US 4,851,501 AGrant
Polyethersulfone Prepregs, Composites, and Blends
Issue Date:1989-07-25
•18 Claims
Abstract
The solvent resistance of polyethersulfone oligomers is enhanced by using difunctional imidophenol end-cap monomers to provide improved crosslinking. The imidophenol monomers include two unsaturated functionalities capable of cross-linking upon thermal or chemical activation. Blends, pregregs, and compositions using the novel end caps are described for linear or multidimensional polyethersulfone oligomers.
Metadata
Assignee
- The Boeing Company
Inventors
- Hyman R. Lubowitz
- Clyde H. Sheppard
Application Information
Application Number:US 1343351
Filing Date:1987-12-17
Priority Date:1983-06-17
Art Unit:153
Classifications
IPC:
C08G 7312
Field of Search:
528428427548170288;290350;385.5435;476;547
Patent Drawings
This patent does not have any drawings.
Description
The following examples are presented to illustrate various features of the invention:
EXAMPLE of 1
Synthesis of 1-hydroxyphenyl-2,4-dinadimide
Under dry N.sub.2, a slurry of 19.71 g (0.1 moles) of purified 2,4-diaminophenol dihydrochloride was prepared containing 10 percent solids in 17.39 g of N,N-dimethylacetamide (DMAC). 16.80 g (0.2 moles) dry NaHCO.sub.3 was added. After foaming subsided, 65.61 g xylene and 32.83 g (0.2 moles) 5-norbornene 2,3-dicarboxylic anhydride were slowly added. Transferred to a Barrett trap filled with xylene, the reaction mixture was refluxed (150.degree. C.) until no more water was collected in the Barrett trap. The product was precipated in water, separated by filtration, and washed.
EXAMPLE 2
Synthesis of 1-hydroxyphenyl-3,5-dinadimide
process of Example 1 was repeated except that 0.1 moles of 3,5-diaminophenol dihydrochloride was substituted for 2,4-diaminophenol dihydrochloride.
EXAMPLE 3
Synthesis of 1-hydroxyphenyl-2, 4-dinadic (cap 10% excess, 20% excess K.sub.2 CO.sub.3, Formula weight 20,000)
In a 1000-ml resin kettle fitted with a mechanical stirrer, thermometer, condenser, Dean Stark trap, and dry N.sub.2 purge, add 405.8 grams of dimethylacetamide was added to 173.9 grams toluene, 5.70 grams (0.014 mole) of 1-hydroxyphenyl-2,4-dinadimide (the compound of Example 1), 98.35 grams (0.273 mole) of 4-chlorophenylsulfone, 60.87 grams (0.267 mole) bisphenol A, and 45.25 grams potassium carbonate. Heated to 140.degree. C. the mixture was refluxed for 72 hours, before raising the temperature to 160.degree.-165.degree. C. to distill off the toluene. Refluxing at 160.degree.-165.degree. C. continued for 1 hour after all toluene was collected. The product was recovered thereafter by conventional steps.
EXAMPLE 4
Synthesis of 1-hydroxyphenyl-3,5-dinadimide (cap 10% excess, 20% excess K.sub.2 CO.sub.3, Formula weight 20,000)
Using the procedure of Example 3, but substituting 1-hydroxyphenyl-3,5-dinadimide (the compound of Example 2) for 1-hydroxyphenyl-2,4-dinadimide yielded the desired product.
EXAMPLE 5
Preparation of composites
The oligomer obtained from either Example 3 or 4 was impregnated on epoxy-sized T300/graphite fabric style (Union Carbide 35 million modulus fiber 24.times.24 weave) by sweeping a 10 to 15% resin solids solution of the oligomer in methylene chloride into the fabric, taking care to wet the fibers as well as possible. The oligomer comprised about 38 wt. % of the resulting prepreg. After drying to less than 1 percent volatile content, the prepreg was cut into 6.times.6-inch pieces and stacked to form a laminated composite of approximately 0.080 inch upon curing in a conventional vacuum bag process under 100 psi in an autoclave at 625.degree. F. for at least 6 hours. The composite exhibited substantial resistance to conventional solvents, such as MEK and methylene chloride.
While preferred embodiments have been described, those skilled in the art will readily recognize alterations, variations, or modifications that might be made to the embodiments without departing from the inventive concept. The description and examples, accordingly, are intended to illustrate the invention. The claims should be construed liberally in view of the description, and should only be limited as is necessary in view of the pertinent prior art.
Claims
We claim:
1. A prepreg comprising an oligmer formed by reacting: (1) 2 moles of A--OH (2) n+1 moles of a dihalogen of the general formula x--R--X and (3) n moles of a bisphenol of the general formula wherein A is selected from the group consisting of: Y.sub.i --.phi.--i=1 or 2; Y= ##STR17## .phi.=phenyl; R.sub.1 =lower alkyl, aryl, substituted alkyl, substituted aryl, lower alkoxy, aryloxy, or mixtures thereof; G=--SO.sub.2 --, --S--, --CH.sub.2 --, or --O--; J=1 or 2; R=an aromatic radical; R'=an aromatic radical; n=an integrer such that the oligomer has an average formula weight of between about 1,000 to about 40,000; Me=methyl; and T=allyl or methallyl and a additive in fiber or particulate form.
2. An oligomer formed by the condensation of: (a) 2 moles of a crosslinkable imidophenol having at least two crosslinking functionalities; (b) n+1 moles of an aromatic dihalogen; and n moles of an aromatic bisphenol.
3. The oligomer of claim 2 wherein the imidophenol is selected from the group consisting of: ##STR18## wherein Y is selected from the group consisting of: ##STR19## R.sub.1 =lower alkyl, aryl, substituted alkyl, substituted aryl, lower alkoxy, aryloxy, or mixtures thereof; G=--SO.sub.2 --, --S--, --CH.sub.2 --, or --O--; j=0, 1 or 2; Me=methyl; and E=allyl or methallyl.
4. The oligomer of claim 3 wherein the dihalogen is selected from the group consisting of: ##STR20## wherein q=--SO.sub.2 --, --S--, --CO--, --(CH.sub.3).sub.2 C--, or --(CF.sub.3).sub.2 C--.
5. The oligomer of claim 3 wherein the bisphenol is selected from the group consisting of: hydroquinone; bisphenol A; p, p'-biphenol 4, 4'-dihydroxydiphenylsulfide; 4, 4'-dihydroxydiphenylether; 4, 4'-dihydroxydiphenylisopropane; 4, 4'-dihydroxydiphenylhexafluoropropane; HO--AR--OH; HO--Ar--L--AR'--L--AR--OH; HO--Ar'--Ar--L--AR'--OH; wherein L=--CH.sub.2 --, --(CH.sub.3).sub.2 C--, --(CH.sub.3).sub.2 C--, --O--, --S--, --SO.sub.2 -- or --CO--; Ar'= ##STR21## Ar= ##STR22## T and T.sub.1 =lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substituted aryl, or mixtures thereof; q=0-4; k=0-3; and j=0, 1, or 2; a dialcohol having a Schiff base segment, the radical being selected from the group consisting of: ##STR23## wherein R is selected from the group consisting of: phenyl; biphenyl; naphthyl; or a radical of the generally formula: ##STR24## wherein W=--CH.sub.2 -- or --SO.sub.2 ; or a dialcohol selected from the group: ##STR25## wherein L is as defined above; Me=CH--.sub.3 ; m=an integer, generally less than 5; and D=any of --CO--, --SO.sub.2 --, or --(CF.sub.3).sub.2 C--.
6. The oligomer of claim 4 wherein the disphenol is selected from the group consisting of: hydroquinone; bisphenol A; p, p'-biphenol 4, 4'-dihydroxydiphenylsulfide; 4. 4'-dihydroxydiphenylether; 4, 4'-dihydroxydiphenylisopropane; 4, 4'-dihydroxydiphenylhexafluoropropane; HO--Ar--OH; HO--Ar--L--AR'--L--AR--OH; HO--Ar'--L--AR--L--Ar'--OH; ##STR26## wherein L=--CH.sub.2 --, --(CH.sub.3).sub.2 C--, --(CH.sub.3).sub.2 C--, --O--, --S--, --SO.sub.2 -- or --CO--; Ar'= ##STR27## AR= ##STR28## T and T.sub.1 =lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substituted aryl, or mixtures thereof; q=0-4; k=0-3; and j=0, 1, or 2; or a dialcohol having a Schiff base segment, the radical being selected from the group consisting of: ##STR29## wherein R is selected from the group consisting of: phenyl; biphenyl; naphthyl; or a radical of the general formula: ##STR30## wherein W=--CH.sub.2 -- or --SO.sub.2 --.
7. The prepreg of claim 1 wherein R= ##STR31## wherein w=--SO.sub.2 --, --S--, or --(CF.sub.3).sub.2 C--; and R'=phenyl, biphenyl, naphthyl, or ##STR32## wherein y=--SO.sub.2 --, --S--, --(CF.sub.3).sub.2 C--, --O--, or --(CH.sub.3).sub.2 C--.
8. A cured, solvent resistant, thermoplastic composite formed by cured the prepreg of claim 1.
9. A composite formed by curing the oligomer of claim 2.
10. A prepreg the oligomer of claim 2 and a reinforcing additive in fiber or particulate form.
11. A prepreg comprising the oligomer of claim 3 and a reinforcing additive in fiber or particulate form.
12. A prepreg comprising the oligomer of claim 6 and a reinforcing additive in fiber or particulate form.
13. The oligomer of claim 2 further comprising a suitable coreactant.
14. A prepreg comprising the oligomer of claim 13 and a reinforcing additive in fiber or particulate form.
15. The oligomer of claim 13 wherein the coreactant is selected from the group consisting of p-phenylenediamine, benzidine, 4,4'-methylenedianiline, an alkyl diamine having from 2-6 carbon atoms in the alkyl chain, or mixtures thereof, and the oligomer includes an imidophenol having maleic crosslinking functionalities.
16. The oligomer of claim 13 wherein the coreactant is selected from the group consisting of: ##STR33## wherein R.sub.1 =lower alkyl, aryl, substituted aryl, lower alkoxy, or mixtures thereof; j=0, 1 or 2; and R=alkyl having 2-6 carbon atoms or an aromatic radical selected from the group consisting of phenyl, biphenyl, and --.phi.--CH.sub.2 --.phi.--, and the oligomer includes an imidophenol having norborene crosslinking functionalities.
17. The oligomer of claim 13 wherein the coreactant is selected from the group consisting of: ##STR34## wherein R=alkyl having 2-6 carbon atoms or an aromatic radical selected from the group consisting of phenyl, biphenyl, and --.phi.--CH.sub.2 --.phi.-- and the oligomer includes acetylenic crosslinking functionalities.
18. A composite formed by during the oligomer of claim 13.