US5470943A
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Polyimide
Assignee: Mitsui Chemicals Inc
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Filing: 1994-12-21
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Granted: 1995-11-28
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Expires: 2014-12-21
Abstract
Abstract This invention relates to a novel fluorine-containing polyimide or polyimide copolymer being colorless and having transparency and very low dielectric characteristics, and has a novel aromatic diamino compound used for the polyimide, a preparation process thereof, a polyimide-based resin composition comprising the polyimide or polyimide copolymer and a fibrous reinforcement, a process for preparing the resin composition, an injection molded article of the resin composition. The polyimide comprise a requisite structural unit having one or more recurring structural units of the formula: <IMAGE> (1) wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond. The polyimide or polyimide copolymer has excellent heat resistance, outstanding melt-flow stability and greatly improved processability, and also is colorless and has high transparency and very low dielectric coefficient, and can be expected to be used as raw materials for electric.electronic appliances and optical instruments due to the above characteristics.
Inventors
- 👤 Yoshihiro Sakata
- 👤 Wataru Yamashita
- 👤 Yuichi Okawa
- 👤 Shoji Tamai
- 👤 Tsutomu Ishida
- 👤 Mitsunori Matsuo
- 👤 Keizaburo Yamaguchi
- 👤 Akihiro Yamaguchi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 19:58
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1039; C08G73/1085; C08L; C08L79/00; C08L79/04; C08L79/08
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
98 words
A polyimide comprising a requisite structural unit consisting of one or more recurring structural units; represented by the formula (1): ##STR46## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond.
Claim 2
Dependent Claim
98 words
A polyimide comprising a requisite structural unit consisting of one or more recurring structural units; represented by the formula (1): ##STR46## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond.
Claim 3
Dependent Claim
67 words
A polyimide comprising a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR47## wherein Ar and positions of the trifluoromethyl radical and the imide nitrogen atom are the same as above, and having at the polymer chain end thereof an aromatic ring which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride.
Claim 4
Dependent Claim
67 words
A polyimide comprising a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR47## wherein Ar and positions of the trifluoromethyl radical and the imide nitrogen atom are the same as above, and having at the polymer chain end thereof an aromatic ring which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride.
Claim 5
Dependent Claim
33 words
The polyimide of claim 2 comprising a requisite structural unit of one or more recurring structural units represented by the formula (1-1): ##STR48## wherein Ar is the same as in the formula (1).
Claim 6
Dependent Claim
30 words
The polyimide of claim 2 comprising a requisite structural unit of one or more recurring structural units represented by the formula (1-2): ##STR49## wherein Ar are the same as above.
Claim 7
Dependent Claim
250 words
A polyimide or a polyimide copolymer comprising a requisite structural unit of 1˜100 mol % of recurring structural units represented by the formula (1): ##STR50## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, and 99˜0 mol % of recurring structural units represented by the formula (2): ##STR51## wherein n is an integer of 0 to 6; Q is a direct bond, --O--, --S--, --CO--, --SO 2 --, --CH 2 --, --C(CH 3 ) 2 -- or --C(CH 3 ) 2 --, and when two or more bonding radicals Q connect aromatic rings to each other, the bonding radicals Q can be the same or different; and Ar' is a tetravalent having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; or said polyimide or said polyimide copolymer having at the polymer chain end a radical which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride.
Claim 8
Dependent Claim
250 words
A polyimide or a polyimide copolymer comprising a requisite structural unit of 1˜100 mol % of recurring structural units represented by the formula (1): ##STR50## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, and 99˜0 mol % of recurring structural units represented by the formula (2): ##STR51## wherein n is an integer of 0 to 6; Q is a direct bond, --O--, --S--, --CO--, --SO 2 --, --CH 2 --, --C(CH 3 ) 2 -- or --C(CH 3 ) 2 --, and when two or more bonding radicals Q connect aromatic rings to each other, the bonding radicals Q can be the same or different; and Ar' is a tetravalent having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; or said polyimide or said polyimide copolymer having at the polymer chain end a radical which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride.
Claim 9
Dependent Claim
216 words
A preparation process of polyimide having a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR52## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, comprising reacting aromatic diamine consisting essentially of one or more aromatic diamino compounds represented by the formula (3): ##STR53## wherein a trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and an amino radical is connected at the 3- or the 4-position to an ether bond, with tetracarboxylic dianhydride essentially represented by the formula (4): ##STR54## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; and thermally or chemically imidizing the resultant polyamic acid.
Claim 10
Dependent Claim
216 words
A preparation process of polyimide having a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR52## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, comprising reacting aromatic diamine consisting essentially of one or more aromatic diamino compounds represented by the formula (3): ##STR53## wherein a trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and an amino radical is connected at the 3- or the 4-position to an ether bond, with tetracarboxylic dianhydride essentially represented by the formula (4): ##STR54## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; and thermally or chemically imidizing the resultant polyamic acid.
Claim 11
Dependent Claim
313 words
A preparation process of a polyimide having a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR55## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, and having at the polymer chain end thereof an aromatic ring which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride, comprising reacting aromatic diamine consisting essentially of one or more aromatic diamino compounds represented by the formula (3): ##STR56## wherein positions of the trifluoromethyl radical and the amino radical is connected at the 3- or the 4-position to an ether bond, with tetracarboxylic dianhydride essentially represented by the formula (4): ##STR57## wherein Ar is the same as above, in the presence of aromatic dicarboxylic anhydride represented by the formula (5): ##STR58## wherein Z is a divalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, or aromatic monoamine represented by the formula (6): Z.sub.1 --NH.sub.2 ( 6) wherein Z 1 is a monovalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; and thermally or chemically imidizing the resultant polyamic acid.
Claim 12
Dependent Claim
313 words
A preparation process of a polyimide having a requisite structural unit consisting of one or more recurring structural units represented by the formula (1): ##STR55## wherein Ar is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, a trifluoromethyl radical is situated at the 3- or the 4-position on the pyridine nucleus, and an imide nitrogen atom is connected at the 3- or the 4-position to an ether bond, and having at the polymer chain end thereof an aromatic ring which is essentially unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride, comprising reacting aromatic diamine consisting essentially of one or more aromatic diamino compounds represented by the formula (3): ##STR56## wherein positions of the trifluoromethyl radical and the amino radical is connected at the 3- or the 4-position to an ether bond, with tetracarboxylic dianhydride essentially represented by the formula (4): ##STR57## wherein Ar is the same as above, in the presence of aromatic dicarboxylic anhydride represented by the formula (5): ##STR58## wherein Z is a divalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, or aromatic monoamine represented by the formula (6): Z.sub.1 --NH.sub.2 ( 6) wherein Z 1 is a monovalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; and thermally or chemically imidizing the resultant polyamic acid.
Claim 13
Dependent Claim
199 words
A preparation process of polyimide or a polyimide copolymer of claim 5, comprising reacting 1˜0.01 parts by mole of aromatic diamine represented by the formula (3): ##STR59## wherein positions of the trifluoromethyl radical and the amino radical are the same as above, with 1˜0.01 parts by mole of tetracarboxylic dianhydride essentially represented by the formula (4): ##STR60## wherein Ar is the same as above, and further reacting 0˜0.99 parts by mole of one or more aromatic diamine represented by the formula (9): ##STR61## wherein n is an integer of 0˜6, and Q is a direct bond, --0--, --S--, --CO--, --SO 2 --, --CH 2 --, --C(CH 3 ) 2 -- or --C(CF 3 ) 2 --, and when two or more bonding radicals Q connect aromatic rings to each other, the bonding radicals Q can be the same or different, with 0˜0.99 parts by mole of tetracarboxylic dianhydride represented by the formula (10): ##STR62## wherein Ar' is a tetravalent radical having 6 to 27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member.
Claim 14
Dependent Claim
166 words
A preparation process of polyimide or a polyimide copolymer of claim 8, comprising carrying out the reaction in the presence of 0.001˜1.0 mol of aromatic dicarboxylic anhydride represented by the formula (5): ##STR63## wherein Z is a divalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member, for 1 mol of total aromatic diamine, or in the presence of 0.001˜1.0 mol of aromatic monoamine represented by the formula (6): Z.sub.1 --NH.sub.2 ( 6) wherein Z 1 is a monovalent radical having 6 to 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed polyaromatic radical having aromatic radicals connected to each other with a direct bond or a bridge member; for 1 mol of total tetracarboxylic dianhydride; and thermally or chemically imidizing the resultant polyamic acid.
Claim 15
Dependent Claim
42 words
An aromatic diamino compound represented by the formula (3): ##STR64## wherein the trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus and the amino radical is connected at the 3- or the 4-position to an ether bond.
Claim 16
Dependent Claim
42 words
An aromatic diamino compound represented by the formula (3): ##STR64## wherein the trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus and the amino radical is connected at the 3- or the 4-position to an ether bond.
Claim 17
Dependent Claim
13 words
The aromatic diamino compound of claim 10 represented by the formula (3-1): ##STR65##
Claim 18
Dependent Claim
13 words
The aromatic diamino compound of claim 10 represented by the formula (3-2): ##STR66##
Claim 19
Dependent Claim
69 words
A preparation process of the aromatic diamino compound represented by the formula (3): ##STR67## wherein the trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and the amino radical is connected at the 3- or the 4-position to an ether bond, comprising carrying out condensation of 2,6-dichloro-3- or 4-trifluoropyridine with 3- or 4-aminophenol in an aprotic polar solvent in the presence of a base.
Claim 20
Dependent Claim
69 words
A preparation process of the aromatic diamino compound represented by the formula (3): ##STR67## wherein the trifluoromethyl radical is situated at the 3- or the 4-position on a pyridine nucleus, and the amino radical is connected at the 3- or the 4-position to an ether bond, comprising carrying out condensation of 2,6-dichloro-3- or 4-trifluoropyridine with 3- or 4-aminophenol in an aprotic polar solvent in the presence of a base.
Claim 21
Dependent Claim
43 words
A polyimide based resin composition comprising 100 parts by weight of polyimide or a polyimide copolymer of claim 5 and 5 to 70 parts by weight of a fibrous reinforcement selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber.
Claim 22
Dependent Claim
14 words
An injection molded article obtained from the polyimide based resin composition of claim 14.
Claim 23
Dependent Claim
13 words
A polyimide film comprising polyimide or the polyimide copolymer of the claim 5.
Claim 24
Dependent Claim
33 words
The polyimide of claim 1 comprising a requisite structural unit of one or more recurring structural units represented by the formula (1-1): ##STR68## wherein Ar is the same as in the formula (1).
Claim 25
Dependent Claim
32 words
The polyimide of claim 1 comprising a requisite structural unit of one or more recurring structural units represented by the formula (1˜2): ##STR69## wherein L and Ar are the same as above.
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JPH01190652A
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1998-11-27 | 1999-05-29 | 1999-11-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2002-11-27 | 2003-05-29 | 2003-11-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2006-11-27 | 2007-05-29 | 2007-11-28 | $7700.00 | Window Closed / Lapsed |