Polysulfone compositions and derivatives thereof

The compositions disclosed herein comprise compounds of the formula: EQU DOOCArO-ArSO.sub.2 Ar'QAr'SO.sub.2 Ar-OArCOOD (I) and also derivatives and polymers therefrom or from the compound: EQU X-ArSO.sub.2 Ar'QAr'SO.sub.2 Ar-X in which compounds D is hydrogen, halogen or a monovalent hydrocarbon radical, preferably of 1-20 carbon atoms; Q is either --O-- or --SO.sub.2 --; Ar and Ar' are divalent aromatic groups including a multiplicity of aromatic groups linked by O, SO.sub.2, hydrocarbon groups, etc.; and X is preferably Cl but may be other halogen atoms. In these compounds, the central core or residue --ArSO.sub.2 Ar'QAr'SO.sub.2 Ar-- may be represented by A. Various derivatives and polymers having the core A are prepared, such as diamides of the formula R.sub.2 NOCArO-A-OArCONR.sub.2 ; polyester polymers of the formula [--OROOCArO-A-OArCO--]; polyarylate polymers of the formula [--ArCOOArO-A-OArOOCArCOO--]; polycarbonate polymers of the formula [--OCOOArO-A-OArOOCO--]; phenolic resins, and many other derivatives. These compositions exhibit many desirable properties and have many uses including the improvement or upgrading of polyethylene terephthalate (PET) and polybutyleneterephthalate (PBT) resins when blended therewith.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to various polysulfone derivatives. More 
specifically it relates to monomeric and polymeric derivatives. Still more 
specifically it relates to such compositions which may be derived from 
compounds having the formula X--ArSO.sub.2 Ar'QAr'SO.sub.2 AR--X wherein 
the various symbols are as defined herein. 
2. State of the Prior Art 
Sulfone monomers and polysulfone polymers having the structure 
--Ar--SO.sub.2 -- therein are known. However applicant is not aware of any 
prior art showing the specific polysulfone structures described herein. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, polysulfone compounds have been 
found which are useful for preparing a variety of derivatives suitable for 
numerous purposes. These polysulfones have the formula: 
EQU DOOCArO--ArSO.sub.2 Ar'QAR'SO.sub.2 Ar--OArCOOD (I) 
wherein D represents hydrogen, halogen or a monovalent hydrocarbon group, 
preferably of 1-20 carbon atoms; Ar and Ar' are divalent aromatic radicals 
including a multiplicity of aromatic groups linked by O, SO.sub.2, 
divalent hydrocarbon groups, etc., and Q represents O or SO.sub.2. These 
compounds may be prepared by the reaction of a hydroxy aromatic carboxylic 
ester with 
EQU X--ArSO.sub.2 Ar'QAr'SO.sub.2 Ar--X 
wherein X is preferably chlorine but may be other halogen atoms, and the 
other symbols are as defined above. Where D is to represent hydrogen, the 
ester groups are hydrolyzed to the acid groups. The acid may be converted 
to the acid halide by reaction with thionyl halide, preferably SOCl.sub.2. 
In these and various other compounds described below, the central core or 
residue --ArSO.sub.2 Ar'QAr'SO.sub.2 Ar-- may be represented by A. 
In addition to saturated aliphatic, cycloaliphatic and alkylaryl esters the 
esters of compound I may also include unsaturated esters, such as allyl 
esters, propargyl esters, vinylaryl esters, propargyl aryl esters, etc. 
In the above Formula I where D is defined as hydrogen, halogen or a 
hydrocarbon group, the halogen may be Br, I, F but is preferably Cl, and 
the hydrocarbon may be aliphatic, aromatic, cycloaliphatic and 
combinations of such radicals, including those which have ethylenic or 
acetylenic unstaturation therein. 
The hydrocarbon groups may have attached thereto any group that will not 
interfere with the preparation and functions of the compounds of this 
invention as described herein. Preferably these groups are hydrocarbon or 
a multiplicity of hydrocarbon groups joined by ether, sulfide, ester and 
sulfonyl groups such as --O--, --S--, --COO--, --OOC--, --S(O).sub.2 --, 
etc. 
Typical monovalent hydrocarbon groups suitable in the above formulas 
include: --CH.sub.3, --C.sub.2 H.sub.5, --C.sub.3 H.sub.7, --C.sub.4 
H.sub.9, --C.sub.6 H.sub.13, --C.sub.10 H.sub.21, --C.sub.18 H.sub.37, 
--C.sub.6 H.sub.11, --C.sub.5 H.sub.9, --C.sub.5 H.sub.8 CH.sub.3, 
--C.sub.6 H.sub.10 C.sub.2 H.sub.5, --CH.sub.2 C.sub.6 H.sub.11, 
--CH.sub.2 CH.sub.2 C.sub.6 H.sub.11, --C.sub.6 H.sub.5, --C.sub.6 H.sub.4 
CH.sub.3, --C.sub.6 H.sub.4 C.sub.3 H.sub.7, --C.sub.6 H.sub.3 
(CH.sub.3).sub.2, --C.sub.6 H.sub.5 OCH.sub.3, --C.sub.6 H.sub.4 OC.sub.2 
H.sub.5, --C.sub.6 H.sub.4 SCH.sub.3, --C.sub.6 H.sub.4 OOCCH.sub.3, 
--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.5, --C.sub.6 H.sub.4 SO.sub.2 
C.sub.6 H.sub.4 CH.sub.3, --C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.5, 
--C.sub.6 H.sub.3 (CH.sub.3)OC.sub.3 H.sub.7, --C.sub.6 H.sub.4 OC.sub.6 
H.sub.4 CH.sub.3, --C.sub.10 H.sub.8, --C.sub.10 H.sub.7 CH.sub.3, 
--C.sub.10 H.sub.7 C.sub.2 H.sub.5, --C.sub.10 H.sub.6 (CH.sub.3).sub.2, 
--C.sub.10 H.sub.6 OCH.sub.3, --C.sub.10 H.sub.6 OOCCH.sub.3, --(C.sub.6 
H.sub.4).sub.3 C.sub.3 H.sub.7, --(C.sub.6 H.sub.4).sub.3 OC.sub.4 
H.sub.9, --(C.sub.6 H.sub.4).sub.3 OC.sub.6 H.sub.5, --C.sub.6 H.sub.4 
(OCH.sub.2 CH.sub.2).sub.2 H, --C.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.3 
H, --(C.sub.6 H.sub.4 O).sub.3 C.sub.3 H.sub.7, --CH.sub.2 CH.sub.2 
OCH.sub.2 CH.sub.2).sub.2 H, --CH.sub.2 CH.sub.2 (OCH.sub.2 
CH.sub.2).sub.3 OOCCH.sub.3, --CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5, 
--CH.sub.2 CH.sub.2 OOCCH.sub.3, --CH.sub.2 CH(CH.sub.3)OOCC.sub.6 
H.sub.5, --C.sub.6 H.sub.4 COOC.sub.2 H.sub.5, --CH.sub.2 COOC.sub.6 
H.sub.5, --C.sub.6 H.sub.4 CH.dbd.CH.sub.2, --C.sub.6 H.sub.3 
(CH.sub.3)CH.dbd.CH.sub.2, --C.sub.6 H.sub.4 C(CH.sub.3).dbd.CH.sub.2, 
--C.sub.6 H.sub.4 C.tbd.CH, etc. 
The divalent aromatic radicals Ar and Ar' are preferably hydrocarbon but 
can contain additional groups which will not interfere with the various 
reactions involved in the preparation and use of the products of this 
invention. 
These are divalent benzenoid radicals advantageously selected from the 
group consisting of: 
##STR1## 
and multiples thereof connected to each other by Z, for example, 
##STR2## 
wherein Z is an alkylene chain of 1-3 carbon atoms, --CH.dbd.CH--, or; 
--O--, --S--, --SO.sub.2 --, 
##STR3## 
wherein R" is selected from the group consisting of alkyl and aryl groups 
of 1-20, preferably 1 to 7 carbon atoms. Ar is preferably: 
##STR4## 
where Z is an alkylene chain of 1-3 carbon atoms, 
##STR5## 
--O--, --S--, --CH.dbd.CH--, --SO.sub.2 --, and y is 1 to 3. Particularly 
preferred for Ar and Ar' is the 
##STR6## 
radical. 
Typical compounds of the formula X--ArSO.sub.2 Ar'QAr'SO.sub.2 Ar--X which 
can be used in the preparation of the compositions of this invention 
include the following: 
Cl--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 
C.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
SO.sub.2 C.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.3 (CH.sub.3)SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 
SO.sub.2 C.sub.6 H.sub.3 (CH.sub.3)--Cl 
Br--C.sub.10 H.sub.6 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 
C.sub.10 H.sub.6 --Br 
Cl--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.3 (C.sub.2 H.sub.5)SO.sub.2 
C.sub.6 H.sub.3 (C.sub.2 H.sub.5)SO.sub.2 C.sub.6 H.sub.4 --Cl 
I--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
SO.sub.2 C.sub.6 H.sub.4 --I 
F--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 
C.sub.6 H.sub.4 --F 
Cl--C.sub.6 H.sub.4 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 
H.sub.4 SO.sub.2 C.sub.6 H.sub.4 C.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 
H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 --Cl 
Cl--C.sub.6 H.sub.4 CH.dbd.CHC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 CH.dbd.CHC.sub.6 H.sub.4 --Cl 
Br--C.sub.6 H.sub.4 SO.sub.2 C.sub.10 H.sub.6 SO.sub.2 C.sub.10 H.sub.6 
SO.sub.2 C.sub.6 H.sub.4 --Br 
These may be prepared in accordance with the procedures described below in 
Examples A and B. 
The compounds of Formula I are easily prepared by the reaction of 
X--ArSO.sub.2 Ar'QAr'SO.sub.2 Ar--X (1 mole) with 2 moles of CH.sub.3 
OOCC.sub.6 H.sub.4 OH (available commercially as Parasept) preferably in 
the presence of an anhydrous medium such as dimethyl sulfoxide or other 
aprotic solvent, and an alkali metal hydroxide, such as NaOH. Other esters 
may be used in which the methyl group is replaced by other hydrocarbon 
groups or in which the phenylene (--C.sub.6 H.sub.4 --) radical is 
replaced by other divalent aromatic radicals. Because of economics and 
availability, Parasept is preferred. The methyl or other hydrocarbon group 
may be replaced to give the corresponding acid, acid halide or other ester 
groups by standard methods of hydrolysis, reaction with SOCl.sub.2 or 
ester interchange, respectively. 
Various types of polymers may be prepared from the compounds of Formula I. 
For example, polyesters and polyamides may be prepared by reaction with 
polyols and polyamines, and additional polymers may be prepared by 
standard, well known free radical polymerization techniques when the D of 
the formula contains an unsaturated group, such as vinyl, propargyl, etc. 
In conducting polymerizations various solvents may be used with the 
polysulfones of this invention. The particular solvent used will depend on 
the specific polysulfone used. In many cases, the solvent may be an 
aprotic organic compound having a dielectric constant between 35 and 45, 
preferably one which is water soluble. Representative aprotic compounds 
are N,N-dimethylformamide, N,N-diethylformamide, 
N,N-dimethylmethoxyacetamide, N-methyl caprolactam, caprolactam, 
N,N-dimethylacetamide, N,N-diethylacetamide, dimethyl sulfoxide, 
N-mexthyl-.alpha.-pyrrolidone, tetramethylurea, hexamethylphosphoramide, 
tetramethylene sulfone, N,N,N',N'-tetramethyl-.alpha.-ethylmalonamide, 
N,N,N',N'-tetramethylglutaramide, N,N,N',N'-tetramethylsuccinamide, 
thiobis(N,N-dimethylacetamide), bis(N,N-dimethylcarbamylmethyl)ether, 
N,N,N',N'-tetramethylfuraramide, methylsuccinonitrile, 
N,N-dimethylcyanoacetamide, N,N-dimethyl-.beta.-cyano-propionamide, 
N-formylpiperidine and butyrolactone, etc. 
Of these solvents, dimethylacetamide is most preferred. Other preferred 
solvents are dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide, 
butyrolactone and caprolactam. 
In many cases, non-aprotic solvents can be used. For example, xylene, 
phenol, anisole, benzonitrile, acetophenone, methylphenylether or mixtures 
of these with each other, the aprotic solvents or with relatively poor 
solvents such as benzene, toluene cyclohexane, cyclohexene, dioxane, butyl 
cellosolve and the like. 
The concentration of the polysulfone in the solvent can be in the range of 
1 to 80% by weight of polysulfone and solvent depending on the 
polysulfone, the solvent and the temperature used. Preferably, the 
concentration is between 10 and 60% by weight. 
Polymerization products of the present invention have application in a wide 
variety of physical shapes and forms, including use as films, molding 
compounds, coatings, etc. The unusual heat stability and resistance to 
deformation at elevated temperatures in the cured state makes these 
compositions especially unique. When used as films or when made into 
molded products, these polymers, including laminated products prepared 
therefrom, not only possess excellent physical properties at room 
temperature, but they retain their strength and excellent response to 
work-loading at elevated temperatures for long periods of time. 
Moreover, solutions of the curable compositions herein described can be 
coated on electrical conductors such as copper, aluminum, etc. and 
thereafter, the coated conductor can be heated at elevated temperatures to 
remove the solvent and to effect curing of the resinous composition. If 
desired, an additional overcoat may be applied to such insulated 
conductors including the use of polymeric coatings such as polyamides, 
polyesters, silicones, polyvinylformal resins, epoxy resins, polyimides, 
polytetrafluoro-ethylene, etc. 
They can also be used as binders for asbestos fibers, carbon fibers and 
other fibrous materials in making brake linings. In addition, molding 
compositions and molded articles may be formed from the polymeric 
compositions in this invention by incorporating such fillers as asbestos, 
glass fibers, talc, quartz, powder, wood flour, finely divided carbon, 
silica, into such compositions prior to molding. Shaped articles are 
formed under heat, or under heat and pressure in accordance with practices 
well known in the art. In addition, various heat-resistant pigments and 
dyes may be incorporated as well as various types of inhibitors, depending 
on the application intended. 
Various other compounds or derivatives of this invention may be prepared 
from compound I or from the starting dihalide compound X--A--X. For 
example, compound I may be reacted with an amine, NHR.sub.2, to give the 
compound: 
EQU R.sub.2 NOCArO--A--OArCONR.sub.2 (II) 
wherein R represents hydrogen or a hydrocarbon radical, preferably of 1-20 
carbon atoms. When a diamine is used, a polymer is produced having a 
plurality of repeating units of the structure: 
EQU --NR--R'--NR(O)CArO--A--OArC(O)-- (III) 
wherein R' is a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon 
radical. 
Polymeric polyesters may be prepared by reacting compound I with 
approximately equimolar proportions of a polyol, HOR'OH, such as ethylene 
glycol, etc. Here again, the R' may be aliphatic, cycloaliphatic or 
aromatic. The resultant polymers have a repeating unit structure of the 
formula: 
EQU --OR'O(O)CArO--A--OArC(O)-- (IV) 
Various unsaturated aromatic ether compounds may be prepared by the 
reaction of vinylaryl, allylaryl and acetylenicaryl hydroxy compounds with 
X--A--X to give diethers having the formula KO--A--OK (V), wherein K 
represents an aromatic group having a terminal vinyl or acetylene radical, 
such as 
CH.sub.2 .dbd.CH--Ar--O--A--O--Ar--CH.dbd.CH.sub.2 
CH.sub.2 .dbd.CHCH.sub.2 ArO--A--OArCH.sub.2 CH.dbd.CH.sub.2 
CH.tbd.CCH.sub.2 ArO--A--OArCH.sub.2 C.tbd.CH 
CH.sub.2 .dbd.C(CH.sub.3)ArO--A--O--Ar--C(CH.sub.3).dbd.CH.sub.2 
Dihydroxy aromatic compounds may be reacted with approximately equimolar 
proportions of X--A--X, preferably with at least two moles of dihydroxy 
compound per mole of X--A--X to give derivatives of the formula: 
EQU HOArO--A--OArOH (VI) 
These derivatives (VI) may be condensed with aldehydes such as formaldehyde 
to produce resins having the repeating unit formula: 
##STR7## 
Derivatives VI may also be reacted with aromatic dicarboxyl dihalides such 
as terephthalic dichloride, to give polymers having the repeating unit: 
EQU --ArO--A--OArOOCArCOO-- (VIII) 
or with phosgene, etc., to give polycarbonate polymers having the repeating 
unit: 
EQU --ArO--A--OArOOCO--. (IX) 
Reaction of polyesters IV derived from aromatic polyols, such as 
hydroquinone, p,p'-dihydroxydiphenyl, bis-phenol-A, etc., may be enhanced 
in heat resistance by reaction with the dihydroxy compounds VI or by the 
direct preparation of polyesters of very good heat resistance by the 
reaction of derivative I with the dihydroxy compound VI to give polymers 
having the repeating unit: 
EQU --OOCArO--A--OArCOOArO--A--OAr--. (X) 
The reaction of X--A--X with HOArNH.sub.2, such as HOC.sub.6 H.sub.4 
NH.sub.2 gives the diamine of the formula: 
EQU NH.sub.2 ArO--A--OArNH.sub.2 (XI) 
which, when reacted with the dicarboxy compound I gives a polyamide polymer 
having repeating units of the formula: 
EQU --NHARO--A--OArNHOCArO--A--OArCO.sub.13 (XII) 
While the formulas of the preceding compounds of this invention have been 
given in full, it is possible in view of the generally symmetrical nature 
of these compounds to abbreviate these by the use of brackets to include 
the duplicated portions. For example, Formula I can also be written as: 
EQU [DOOCArO--ArSO.sub.2 Ar'].sub.2 Q (I) 
By reacting the X--A--X compounds with an acyl aromatic hydroxy compound 
such as a p-acyl-aryl hydroxide, for example m- or p-hydroxy-acetophenone, 
m- or p-benzoyl-phenol, 3-, 4- or 6-acetyl-naphthol-1,1-, 5- or 
6-acetyl-naphthol-2, 4-acetyl-4'-hydroxy-diphenyl, 
3-acetyl-4'-hydroxy-diphenyl oxide, etc. Compounds of this invention are 
preferred having terminal acyl groups. For example, the reaction of 
p-hydroxy-acetophenone with the X--A--X compound produced below in Example 
A gives the product: 
EQU [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
].sub.2 O (XIIIa) 
and with p-hydroxybenzophenone, the product is: 
EQU [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 
H.sub.4 ].sub.2 O (XIIIb) 
With the X--A--X compound produced below in Example B, the products are 
respectively: 
EQU [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 
].sub.2 SO.sub.2 (XIIIc) 
and 
EQU [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 
H.sub.4 ].sub.2 SO.sub.2 (XIIId) 
Also included within the scope of this invention are compounds in which the 
terminal aromatic groups have a second --COOD group such as 
Ar(COOR).sub.2, Ar(COOH).sub.2 and Ar(COOX).sub.2. For example, in the 
preparation described in Example I, the p-hydroxy phenyl benzoate may be 
replaced by an equivalent amount of 4-hydroxy dimethyl phthalate to give 
the product 
EQU (CH.sub.3 OOC).sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 
H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3 
(COOCH.sub.3).sub.2 
These may be converted to the tetraacids and the tetraacid halides by the 
procedures described above. 
This group of compounds may be represented by the formula: 
EQU (DOOC).sub.2 ArO--A--OAr(COOD).sub.2 (XIV) 
In turn these tetrafunctional compounds, by using the techniques described 
above, may be converted to: 
EQU tetraamides: (R.sub.2 NOC).sub.2 ArO--A--OAr(CONR.sub.2) (XIVe) 
##STR8## 
and unsaturated polymerizable derivatives: 
EQU (CH.sub.2 .dbd.CHOOC).sub.2 ArO--A--OAr(COOCH.dbd.CH.sub.2).sub.2 (XIVg) 
and 
EQU (CH.tbd.CCH.sub.2 OOC).sub.2 ArO--A--OAr(COOC.tbd.CH).sub.2 (XIVh) 
The polymers of formula XIVf and those produced by free radical 
polymerization of XIVg and XIVh are tractable products and may be of both 
thermoplastic and thermosetting types useful as coating materials to give 
solvent and heat resistant films. 
The dicarboxylate groups of formula XIV wherein the members of respective 
pairs of carboxy groups are positioned ortho or peri to each other may be 
converted to polyimide polymers by using one mole of a diamine 
R'(NH.sub.2).sub.2 per mole of formula XIV, which has been first converted 
to the tetraacid chloride compound by reaction with thionyl chloride. 
Completion of reaction and removal of by-products and solvent gives a 
polymer having the repeating unit structure: 
EQU --OAr(CO).sub.2 N--R'--N(OC).sub.2 ArO--A-- (XV) 
The R' in the diamine is preferably aromatic in which case R' may be 
defined as Ar. Typical diamines of the NH.sub.2 --Ar--NH.sub.2 formula are 
those having the Ar groups as defined above. 
Examples of aromatic diamines which are suitable to provide the divalent Ar 
radicals include 4,4'-diaminodiphenyl propane, 4,4'-diamino-diphenyl 
methane, benzidine, 3,3'-dichlorobenzidene, 4,4'-diamino-diphenyl sulfide, 
3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl sulfone, 
4,4'-diamino-diphenyl ether, 1,5-diamino naphthalene, 4,4'-diaminodiphenyl 
diethylsilane, 4,4'-diamino-diphenyl diphenylsilane, 4,4'-diamino-diphenyl 
ethyl phosphine oxide, 4,4'-diamino-diphenyl phenyl phosphine oxide, 
4,4'-diamino-diphenyl N-methyl amine, 4,4'-diamino-diphenyl N-phenyl amine 
and mixtures thereof, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 
3,3'-diethyl-4,4'-diaminodiphenylmethane, 
3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 
3,3'-diethoxy-4,4'-diaminodiphenylmethane, 
3,3'-dichloro-4,4',4,4'-diaminodiphenylmethane, 
3,3'-dibromo-4,4'-diaminodiphenylmethane, 
3,3'-dicarboxy-4,4'-diaminophenylmethane, 
3,3'-dihydroxy-4,4'-diaminophenylmethane, 
3,3'-disulpho-4,4'-diaminodiphenylmethane, 
3,3'-dimethyl-4,4'-diaminodiphenylether, 
3,3'-diethyl-4,4'-diaminodiphenylether, 
3,3'-dimethoxy-4,4'-diaminodiphenylether, 3,3'-dibromo-4,4'-diamino 
diphenylether, 3,3'-dicarboxy-4,4'-diaminodiphenylether, 
3,3'-dihydroxy-4,4' -diaminodiphenylether, 
3,3'-disulfo-4,4'-diaminodiphenylether, 
3,3'-dimethyl-4,4'-diaminodiphenylsulfide, 
3,3'-diethyl-4,4'-diaminodiphenylsulfide, 
3,3'-dimethoxy-4,4'-diaminodiphenylsulfide, 
3,3'-diethoxy-4,4'-diaminodiphenylsulfide, 
3,3'-dichloro-4,4'-diaminodiphenylsulfide, 
3,3'-dibromo-4,4'-diaminodiphenylsulfide, 
3,3'-dicarboxyl-4,4'-diaminodiphenylsulfide, 
3,3'-dihydroxy-4,4'-diaminodiphenylsulfide, 
3,3'-disulfo-4,4'-diaminodiphenylsulfide, 
3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 
3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 
3,3'-dichloro-4,4'-diaminodiphenylfulfone, 
3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 
3,3'-dihydroxy-4,4'-diaminodiphenylsulfone, 
3,3'-disulfo-4,4'-diaminodiphenylsulfone, 
3,3'-diethyl-4,4'-diaminodiphenylpropane, 
3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 
3,3'-dichloro-4,4'-diaminodiphenylpropane, 
3,3'-dicarboxy-4,4'-diaminodiphenylpropane, 
3,3'-dihydroxy-4,4'-diaminodiphenylpropane, 
3,3'-disulfo-4,4'-diaminodiphenylpropane, 
3,3'-dimethyl-4,4'-diaminobenzophenone, 
3,3'-dimethoxy-4,4'-diaminobenzophenone, 
3,3'-dichloro-4,4'-diaminobenzophenone, 
3,3'-dibromo-4,4'-diaminobenzophenone, 
3,3'-dicarboxy-4,4'-diaminobenzophenone, 
3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-disulphodiaminobenzophenone, 
3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylether, 
3,3'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 
3,3'-diaminodiphenylpropane, 3,3'-diaminobenzophenone, 2,4-diaminotoluene, 
2,6-diaminotoluene, 1-isopropyl-2,4-phenylenediamine, diaminoanisole, 
2,4-diaminomonochlorobenzene, 4,4-diaminofluorobenzene, 2,4-diaminobenzoic 
acid, 2,4-diaminophenol and 2,4-diaminobenzenesulfonic acid and phenylene 
diamines. Preferred diamines are 4,4'-oxydianiline, 
4,4'-sulfonyldianiline, 4,4'-methylene dianiline, 
4,4'-diaminobenzophenone, 4,4; diaminostilbene and the phenylene diamines, 
2,4-diaminotoluene and all the meta and para isomers of H.sub.2 NC.sub.6 
H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 NH.sub.2 . 
SPECIFIC EMBODIMENT 
The practice of this invention is illustrated by the following examples. 
These examples are given merely by way of illustration and are not 
intended to limit the scope of the invention in any way nor the manner in 
which the invention can be practiced. Unless specifically indicated 
otherwise, parts and percentages are given as parts and percentages by 
weight.