Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
1999-05-21
2001-01-30
Hampton-Hightower, P. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S125000, C528S128000, C528S172000, C528S173000, C528S176000, C528S183000, C528S188000, C528S220000, C528S229000, C528S350000, C528S353000
Reexamination Certificate
active
06180746
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to polyimides. It relates in particular to a polyimide precursor solid residuum, which is effectively employed in the preparation of polyimide foam and the fabrication of polyimide foam structures.
2. Description of the Related Art
High performance polyimides are presently used in the aerospace industry, for example, in joining metals to metals, or metals to composite structures. In addition, polyimides are rapidly finding new uses as foam insulation in cryogenic applications, and as structural foam having increased structural stiffness without large weight increases, in aerospace structures.
Polyimide foam materials have a number of beneficial attributes for next generation space vehicles, such as high temperature and solvent resistance, flame resistance, low smoke generation, high modulus and chemical and hot water resistance. Another area for polyimide foams is in the manufacture of low density insulation for thermal and acoustic applications, and reinforcement for the maritime industry.
U.S. Pat. Nos. 5,147,966 and 5,478,916 disclose polyimides that can be melt processed into various useful forms such as coatings, adhesives, composite matrix resins and films. These polyimides are prepared from various diamines and dianhydrides in various solvents. The use of monoanhydrides as endcapping agents is also disclosed in these patents to control the molecular weight of the polymers and, in turn, to make them easier to process in molten form. The use of ethers to make polyimide adhesives was disclosed in U.S. Pat. No. 4,065,345, which demonstrates another method to produce polyimide resin systems.
FIG. 1
shows the method employed by these patents to produce polyimides.
U.S. Pat. No. 3,483,144 discloses a process for making polyimide foam by ball milling a mixture of monomers and heating the mixture to 300° C. In all cases, the foams produced by this patent are the result of dianhydricles or tetraacids being dissolved by a diamine upon melting. The ensuing reaction produces water and thus foams the molten material.
FIG. 2
illustrates the process to make foam by this patent.
The state-of-the-art technology for making polyimide foams as disclosed in U.S. Pat. Nos. 5,298,531, 5,122,546, 5,077,318, and 4,900,761 utilizes solutions of diamines and dianhydride derivatives in a low molecular weight alkyl alcohol solvent. Polyimide precursor solutions and powders therefrom are then processed into foams through the expulsion of water and alcohol (R-OH) during the thermal imidization process. In these cases the alcohol solvent reacts initially with the dianhydride to form a covalently bonded specie referred to as a dialkylester-diacid (DADA) before the aromatic diamine is added. The aforementioned patents also illustrate the use of blowing agents to aid in the foaming process. The blowing agents utilized by these patents serve as a separate entity and usually result in a foam that has residual blowing agent within its cell walls.
FIG. 3
demonstrates the state-of-the-art in this foam technology.
Howsoever useful, these related art processes for preparing foams from polyimide precursors are all found wanting, in that none provide foam densities over a wide range. Indeed, many commercially-available polyimide foams are made by employing an added step of densifying a low density foam to produce a foam of desired higher density. Moreover, in many of these related art processes undesirably high foaming temperatures are required, because the foaming agents are volatile by-products generated in the polycondensation reaction. Furthermore, many of these related art processes do not provide for uniformity in the blowing of the foam, and they result in non-uniformity of the foamed product. In particular, many of these foaming processes start out slowly, build tip to a maximum, and then taper off toward the end. The foamed products produced often exhibit non-uniformity of density and cell size throughout the foamed structure, which results in low yields of acceptable product. Additionally, some of the polyimide precursors employed in these related art processes (especially those involving isocyanate chemistry) have poor hydrolytic stability and poor stability toward other types of decomposition.
SUMMARY OF THE INVENTION
It is accordingly a primary object of the present invention to provide what is lacking in the related art. viz., a polyimide precursor solid residuum which has particular utility and special effectiveness in the preparation of polyimide foam and the fabrication of polyimide foam structures. It is another primary object of the present invention to provide a polyimide precursor solid residuum which possesses hydrolytic stability and storage stability toward other types of decomposition, and which affords a uniform foaming action, especially in respect of the length and intensity of the blowing process. It is another primary object of the present invention to provide a polyimide precursor solid residuum which affords the preparation of polyimide foams at moderate temperatures to effect foam products having a wide range of densities and a high degree of product uniformity, especially in respect of uniformity of density and cell size throughout the foamed structure. It is another primary object of the present invention to provide a polyimide precursor solid residuum which affords an efficient and efficacious foaming process, and which provides a polyimide foam having high temperature and solvent resistance, flame resistance, low smoke generation, high modulus, low density, and chemical and hot water resistance.
These objects and their attending benefits are achieved, and the disadvantages of the related art are avoided, by the present invention, which is a polyimide precursor solid residuum. This residuum is an admixture of an aromatic compound (A), which is an aromatic dianhydride or derivative thereof and aromatic compound (B), which is an aromatic diamine or derivative thereof, plus a complexing agent (C), which is complexed with the admixture by hydrogen bonding, the complexing agent (C) being present in an amount sufficient to provide from about 1 to about 15% by weight, based on the total weight of the polyimide precursor solid residuum.
Especially beneficial results are obtained if the polyimide precursor solid residuum according to the present invention is an admixture of an aromatic compound (A)
and an aromatic compound (B)
wherein n is an integer from 0 to 3, and R
1
is hydrogen or an alkyl group, and R
2
is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms, R
3
is a divalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms, along with a complexing agent (C) being present in an amount sufficient to provide from about 1 to about 15% by weight, based on the total weight of the polyimide precursor solid residuum.
Outstanding results are obtained if the aromatic compound (A) and the aromatic compound (B) as specified above are present in the admixture in approximately equimolar amounts.
Especially good results are obtained if the coinplexing agent is an ether, especially one of, or a suitable mixture of tetrahydroftiran, glyme, diglyine, dioxane, 2-methoxy ethanol and 2-ethoxy ethanol.
The polyimide precursor solid residuum of the present invention advantageously has an apparent density of from about 1 to about 40 pounds/ft
3
, and is beneficially in the fonn of a powder, or friable balloons (as hereinafter described), or flake (as hereinafter described).
Very beneficial results are obtained if the aromatic compound (A) is at least one derivative of a dianhydride selected from ODPA; BPDA; BTDA; DSDA; PMDA and BPADA; and the aromatic compound (B) is at least one diamine which is selected from 3,4′ODA; 4,4′ODA; APB; BPB; m-PDA; p-PDA; 3,3′DDS; 4,4′DDS; 4,4 BAPS; 4,3 BAPS; 3 BAPB; 4 BAPB and BAPP.
Equally beneficial results are obtained if the polyimide precursor solid residuum is a combination
Echigo Yoshiaki
Kaneshiro Hisayasu
St. Clair Terry L.
Weiser Erik S.
Hampton-Hightower P.
Hawkins Hillary W.
The United States of America as represented by the Administrator
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