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United States Patent Office Patented May 3, 1966 1 3,249,561 United States Patent Office Patented May 3, 1966 1. 2 fic temperature for forming the polyamide-acid of a speci FORMING A FoAME53,249,561 roi YIMEDE ARTICLE fied diamine and a specified dianhydride, several factors William Robert Hendrix, Buffalo, N.Y., assignor to E. must be considered. The maximum permissible tem du Pont de Nemours and Company, Wilmington, Del., perature will depend on the diamine used, the dianhydride a corporation of Delaware used, the particular solvent, the percentage of polyamide No Drawing. Fied Mar. 18, 1963, Ser. No. 266,065 acid desired and the minimum period of time that one 1. Claims. (CI. 260-2.5) desires for the reaction. For most combinations of dia mines and dianhydrides falling with the definitions given This invention relates to cellular structures of poly above, it is possible to form polymeric components of imides and a process for making them. O 100% polyamide-acid by conducting the reaction below In the prior art, resinous compositions have been made 100 C. However, temperatures up to 175° C. may be into foams by physically mixing the molten or plasticized tolerated to provide shapeable compositions. The partic resin with gases or blowing agents. However, obtaining ular temperature below 175 C. that must not be exceeded polyimide resins in the molten state is not easily possible for any particular combination of diamine, dianhydride, since the resins are resistant to heat and tend to degrade 5 Solvent and reaction time to provide a reaction product before or during melting. Using a plasticizer is also composed of sufficient polyamide-acid to be shapeable will difficult since the resins are quite resistant to most chemi Vary but can be determined by a simple test by any person cals. In other words, the same outstanding physical and of ordinary skill in the art. However, to obtain the maxi chemical properties that would make these foamed poly mum inherent viscosity, i.e. maximum degree of polym mers extremely useful in the form of shaped cellular arti 20 erization, for any particular combination of diamine, cles make it extremely difficult to obtain these articles in dianhydride, solvent, etc., it has been found that the tem the first instance. perature throughout the reaction should be maintained An object of the present invention is to form foamed below 60° C., preferably below 50° C. polyimides and articles thereof. Other objects will ap The degree of polymerization of the polyamide-acid is pear hereinafter. 25 Subject to deliberate control. The use of equal molar The objects are accomplished by first forming a solution amounts of the reactants under the prescribed conditions containing at least one polyamide-acid having an inherent provides polyamide-acids of very high molecular weight. viscosity of at least 0.1, preferably 0.3-5.0; adding a lower The use of either reactant in large excess limits the extent fatty acid anhydride or an aromatic monobasic acid an of polymerization. Besides using an excess of one reac hydride, preferably with a tertiary amine, to the solution; 30 tant to limit the molecular weight of the polyamide-acid, adding an acid selected from the group consisting of form a chain terminating agent such as phthalic anhydride may ic oxalic, trichloroacetic, malonic, citric and alpha-hy be used to 'cap' the ends of the polymer chains. droxybutyric acids, preferably formic acid, to the solution; In the preparation of the polyamide-acid intermediate, agitating the solution until gelation occurs to form a it is essential that the molecular weight be such that the foamed polymeric composition; then shaping the foamed 35 inherent viscosity of the polymer is at least 0.1, preferably polymeric composition into a structure; and thereafter, 0.3-5.0. The inherent viscosity is measured at 30° C. at heating the structure. a concentration of 0.5% by weight of the polymer in a In the first step of this process, a polyamide-acid solu Suitable solvent, e.g. N,N-dimethylacetamide. To calcu tion is prepared. The process for preparing the poly late inherent viscosity, the viscosity of the polymer solu amide-acid solution involves reacting at least one organic 40 tion is measured relative to that of the solvent alone. diamine having the structural formula H2N-R-NH2 wherein R is a divalent radical containing at least 2 carbon Inherent viscosity = atoms, the two amine groups of said diamine each attached to separate carbon atoms of said divalent radical; with at natural logarithm Wiscosity of solution least one tetracarboxylic acid dianhydride having the struc Wiscosity of solvent tural formula C O O where C is the concentration expressed in grams of poly C C mer per 100 milliliters of solution. As known in the poly 50 mer art, inherent viscosity is directly related to the molec ular weight of the polymer. C C The quantity of organic solvent used in the process need O O only be Sufficient to dissolve enough of one reactant, pref erably the diamine, to initiate the reaction of the diamine wherein R is a tetravalent radical containing at least 2 55 and the dianhydride. For forming the shaped articles, carbon atoms, no more than 2 carbonyl groups of said it has been found that the most successful results are dianhydride attached to any one carbon atom of said tetra obtained when the solvent represents at least 60% of the valent radical; in an organic solvent for at least one of final polymeric solution. That is, the solution should the reactants, the solvent being inert to the reactants, pref contain 0.05-40% of the polymeric component. The vis erably under anhydrous conditions, for a time and at a 60 cous Solution of the polymeric composition containing temperature sufficient to provide a shapeable polymeric polyamide-acid in the polymeric component dissolved composition containing polyamide-acid. in the solvent is the result of the first step. It should be understood that it is not necessary that The starting materials for forming the products of the the polymeric component be composed entirely of the present invention are organic diamines and tetracarboxylic polyamide-acid. This is particularly true since conver 65 acid dianhydrides. The organic diamines are character sion to the polyimide is contemplated subsequent to shap ized by the formula: H2N-R-NH2, wherein R', the dival ing. To retain its shapeability, it has been found that in ent radical, may be selected from the following groups: most instances the polymeric component should contain aromatic, aliphatic, cycloaliphatic, combination of aromat at least 50% of the polyamide-acid; and, in a few in ic and aliphatic, heterocyclic, bridged organic radicals stances, less than 50% of the polyamide-acid in the poly 70 Wherein the bridge is oxygen, nitrogen, sulfur, silicon or meric component will operate. - phosphorous, and substituted groups thereof. The pre Furthermore, in determining a specific time and a speci ferred R' groups in the diamines are those containing at 3,249,561 3 4. least 6 carbon atoms characterized by benzenoid unsatura 2,5-dimethylheptamethylene diamine; tion. Such R groups include 5-methylnonamethylene diamine; 1,4-diamino-cyclohexane; 1,12-diamino-octadecane; 5 2,5-diamino-1,3,4-oxadiazole; HN(CH2)3O(CH2)2O(CH2)3NH2: HN(CH2)3S(CH2)3NH2, HN(CH2)N(CH3) (CH2)3NH2; 3,3'-dichlorobenzidine; 00000 O Bis-(4-amino-phenyl) ethyl phosphine oxide; Bis-(4-amino-phenyl) phenyl phosphine oxide; Bis-(4-amino-phenyl)-N-phenylamine; and mixtures thereof. CO The tetracarboxylic acid dianhydrides are characterized wherein R' is selected from the group consisting of 5 by the following formula: carbon in an alkylene chain having 1-3 carbon atoms, -O-, silicon in O O R C C c-Si o/ YR^ Yo kn 20 N / N / and O O wherein R is a tetravalent organic radical selected from R. the group consisting of aromatic, aliphatic, cycloaliphatic, -O-Si-O- 25 heterocyclic, combination of aromatic and aliphatic, and kn substituted groups thereof. However, the preferred di phosphorous in anhyrides are the aromatic tetracarboxylic acid dianhy drides, those in which the R groups have at least one ring R of 6 carbon atoms characterized by benzenoid unsatura 30 tion (alternate double bonds in a ring structure), and particularly those aromatic dianhydrides wherein the 4 carbonyl groups of the dianhydride are each attached to separate carbon atoms in a benzene ring and wherein the carbon atoms of each pair of carbonyl groups is directly 35 attached to adjacent carbon atoms in a benzene ring of the R group to provide a 5-membered ring as follows: -S-, and -SO - wherein R'' and R'' are alkyl or | aryl. Among the diamines which are suitable for use in the present invention are: 40 Meta-phenylene diamine; O Para-phenylene diamine; 4,4'-diamino-diphenyl propane; g-o-; 4,4'-diamino-diphenylmethane; -C C Benzidine; 45 4,4'-diamino-diphenyl sulfide, Illustrations of dianhydrides suitable for use in the pres 4,4'-diamino-diphenyl sulfone; ent invention include: 3,3'-diamino-diphenyl sulfone; Pyromellitic dianhydride; 4,4'-diamino-diphenyl ether; 2,3,6,7-naphthalene tetracarboxylic dianhydride; 2,6-diamino-pyridine; 50 3,3,4,4'-diphenyl tetracarboxylic dianhydride; Bis-(4-amino-phenyl) diethylsilane; 1,2,5,6-naphthalene tetracarboxylic dianhydride; Bis-(4-amino-phenyl) diphenyl silane; 2,2',3,3'-diphenyl tetracarboxylic dianhydride; Bis-(4-amino-phenyl)-N-methylamine; 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; 1,5-diamino naphthalene; Bis(3,4-dicarboxyphenyl) sulfone dianhydride; 3,3'-dimethyl-4,4'-diamino-biphenyl; 55 3,4,9,10-perylene tetracarboxylic
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