Aromatic diamines containing three ether-linked-benzonitrile moieties, polymers thereof, and methods of making the same
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IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08G-073/00
C08G-073/10
C07C-255/54
C07C-253/30
C07C-231/06
C08G-073/14
출원번호
US-0229251
(2014-03-28)
등록번호
US-9139696
(2015-09-22)
발명자
/ 주소
Tan, Loon-Seng
Wang, David Huabin
출원인 / 주소
The United States of America, as represented by the Secretary of the Air Force
대리인 / 주소
AFMCLO/JAZ
인용정보
피인용 횟수 :
0인용 특허 :
52
초록▼
The present invention includes compositions and methods of preparation for symmetrical and unsymmetrical diamines containing three ether-linked benzonitrile moieties that may be used as monomers for the manufacture of a variety of functional polymers. For example, the presently disclosed multi(ether
The present invention includes compositions and methods of preparation for symmetrical and unsymmetrical diamines containing three ether-linked benzonitrile moieties that may be used as monomers for the manufacture of a variety of functional polymers. For example, the presently disclosed multi(ether-benzonitrile) diamines may polymerize with: (i) a dianhydride to form a polyimide; (ii) a diacid chloride directly or with a dicarboxylic acid (diacid) in conjunction with a suitable promoter/catalyst combination such as triethylphosphite/pyridine to form a polyamide; and (iii) 1,2,4-benzenetricarboxylic anhydride (trimellitic anhydride), trimellitic anhydride chloride, or a diacid/diacid chloride derived from trimellitic anhydride and an aromatic diamine to form a poly(amide-imide).
대표청구항▼
1. A tri(benzonitrile)-diamine having a general structure: wherein NH2 is meta or para with reference to oxygen and wherein R is selected from the group consisting of H, CH3, Cl, F, and CF3. 2. A polyimide derived from the tri(benzonitrile)-diamine of claim 1 and a dianhydride, the polyimide having
1. A tri(benzonitrile)-diamine having a general structure: wherein NH2 is meta or para with reference to oxygen and wherein R is selected from the group consisting of H, CH3, Cl, F, and CF3. 2. A polyimide derived from the tri(benzonitrile)-diamine of claim 1 and a dianhydride, the polyimide having the general structure: Ar is selected from the group consisting of: 3. Polyamides and poly(amide-imide)s derived from the tri(benzonitrile)-diamine of claim 1 having the general structure: wherein the polyamide is derived from the tri(benzonitrile)-diamine of claim 1 and an aromatic diacid or a diacid chloride, wherein Z is wherein the poly(amide-imide) is derived from the tri(benzonitrile)-diamine of claim 1 and trimellitic anhydride, trimellitic anhydride chloride, or a diacid or diacid chloride derived from trimellitic anhydride, wherein Z is selected from the group consisting of: Ar being selected from the group consisting of: wherein X and Y are selected from the group consisting of C(CH3)2, C(CF3)2, O, S, SO2, and C═O. 4. A method for synthesizing a symmetrical tri(benzonitrile)-diamine according to claim 1 comprising the steps of: a. demethylating 2,6-dimethoxybenzonitrile to obtain 2,6-dihydroxybenzonitrile;b. combining the 2,6-dihydroxybenzonitrile with a fluorine-containing benzonitrile to obtain 2,6-bis(2-cyano-3-fluorophenoxy)benzonitrile; andc. mixing the 2,6-bis(2-cyano-3-fluorophenoxy)benzonitrile with at least two molar amounts of an aminophenolate to obtain the symmetrical tri(benzonitrile)-diamine of claim 1. 5. A method for synthesizing an unsymmetrical tri(benzonitrile)-diamine according to claim 1 comprising the steps of: a. demethylating 2,6-dimethoxybenzonitrile to obtain 2,6-dihydroxybenzonitrile;b. combining the 2,6-dihydroxybenzonitrile with a fluorine-containing benzonitrile to obtain 2,6-bis(2-cyano-3-fluorophenoxy)benzonitrile;c. mixing the 2,6-bis(2-cyano-3-fluorophenoxy)benzonitrile with an equimolar amount of para-aminophenolate at 80-100° C. to obtain a reaction mixture;d. allowing the reaction mixture to cool to room temperature; ande. adding and mixing an equimolar amount of meta-aminophenolate at 80-100° C. to obtain the unsymmetrical tri(benzonitrile)-diamine of claim 1. 6. The method of claim 4 wherein the tri(benzonitrile)-diamine is selected from the group consisting of 2,6-bis[3-(3-aminophenoxy)-2-cyanophenoxy]b enzonitrile and 2,6-bis[3-(4-aminophenoxy)-2-cyanophenoxy]benzonitrile. 7. A method for synthesizing the polyimide of claim 2 comprising the steps of: a. mixing a tri(benzonitrile)-diamine according to claim 1 with a dianhydride in a 1:1 molar ratio in a polar solvent to generate a poly(amic acid) precursor; andb. imidizing the poly(amic acid) precursor to obtain the polyimide of claim 2. 8. The method of claim 7 wherein the dianhydride is selected from the group consisting of 2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, bis(3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 5,5′-[(1-methylethylidene)bis(4,1-phenyleneoxy)]bis-1,3-isobenzofurandione, and 5,5′-[[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(4,1-phenyleneoxy)]bis-1,3-isobenzofurandione. 9. The method of claim 7 wherein the step of imidizing the poly(amic acid) precursor comprises thermal curing. 10. The method of claim 7 wherein the step of imidizing the poly(amic acid) precursor comprises chemical imidization using at least one of a dehydrating agent and a promoter. 11. A method for synthesizing a polyamide according to claim 3 comprising the step of mixing the tri(benzonitrile)-diamine of claim 1 and a diacid chloride in a 1:1 molar ratio in a polar solvent at low temperature to obtain the polyamide. 12. A method for synthesizing a polyamide according to claim 3 comprising the steps of: a. mixing the tri(benzonitrile)-diamine of claim 1 and a diacid in a 1:1 molar ratio in a polar solvent;b. adding a promoter-catalyst composition comprising triphenyl phosphite (TPP) and pyridine (py) in a molar ratio of diacid:TPP:py of 1:2:2; andc. heating to 100-120° C. to obtain the polyamide. 13. A method for synthesizing a poly(amide-imide) according to claim 3 comprising the steps of: a. mixing the tri(benzonitrile)-diamine of claim 1 and an acid chloride-anhydride or a diacid chloride in a polar solvent in stoichiometric ratio at 0° C. to generate a mixture comprising an amine-anhydride AB-monomer;b. warming the mixture to room temperature to generate a solution comprising poly(amic acid) precursor; andc. heating the solution to 160-200° C. to generate the poly(amide-imide). 14. A method for synthesizing a poly(amide-imide) according to claim 3 comprising the steps of: a. mixing the tri(benzonitrile)-diamine of claim 1 and an acid-anhydride or a diacid in a stoichiometric ratio in a polar solvent to form a mixture comprising diacid-di(amic acid);b. adding a chloride and a promoter-catalyst composition to the mixture, wherein the promoter-catalyst composition comprises triphenyl phosphite (TPP) and pyridine (py) in a molar ratio of 1 (diacid): 2 (TPP): 2 (py); andc. heating the mixture to 100-120° C. and then 160-200° C. to sequentially form amide and imide moieties to generate the poly(amide-imide). 15. A method for synthesizing a poly(amide-imide) according to claim 3 comprising the steps of: a. mixing the tri(benzonitrile)-diamine of claim 1 and an acid-anhydride or a diacid in a stoichiometric ratio in a polar solvent to form a mixture comprising diacid-di(amic acid);b. adding a chloride and a promoter-catalyst composition to the mixture, wherein the promoter-catalyst composition comprises triphenyl phosphite (TPP) and pyridine (py) in a molar ratio of 1 (diacid): 2 (TPP): 2 (py);c. adding acetic anhydride and triethylamine in excess; andd. heating the mixture to 100-120° C. to generate the poly(amide-imide).
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