multilayer composite film construction of display panels requires that the substrate material have high temperature dimensional stability to accommodate other film layer materials, i.e., have a low coefficient of linear thermal expansion (CTE <15 ppm/K). Maintaining dimensional stability will affect the quality and reliability of the display device. If the substrate has too large a dimensional change at high temperature, internal stress will be generated between the interfaces of the material layers, resulting in a decrease in display accuracy of the device and layer-to-layer peeling upon bending.
In the polymer substrate material prepared by the prior art, the requirements of high heat resistance, high modulus, high strength, low thermal expansion coefficient and enough transparency required by flexible display are met, and the difficulty of technical development is remained.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a high-strength low-thermal expansion transparent polyimide and a preparation method thereof, wherein the high-strength low-thermal expansion transparent polyimide provided by the present invention has high heat resistance, high modulus, high strength, low thermal expansion coefficient and sufficient transparency.
The invention provides a high-strength low-thermal-expansion transparent polyimide which is a polymer containing a structural group shown in a formula I;
Figure BDA0002541445310000011
wherein the content of the first and second substances,
Figure BDA0002541445310000012
selected from one of the groups with the structures shown in formulas II to IV,
Figure BDA0002541445310000013
in the formula II, R1Is composed of
Figure BDA0002541445310000014
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3or-CF3；
In the formula III, R3And R4Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000021
R3and R4At least one of which is
Figure BDA0002541445310000022
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000023
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group;
in the formula IV, R7、R8And R9Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000024
R7、R8and R9At least one of which is
Figure BDA0002541445310000025
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000026
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group; (ii) a
—Ar2-one selected from the group having a structure according to formula V to formula VII,
Figure BDA0002541445310000027
in the formula V, R12Is composed of
Figure BDA0002541445310000028
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3or-CF3；
In the formula VI, R14And R15Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000031
R14and R15At least one of which is
Figure BDA0002541445310000032
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000033
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group;
in the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000034
R18、R19and R20At least one of which is
Figure BDA0002541445310000035
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000036
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group;
preferably, the compound further comprises a group having a structure represented by formula VIII
Figure BDA0002541445310000037
Wherein the content of the first and second substances,
Figure BDA0002541445310000038
is a radical of the structure
Figure BDA0002541445310000039
Figure BDA0002541445310000041
R23、R25、R26、R29、R30、R31Independently selected from the following structures:
Figure BDA0002541445310000042
R24、R27、R28、R32、R33independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000043
Independently selected from a substituted aromatic group, heterocyclic group, cycloaliphatic group, aliphatic group, or combinations thereof, preferably a substituted aromatic group, cycloaliphatic group.
Preferably, the compound further comprises a group having a structure represented by formula IX
—Ar10Formula IX
wherein-Ar is10-is a group of the following structure:
Figure BDA0002541445310000044
R34、R36、R37、R40、R41、R42selected from the following structures:
Figure BDA0002541445310000051
R35、R38、R39、R43、R44、R45selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000052
Independently selected from a substituted aromatic group, heterocyclic group, cycloaliphatic group, aliphatic group, or combinations thereof, preferably a substituted aromatic group, cycloaliphatic group.
The invention also provides a preparation method of the high-strength low-thermal-expansion transparent polyimide, which comprises the following steps:
carrying out condensation polymerization on a dianhydride monomer and a diamine monomer and then imidizing to obtain polyimide;
the dianhydride monomer has a structure represented by formula X:
Figure BDA0002541445310000053
wherein the content of the first and second substances,
Figure BDA0002541445310000054
selected from one of the groups with the structures shown in formulas II to IV,
Figure BDA0002541445310000055
in the formula II, R1Is composed of
Figure BDA0002541445310000056
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo; preferably, -H, -F, CH3、-CF3；
In the formula III, R3And R4Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000057
R3and R4At least one of which is
Figure BDA0002541445310000061
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably, -H, -F, CH3、-CF3；
Figure BDA0002541445310000062
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group;
in the formula IV, R7、R8And R9Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000063
R7、R8and R9At least one of which is
Figure BDA0002541445310000064
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably, -H, -F, CH3、-CF3；
Figure BDA0002541445310000065
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group; (ii) a
The diamine monomer has a structure represented by formula XI:
H2N-Ar2-NH2formula XI
—Ar2-one selected from the group having a structure according to formula V to formula VII,
Figure BDA0002541445310000066
in the formula V, R12Is composed of
Figure BDA0002541445310000067
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo; preferably-H, -F, CH3、-CF3；
In the formula VI, R14And R15Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000071
R14and R15At least one of which is
Figure BDA0002541445310000072
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000073
Selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or a combination thereof, preferably a substituted aromatic group, alicyclic group;
in the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000074
R18、R19and R20At least one of which is
Figure BDA0002541445310000075
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000076
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups, alicyclic groups.
Preferably, the dianhydride monomer is selected from one of first dianhydride compounds having the following structure;
Figure BDA0002541445310000077
Figure BDA0002541445310000081
Figure BDA0002541445310000091
the diamine compound is selected from one of first diamine compounds having the following structure;
Figure BDA0002541445310000092
Figure BDA0002541445310000101
Figure BDA0002541445310000111
preferably, the dianhydride monomer further comprises a second dianhydride monomer containing fluorine, trifluoromethyl, ether, sulfone or alicyclic group, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 10: (0 to 50);
the second dianhydride monomer is selected from one of the dianhydride compounds having the following structure:
Figure BDA0002541445310000112
preferably, the diamine monomer further comprises a second diamine monomer containing fluorine, trifluoromethyl, ether, sulfone or alicyclic group, and the molar ratio of the first diamine monomer to the second diamine monomer is 10: (0 to 50);
the second diamine monomer is one selected from diamine compounds having the following structures:
Figure BDA0002541445310000113
Figure BDA0002541445310000121
preferably, the dianhydride monomer further comprises a third dianhydride monomer, the molar amount of the third dianhydride monomer is not more than 10% of the total molar amount of the dianhydride monomers;
the third dianhydride monomer is selected from one of 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride, bis (dicarboxyphenyldimethyl) silane dianhydride, bis (dicarboxybenzoic acid) terephthalate dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenoxy diphenyl) sulfide dianhydride, isopropylidene diphenoxy bisphthalic anhydride, bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and bicyclohexane tetracarboxylic dianhydride.
Preferably, the diamine monomer further comprises a third diamine monomer, wherein the molar amount of the third diamine monomer is not more than 10% of the total molar amount of the diamine monomer;
the third diamine monomer is selected from p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4-aminobenzoic acid (4-aminophenol) ester, 1, 3-bis (4,4' -aminophenoxy) benzene, 4' -diamino-1, 5-phenoxypentane, 3' -dimethyl-4, 4' -benzidine, 3' -dimethoxy-4, 4' -benzidine, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4' -diaminodiphenylmethane, 2' -diaminodiphenylpropane, bis (3, 5-diethyl-4-aminophenyl) methane, 4' -diaminodiphenylsulfone, N-phenylenediamine, N-1-phenylenediamine, N-1-3, 4-diamino-4-phenoxypentane, 3, 4-phenoxypentane, 4-diphenylpropane, 3, 4-diphenyl amine, 4-dimethoxybenzene, 4-diphenylpropane, 4-amino-diphenyl amine, 4-diphenyl amine, 4-amino-phenylene, 4-diphenyl ether, 4-diphenyl ether, 4-amino benzene, 4-phenylene, 4-phenylene, 4-diphenylsulfone, 4-phenylene, 4-phenylene, and benzene, 4-phenylene, 4-diphenylsulfone, 4-phenylene, 4, and benzene, 4, one, and benzene, one, and one, and one, 3,3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -diaminodiphenyl propane, 1, 4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-cyclohexanedi (methylamine), 4' -diaminodicyclohexylmethane, 4' -methylenebis (2-methylcyclohexylamine).
The invention also provides a polyimide film prepared from the high-strength low-thermal-expansion transparent polyimide.
Compared with the prior art, the colorless transparent polyimide with high strength and low thermal expansion coefficient is based on that the polyimide molecular structure contains an amide structure, the prepared polyimide containing the amide structure can form intermolecular hydrogen bonds, and further forms a hydrogen bond cross-linked network, and the strong intermolecular interaction enables the transparent polyimide to show high modulus, high strength and low thermal expansion coefficient, and simultaneously retains the transparency of the polyimide. According to the present invention, a polyimide and a polyimide film containing the polyimide can be provided, and thus can be used in the field of transparent films requiring resistance to bending, such as cover materials for flexible displays, substrate materials, and the like.
The result shows that the average light transmittance of the transparent polyimide prepared by the invention at the wavelength of 380-780 nm is 86% or more than 86% based on the film thickness of 50 μm measured by a UV spectrometer, the Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is <15 ppm/DEG C, the tensile strength is greater than 200MPa, the modulus is greater than 6.0GPa, and the elongation at break is greater than 30%.
Detailed Description
The invention provides a high-strength low-thermal-expansion transparent polyimide which is a polymer containing a structural group shown in a formula I;
Figure BDA0002541445310000122
wherein the content of the first and second substances,
Figure BDA0002541445310000123
selected from one of the groups with the structures shown in formulas II to IV,
Figure BDA0002541445310000124
Figure BDA0002541445310000131
in the formula II, R1Is composed of
Figure BDA0002541445310000132
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3or-CF3；
In the formula III, R3And R4Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000133
R3and R4At least one of which is
Figure BDA0002541445310000134
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000135
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000136
In the formula IV, R7、R8And R9Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000137
R7、R8and R9At least one of which is
Figure BDA0002541445310000138
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000139
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000141
—Ar2Selected from structures of formulae V to VIIOne of the groups of (a) or (b),
Figure BDA0002541445310000142
in the formula V, R12Is composed of
Figure BDA0002541445310000143
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3or-CF3；
In the formula VI, R14And R15Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000144
R14and R15At least one of which is
Figure BDA0002541445310000145
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000146
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000147
In the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000148
R18、R19and R20At least one of which is
Figure BDA0002541445310000151
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000152
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000153
In some embodiments of the present invention, the polyimide further comprises a group having a structure represented by formula VIII
Figure BDA0002541445310000154
Wherein the content of the first and second substances,
Figure BDA0002541445310000155
is a radical of the structure
Figure BDA0002541445310000156
R23、R25、R26、R29、R30、R31Independently selected from the following structures:
Figure BDA0002541445310000157
R24、R27、R28、R32、R33independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo; preferably-H, -F, CH3or-CF3；
Figure BDA0002541445310000158
Independently selected from the group consisting of substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups, alicyclic groups, and more preferably substituted aromatic groups, alicyclic groups, and combinations thereof
Figure BDA0002541445310000159
In the present invention, also included are groups having the structure of formula IX
—Ar10Formula IX
wherein-Ar is10-is a group of the following structure:
Figure BDA0002541445310000161
R34、R36、R37、R40、R41、R42selected from the following structures:
Figure BDA0002541445310000162
R35、R38、R39、R43、R44、R45selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000163
Independently selected from substituted aromatic groups,A heterocyclic group, an alicyclic group, an aliphatic group, or a combination thereof, preferably a substituted aromatic group or alicyclic group, and more preferably a substituted aromatic group or alicyclic group
Figure BDA0002541445310000164
The invention also provides a preparation method of the high-strength low-thermal-expansion transparent polyimide, which comprises the following steps:
carrying out condensation polymerization on a dianhydride monomer and a diamine monomer and then imidizing to obtain polyimide;
the dianhydride monomer has a structure represented by formula X:
Figure BDA0002541445310000165
wherein the content of the first and second substances,
Figure BDA0002541445310000166
selected from one of the groups with the structures shown in formulas II to IV,
Figure BDA0002541445310000167
in the formula II, R1Is composed of
Figure BDA0002541445310000171
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo; preferably, -H, -F, CH3、-CF3；
In the formula III, R3And R4Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000172
R3and R4At least one of which is
Figure BDA0002541445310000173
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably, -H, -F, CH3、-CF3；
Figure BDA0002541445310000174
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000175
In the formula IV, R7、R8And R9Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000176
R7、R8and R9At least one of which is
Figure BDA0002541445310000177
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably, -H, -F, CH3、-CF3；
Figure BDA0002541445310000178
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000179
The diamine monomer has a structure represented by formula XI:
H2N-Ar2-NH2formula XI
—Ar2-one selected from the group having a structure according to formula V to formula VII,
Figure BDA00025414453100001710
Figure BDA0002541445310000181
in the formula V, R12Is composed of
Figure BDA0002541445310000182
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo; preferably-H, -F, CH3、-CF3；
In the formula VI, R14And R15Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000183
R14and R15At least one of which is
Figure BDA0002541445310000184
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000185
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups, alicyclic groups, and more preferably substituted aromatic groups, alicyclic groups, and combinations thereofIs selected as
Figure BDA0002541445310000186
In the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
Figure BDA0002541445310000187
R18、R19and R20At least one of which is
Figure BDA0002541445310000188
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo; preferably-H, -F, CH3、-CF3；
Figure BDA0002541445310000189
Selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, preferably substituted aromatic groups and alicyclic groups, and more preferably substituted aromatic groups and alicyclic groups
Figure BDA0002541445310000191
In some embodiments of the present invention, the dianhydride monomer is selected from one of the first dianhydride compounds having the structure;
Figure BDA0002541445310000192
Figure BDA0002541445310000201
the diamine compound is selected from one of first diamine compounds having the following structure;
Figure BDA0002541445310000202
Figure BDA0002541445310000211
Figure BDA0002541445310000221
from the viewpoint of high transparency, high modulus and low thermal expansion coefficient, the dianhydride monomer also comprises a second dianhydride monomer containing fluorine, trifluoromethyl, ether, sulfuryl or alicyclic group, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 10: (0 to 50); preferably 10: (2-40).
The second dianhydride monomer is selected from one of the dianhydride compounds having the following structure:
Figure BDA0002541445310000222
from the viewpoint of high transparency, high modulus and low thermal expansion coefficient, the diamine monomer further comprises a second diamine monomer containing fluorine, trifluoromethyl, ether, sulfone or alicyclic group, and the molar ratio of the first diamine monomer to the second diamine monomer is 10: (0 to 50); preferably 10: (2-40).
The second diamine monomer is one selected from diamine compounds having the following structures:
Figure BDA0002541445310000231
the present invention may also add a third dianhydride monomer or a third diamine monomer for the purpose of improving heat resistance, etc. The amount of the third dianhydride monomer added is no more than 10% of the total dianhydride molar amount added, and likewise, the amount of the third diamine monomer added is no more than 10% of the total diamine molar amount added.
The third dianhydride monomer is selected from one of 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride, bis (dicarboxyphenyldimethyl) silane dianhydride, bis (dicarboxybenzoic acid) terephthalate dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenoxy diphenyl) sulfide dianhydride, isopropylidene diphenoxy bisphthalic anhydride, bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and bicyclohexane tetracarboxylic dianhydride.
The third diamine monomer is selected from p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4-aminobenzoic acid (4-aminophenol) ester, 1, 3-bis (4,4 '-aminophenoxy) benzene, 4' -diamino-1, 5-phenoxypentane, 3 '-dimethyl-4, 4' -benzidine, 3 '-dimethoxy-4, 4' -benzidine, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane, 2' -diaminodiphenylpropane, bis (3, 5-diethyl-4-aminophenyl) methane, 4 '-diaminodiphenylsulfone, 2, 4' -diaminodiphenylsulfone, and mixtures thereof, 3,3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -diaminodiphenyl propane, 1, 4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-cyclohexanedi (methylamine), 4' -diaminodicyclohexylmethane, 4' -methylenebis (2-methylcyclohexylamine).
In the present invention, the method for obtaining the polyamic acid is not particularly limited, and can be synthesized by a known general method.
Such as a preparation method from dianhydride monomers and diamine monomers by solution polymerization of polyimide, which is well known to those skilled in the art.
Dispersing a diamine monomer and a dianhydride monomer in an organic solvent, specifically comprising:
dissolving or dispersing diamine monomer in organic solvent to obtain slurry, preparing diamine monomer solution, and adding dianhydride monomer into the diamine solution. The tetracarboxylic dianhydride may be added in a solid state or may be added in a state of being dissolved or dispersed in an organic solvent in a slurry state.
Specific examples of the organic solvent may include N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, m-cresol, N-methylcaprolactam, sulfolane, Dimethylsulfoxide (DMSO), cyclohexanone, hexamethylphosphoramide, and γ -butyrolactone. These solvents may be used alone or in combination of two or more. Further, even a solvent which does not dissolve the polyamic acid may be added to the above solvent within the range where a homogeneous solution is obtained.
The molecular weight of the polyamic acid can be controlled by changing the molar ratio of the sum of all dianhydrides to the sum of all diamines in the polymerized monomers in the reaction, such as in a normal polycondensation reaction, the ratio of the amount of the dianhydride to the diamine in the polymerized monomers is 100 (95-105), preferably the molar ratio is close to 100:100, and the molecular weight of the polyamic acid obtained becomes larger. In some embodiments of the invention, the molecular weight, expressed as weight average molecular weight, is greater than 5X 104g/mol。
The temperature conditions for the reaction are not particularly limited. The reaction temperature is preferably 80 ℃ or lower from the viewpoint of suppressing the decrease in the molecular weight of the polyamic acid due to depolymerization. From the viewpoint of properly proceeding the polymerization reaction, the reaction temperature is more preferably 0 to 50 ℃. The reaction time may be set arbitrarily within the range of 10 minutes to 30 hours.
The polyimide is produced from a polyamic acid via dehydrocyclized imidization, which is not particularly limited, and may be thermal imidization or chemical imidization. As with the usual polyamic acid, imidization can be carried out by heating or chemical cyclization using a known dehydration reaction. The temperature can be increased gradually from 80 ℃ to 400 ℃ by using a heating method, and in some embodiments of the invention, the temperature is increased at a gradient heating rate of 1-10 ℃/min to perform imidization reaction for forming imide by dehydration and cyclization of amic acid.
The chemical cyclization imidization method is a reaction for forming imide by adding a chemical dehydrating agent to perform amic acid dehydration cyclization. The dehydrating agent may be selected from acetic anhydride. Catalysis can be carried out using organic bases such as pyridine or triethylamine. The processing temperature may be in the range of-20 ℃ to 200 ℃. In this reaction, the polymerization solution of polyamic acid may be used without change, or may be diluted.
The polyimide-containing solution thus obtained may be used, or may be used by: the polymer is precipitated using a solvent such as methanol or ethanol and then isolated in the form of powder, or the resulting powder is redissolved in an appropriate solvent before use. The solvent for re-dissolution is not particularly limited as long as the resulting polymer can be dissolved, and includes one or more of m-cresol, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone, and γ -butyrolactone.
The invention also comprises the step of adding a filler into the polyimide, wherein the filler comprises silicon dioxide, tetraalkoxysilane, polysiloxane, siloxane surfactant and siloxane coupling agent, and specifically can be 1-3 selected from nano silicon dioxide, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, polyether siloxane and polysilsesquioxane. The filler is added before or after the polymerization to obtain the polyamic acid. The filler is added in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the polyamic acid. Preferably 0.1 to 15 parts by weight.
In addition, the invention also provides a polyimide film, and the preparation method comprises the following steps: the polyamic acid is cast on a support and then subjected to the above-described dehydration ring-closing imidization reaction. In this manner, the polyamic acid is converted into polyimide.
In the present invention, the polyimide film formed by the dehydrocyclization reaction may be again subjected to a high-temperature heating treatment to remove thermal hysteresis and residual stress from the film, thereby securing high thermal stability and achieving a low thermal expansion coefficient.
The thickness of the polyimide film thus produced is not particularly limited, but is preferably 10 to 250 μm, and more preferably 10 to 100 μm.
The functional layer necessary for flexible display can be directly formed on the surface of the formed polyimide film material; the polyimide film may be peeled off from the surface of the carrier to obtain a self-supporting film material, which is a functional layer required for flexible display in surface processability.
In the molecular structure of polyimide, the residue of dianhydride as one of the polycondensation monomers shows an electron-deficient characteristic, and the residue of diamine as the other polycondensation monomer shows an electron-rich characteristic, and the opposite electronic characteristic forms the shifting and stacking characteristic of polyimide molecular chains during film forming, namely, the residue of dianhydride of one polyimide molecular chain and the stacking adjacent are the residue of diamine of the other polyimide molecular chain. This shifted stacking feature is the structural basis for polyimides with good film forming properties. Meanwhile, the displacement accumulation of dianhydride residues and diamine residues also forms intermolecular charge transfer complexes, which is also an important structural source for forming polyimide colors. In the invention, diamine and dianhydride which are used as polycondensation monomers of transparent polyimide at least simultaneously contain an amide structure, and amide in the dianhydride structure is more easily to form hydrogen bonds with amide in the diamine structure based on the displacement and accumulation characteristics of a polyimide molecular chain, namely, compared with the hydrogen bonds formed between dianhydride containing an amide structure or diamine containing an amide structure, the dianhydride containing the amide structure and diamine containing the amide structure have higher efficiency in forming the hydrogen bonds, and the displacement and accumulation function is beneficial to approaching the structure so as to form intermolecular hydrogen bonds. This hydrogen bond between amide based structures is the molecular basis for transparent polyimides to have high strength, high modulus, and low coefficient of thermal expansion. One embodiment of the higher efficiency is that stronger hydrogen bonding interactions can be achieved when relatively few hydrogen bonds are present in the molecular chain. As one of the advantageous embodiments, the negative effects of increased hygroscopicity, decreased heat resistance, and the like, which may be caused by an excessive amide structure in the molecular chain, in some applications, can be reduced.
The average light transmittance of the transparent polyimide prepared by the invention at 380-780 nm wavelength is 86% or more than 86% based on the film thickness of 50 μm measured by a UV spectrometer, the Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is <15 ppm/DEG C, the tensile strength is more than 200MPa, the modulus is more than 6.0GPa, and the elongation at break is more than 30%.
For further understanding of the present invention, the high strength low thermal expansion transparent polyimide and the preparation method thereof provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
In the following examples, the test apparatus and conditions for the performance test of the samples were as follows:
coefficient of Thermal Expansion (CTE): the test was carried out using a Thermo-plastics TMA thermomechanical analyzer (TMA, TA Q400); and (3) testing conditions are as follows: 10 ℃/min, 100-300 ℃.
Glass transition temperature (Tg): dynamic thermomechanical properties analyzer, Rheometric Scientific Inc, heating rate 2 ℃/min, frequency 1 Hz.
③ optical transmittance: shimadzu Uv-2550 ultraviolet visible spectrum tester, average light transmittance at 380-780 nm wavelength.
And fourthly, tensile test: an electronic universal tester of NSTRON-1121 type with a tensile rate of 5 mm/min.
Rotational viscosity: digital viscometer, room temperature.
Sixthly logarithmic viscosity ([ eta ]]inh): ubbelohde viscometer, 30 ℃.
Number average molecular weight (M)n) And weight average molecular weight (M)W): PL-GPC120 gel permeation chromatograph
In the following examples, the structures of the raw materials are as follows
Figure BDA0002541445310000251
Figure BDA0002541445310000261
Example 1
2.27g of the diamine compound (1), 3.20g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 80.0g of dimethylacetamide were added to a reaction vessel, and dissolved with stirring at 20 ℃. 2.31g of dianhydride compound (8) and 6.66g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride were added in this order and polymerized for 24 hours to obtain a rotary viscosity of 4.5X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
10.20g of acetic anhydride and 5.05g of triethylamine were added to the precursor solution to conduct chemical imidization for 2 hours. After the imidization was completed, a polyimide solution was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured. The solution was slowly poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 2
4.14g of the diamine compound (2), 10.02g of 2, 2-bis (4-aminophenyl) hexafluoropropane and 90g of N-methylpyrrolidone were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 5.24g of dianhydride compound (7) and 6.72g of cyclohexane tetracarboxylic dianhydride were added in this order to conduct polymerization for 24 hours, and the rotational viscosity was measured to be 3.6X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
20.0g of acetic anhydride and 10.1g of triethylamine were added to this precursor solution, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 3
3.52g of the diamine compound (3), 2.85g of 4,4' -diaminocyclohexane and 100g N-methylpyrrolidone were charged into a reaction vessel, and dissolved with stirring at 20 ℃. 6.74g of dianhydride Compound (6) and 1.69g of dicarboxy benzoic acid (dicarboxyphenol) ester dianhydride were added in this order, and polymerized for 24 hours to test that the rotational viscosity thereof reached 4.2X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
18.4g of acetic anhydride and 8.84g of triethylamine were added to this precursor solution, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 4
Into a reaction vessel were added 3.46g of the diamine compound (4), 0.496g of 2, 4' -diaminodiphenyl sulfone and 50g of N-methylpyrrolidone, and the mixture was dissolved with stirring at 20 ℃. 4.56g of dianhydride compound (9) and 0.588g of biphenyl dianhydride are added in sequence for polymerization reaction for 24 hours, and the rotational viscosity is tested to reach 4.2 multiplied by 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
6.12g of acetic anhydride and 3.03g of triethylamine were added to the precursor solution, and the reaction was continued for 2 hours. After the imidization was completed, a polyimide solution was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured. The solution was poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 5
3.52g of the diamine compound (5), 9.60g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 70g of N-methylpyrrolidone were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 6.74g of dianhydride compound (6) and 4.44g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride were added in this order, and polymerization was carried out for 24 hours to test that the rotational viscosity reached 4.2X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
5.10g of acetic anhydride and 5.05g of triethylamine were added to the precursor solution, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was slowly poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured. The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 6
2.27g of the diamine compound (1), 2.84g of 4,4' -bis (3-trifluoromethyl-4-aminophenoxy) diphenylsulfone and 60g of N-methylpyrrolidone were charged into a reaction vessel and dissolved with stirring at 20 ℃. 2.31g of dianhydride compound (10) and 1.96g of cyclobutanetetracarboxylic dianhydride were added in this order, and polymerization was carried out for 24 hours to test that the rotational viscosity reached 3.2X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
20.4g of acetic anhydride and 5.05g of triethylamine were added to the precursor solution, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was slowly poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured. The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 7
2.27g of the diamine compound (1), 6.40g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 84g N-methylpyrrolidone were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 3.37g of dianhydride compound (6) and 7.16g of diphenylsulfone tetracarboxylic dianhydride were added in this order, and polymerization was carried out for 24 hours to test that the rotational viscosity reached 4.4X 104mPa/s, a precursor solution of transparent polyimide was formed, and the logarithmic viscosity, number average molecular weight and weight average molecular weight thereof were measured.
And (3) coating the reaction mixture on the surface of a glass plate, placing the glass plate in a vacuum oven, and heating to 300 ℃ by gradient temperature rise to form a transparent polyimide film with the thickness of 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 8
2.27g of the diamine compound (1), 12.8g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1.5g of fumed silica nanoparticles, 0.2g of 3-aminopropyltriethoxysilane solvent and 150g of dimethylacetamide were charged into a reaction vessel and dissolved with stirring at 20 ℃. 3.37g of dianhydride compound (6) and 17.76g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride were successively added thereto and polymerized for 24 hours. The rotational viscosity is tested to reach 4.5 multiplied by 104mPa/s, a precursor solution of transparent polyimide was formed, and the number of logarithmic viscosity, average molecular weight and weight average molecular weight thereof were measured.
And (3) coating the reaction mixture on the surface of a glass plate, placing the glass plate in a vacuum oven, and heating to 300 ℃ by gradient temperature rise to form a transparent polyimide film with the thickness of 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 9
2.27g of the diamine compound (1), 6.40g of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 0.100g of 4,4' -diaminodiphenyl ether and 90g N-methylpyrrolidone were charged into a reaction vessel, and dissolved with stirring at 20 ℃. 3.37g of dianhydride compound (6) and 9.10g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride were added in this order to conduct polymerization for 24 hours, and the rotational viscosity was measured to be 3.2X 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
To this precursor solution were added 15.3g of acetic anhydride and 6.06g of triethylamine, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was slowly poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
Example 10
2.27g of the diamine compound (1), 9.60g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 113g N-methylpyrrolidone were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 3.37g of dianhydride compound (6), 13.1g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride and 0.147g of biphenyltetracarboxylic dianhydride were successively added thereto and subjected to polymerization reaction for 24 hours. The rotational viscosity is tested to reach 3.2 multiplied by 104mPa/s, forming a precursor solution of a transparent polyimide, the logarithmic viscosity of which was tested.
20.4g of acetic anhydride and 10.2g of triethylamine were added to this precursor solution, and the reaction was continued for 2 hours. After imidization was completed, a polyimide solution was obtained. The solution was slowly poured into ethanol. White thready precipitate separated out. Filtering out the filiform precipitate and drying. A transparent polyimide resin was obtained, and the number average molecular weight and the weight average molecular weight thereof were measured.
The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, the glass plate is placed in an oven and heated to 200 ℃, and a transparent polyimide film is formed, wherein the thickness of the film is 30 microns. The glass transition temperature, transparency, thermal expansion coefficient and mechanical properties were analyzed.
The properties of the film are shown in Table 1, and Table 1 shows the results of the property measurement of the polyimide film.
TABLE 1 measurement results of polyimide film Properties
Figure BDA0002541445310000281
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A high-strength low-thermal expansion transparent polyimide is characterized by comprising a polymer with a structural group shown as a formula I;
Figure FDA0003474129330000011
wherein the content of the first and second substances,
Figure FDA0003474129330000012
selected from one of the groups with the structures shown in formulas II to IV,
Figure FDA0003474129330000013
in the formula II, R1Is composed of
Figure FDA0003474129330000014
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo;
in the formula III, R3And R4Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000015
Figure FDA0003474129330000016
R3and R4At least one of which is
Figure FDA0003474129330000017
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000018
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof,
in the formula IV, R7、R8And R9Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000021
Figure FDA0003474129330000022
R7、R8and R9At least one of which is
Figure FDA0003474129330000023
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000024
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof;
—Ar2-one selected from the group having a structure according to formula V to formula VII,
Figure FDA0003474129330000025
in the formula V, R12Is composed of
Figure FDA0003474129330000026
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo;
in the formula VI, R14And R15Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000027
Figure FDA0003474129330000028
R14and R15At least one of which is
Figure FDA0003474129330000031
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000032
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof;
in the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000033
Figure FDA0003474129330000034
R18、R19and R20At least one of which is
Figure FDA0003474129330000035
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000036
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof; also included are groups having the structure of formula VIII
Figure FDA0003474129330000037
Wherein the content of the first and second substances,
Figure FDA0003474129330000038
is a radical of the structure
Figure FDA0003474129330000039
Figure FDA0003474129330000041
R23、R25、R26、R29、R30、R31Independently selected from the following structures or linkages:
-O-
Figure FDA0003474129330000042
Figure FDA0003474129330000043
R24、R27、R28、R32、R33independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000044
independently selected from a substituted aromatic group, heterocyclic group, cycloaliphatic group, aliphatic group, or combinations thereof;
also included are groups having the structure of formula IX
—Ar10Formula IX
wherein-Ar is10-is a group of the following structure:
Figure FDA0003474129330000045
R34、R36、R37、R40、R41、R42selected from the following structures or linkages:
-O-
Figure FDA0003474129330000051
Figure FDA0003474129330000052
R35、R38、R39、R43、R44、R45selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo;
Figure FDA0003474129330000053
independently selected from a substituted aromatic group, a heterocyclic group, an alicyclic group, an aliphatic group, or a combination thereof.
2. The high strength low thermal expansion transparent polyimide as claimed in claim 1, wherein R is R2Selected from-H, -F, CH3or-CF3；
R5And R6Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000054
Selected from substituted aromatic groups, cycloaliphatic groups;
R10and R11Independently selected from-H, -F, CH3、-CF3；
Figure FDA0003474129330000055
Selected from substituted aromatic groups, cycloaliphatic groups;
R13selected from-H, -F, CH3or-CF3；
R16And R17Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000056
Selected from substituted aromatic groups, cycloaliphatic groups;
R21and R22Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000057
Selected from substituted aromatic groups, cycloaliphatic groups;
R24、R27、R28、R32、R33independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000058
Independently selected from substituted aromatic groups, cycloaliphatic groups;
R35、R38、R39、R43、R44、R45selected from-H, -F, CH3、-CF3；
Figure FDA0003474129330000059
Independently selected from substituted aromatic groups, alicyclic groups.
3. A method for preparing a high-strength low-thermal expansion transparent polyimide according to any one of claims 1 to 2, comprising the steps of:
carrying out condensation polymerization on a dianhydride monomer and a diamine monomer and then imidizing to obtain polyimide;
the dianhydride monomer has a structure represented by formula X:
Figure FDA0003474129330000061
wherein the content of the first and second substances,
Figure FDA0003474129330000062
selected from one of the groups with the structures shown in formulas II to IV,
Figure FDA0003474129330000063
in the formula II, R1Is composed of
Figure FDA0003474129330000064
R2Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo;
in the formula III, R3And R4Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000065
Figure FDA0003474129330000066
R3and R4At least one of which is
Figure FDA0003474129330000067
R5And R6Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo;
Figure FDA0003474129330000068
selected from substituted aromatic groups, heterocyclic groups, alicyclic groups, aliphatic groups, or combinations thereof, formula IV, R7、R8And R9Independently selected from the group having the structureGroup or linkage:
-O-
Figure FDA0003474129330000071
Figure FDA0003474129330000072
R7、R8and R9At least one of which is
Figure FDA0003474129330000073
R10And R11Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo;
Figure FDA0003474129330000074
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof;
the diamine monomer has a structure represented by formula XI:
H2N-Ar2-NH2formula XI
—Ar2-one selected from the group having a structure according to formula V to formula VII,
Figure FDA0003474129330000075
in the formula V, R12Is composed of
Figure FDA0003474129330000076
R13Selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, halo;
in the formula VI, R14And R15Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000081
Figure FDA0003474129330000082
R14and R15At least one of which is
Figure FDA0003474129330000083
R16And R17Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo;
Figure FDA0003474129330000084
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof;
in the formula VII, R18、R19And R20Independently selected from groups or linkages having the structure:
-O-
Figure FDA0003474129330000085
Figure FDA0003474129330000086
R18、R19and R20At least one of which is
Figure FDA0003474129330000087
R21And R22Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, halo;
Figure FDA0003474129330000088
selected from a substituted aromatic group, heterocyclic group, alicyclic group, aliphatic group, or combinations thereof;
the dianhydride compound also includes compounds having the structure shown in the following formula
Figure FDA0003474129330000089
Wherein the content of the first and second substances,
Figure FDA00034741293300000810
is a radical of the structure
Figure FDA00034741293300000811
Figure FDA0003474129330000091
R23、R25、R26、R29、R30、R31Independently selected from the following structures or linkages:
-O-
Figure FDA0003474129330000092
Figure FDA0003474129330000093
R24、R27、R28、R32、R33independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester group, or halo;
Figure FDA0003474129330000094
independently selected from a substituted aromatic group, heterocyclic group, cycloaliphatic group, aliphatic group, or combinations thereof;
the diamine compound also includes compounds having a structure represented by the following formula;
H2N- Ar10- NH2
wherein-Ar is10-is a group of the following structure:
Figure FDA0003474129330000095
Figure FDA0003474129330000101
R34、R36、R37、R40、R41、R42selected from the following structures or linkages:
-O-
Figure FDA0003474129330000102
Figure FDA0003474129330000103
R35、R38、R39、R43、R44、R45selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halo;
Figure FDA0003474129330000104
independently selected from a substituted aromatic group, a heterocyclic group, an alicyclic group, an aliphatic group, or a combination thereof.
4. The method of claim 3, wherein R is2Is selected from-H-F、CH3or-CF3；
R5And R6Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000105
Selected from substituted aromatic groups, cycloaliphatic groups;
R10and R11Independently selected from-H, -F, CH3、-CF3；
Figure FDA0003474129330000106
Selected from substituted aromatic groups, cycloaliphatic groups;
R13selected from-H, -F, CH3or-CF3；
R16And R17Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000107
Selected from substituted aromatic groups, cycloaliphatic groups;
R21and R22Independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000108
Selected from substituted aromatic groups, cycloaliphatic groups;
R24、R27、R28、R32、R33independently selected from-H, -F, CH3or-CF3；
Figure FDA0003474129330000109
Independently selected from substituted aromatic groups, cycloaliphatic groups;
R35、R38、R39、R43、R44、R45selected from-H, -F, CH3、-CF3；
Figure FDA0003474129330000111
Independently selected from substituted aromatic groups, alicyclic groups.
5. The method according to claim 3, wherein the dianhydride monomer is one selected from first dianhydride compounds having the following structures;
Figure FDA0003474129330000112
Figure FDA0003474129330000121
Figure FDA0003474129330000131
the diamine compound is selected from one of first diamine compounds having the following structure;
Figure FDA0003474129330000132
Figure FDA0003474129330000141
the dianhydride monomers also include a second dianhydride monomer, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 10: (0 to 50);
the second dianhydride monomer is selected from one of the dianhydride compounds having the following structure:
Figure FDA0003474129330000142
Figure FDA0003474129330000151
the diamine monomer also comprises a second diamine monomer, and the molar ratio of the first diamine monomer to the second diamine monomer is 10: (0 to 50);
the second diamine monomer is one selected from diamine compounds having the following structures:
Figure FDA0003474129330000152
6. the method of claim 5, wherein the dianhydride monomers further comprise a third dianhydride monomer, wherein the molar amount of the third dianhydride monomer is no more than 10% of the total molar amount of the dianhydride monomers;
the third dianhydride monomer is selected from one of 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride, bis (dicarboxyphenyldimethyl) silane dianhydride, bis (dicarboxybenzoic acid) terephthalate dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenoxy diphenyl) sulfide dianhydride, isopropylidene diphenoxy bisphthalic anhydride, bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and bicyclohexane tetracarboxylic dianhydride.
7. The method of claim 5, wherein the diamine monomer further comprises a third diamine monomer, wherein the molar amount of the third diamine monomer is not more than 10% of the total molar amount of the diamine monomer;
the third diamine monomer is selected from p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4-aminobenzoic acid (4-aminophenol) ester, 1, 3-bis (4,4' -aminophenoxy) benzene, 4' -diamino-1, 5-phenoxypentane, 3' -dimethyl-4, 4' -benzidine, 3' -dimethoxy-4, 4' -benzidine, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4' -diaminodiphenylmethane, 2' -diaminodiphenylpropane, bis (3, 5-diethyl-4-aminophenyl) methane, 4' -diaminodiphenylsulfone, N-phenylenediamine, N-1-phenylenediamine, N-1-3, 4-diamino-4-phenoxypentane, 3, 4-phenoxypentane, 4-diphenylpropane, 3, 4-diphenyl amine, 4-dimethoxybenzene, 4-diphenylpropane, 4-amino-diphenyl amine, 4-diphenyl amine, 4-amino-phenylene, 4-diphenyl ether, 4-diphenyl ether, 4-amino benzene, 4-phenylene, 4-phenylene, 4-diphenylsulfone, 4-phenylene, 4-phenylene, and benzene, 4-phenylene, 4-diphenylsulfone, 4-phenylene, 4, and benzene, 4, one, and benzene, one, and one, and one, 3,3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -diaminodiphenyl propane, 1, 4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-cyclohexanedi (methylamine), 4' -diaminodicyclohexylmethane, 4' -methylenebis (2-methylcyclohexylamine).
8. A polyimide film comprising the high-strength low-thermal expansion transparent polyimide according to any one of claims 1 to 2.
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