CA1065995A

CA1065995A - Catalysis of amine curable polymers by high dielectric constant compounds

Info

Publication number: CA1065995A
Application number: CA228,111A
Authority: CA
Inventors: Steven E. Schonfeld
Original assignee: Firestone Tire and Rubber Co
Current assignee: Bridgestone Firestone Inc
Priority date: 1974-06-05
Filing date: 1975-05-30
Publication date: 1979-11-06
Also published as: JPS5130297A; DE2524083C2; DE2524083A1; FR2273838A1; FR2273838B1; GB1499215A; JPS561330B2; IT1036151B

Abstract

ABSTRACT OF THE DISCLOSURE

A catalyst cured polymer is obtained by adding by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of (a) urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and haloformate groups, and polymers containing anhydride groups which on reaction with diamines, yield amide-acide linkages, or (b) halogen containing hydrocarbon polymers, chlorosulfonated polymers and organo-polysiloxanes; an amine containing curing agent in an amount of 0.8 to 1.2 equivalents based upon the free active groups of the amine curable polymer or prepolymer of group (a), or of 0.0005 to about 0.05 equiva-lents based upon the active groups of the amine curable polymer or prepolymer of group (b), the curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, the salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-amino-phenyl) butane and a salt selected from the group consisting of sodium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of the dianiline or butane to the salt in the complex being about 3 moles per 1 mole; and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethyl-siloxane and diethylsulfate, and curing the polymer or pre-polymer composition. The use of the above selected catalyst causes the polymerization to proceed rapidly at reasonably low temperatures and at temperatures lower than normally other-wise possible. The preferred polyurethanes can be used for numerous applications such as automotive parts, bumpers, commercial and passenger tires, shoe soles, wearing apparel, roller wheels and the like.

Description

lO~S995 The present invention relates to the catalyzation of methylene dianiline complexes utilized in the curing of amine curable polymers and particularly polyurethane polymers so that cure proceeds rapidly and at reasonably low temperatures.
Heretofore, the curing of amine curable polymers or prepolymers such as epoxy resins, millable halogen containing hydrocarbon polymers and particularly isocyanate terminated poly-urethane prepolymers have generally involved the blending of an amine curing agent, forming of the resulting mixture into a useful form and heating to complete the curing reaction.
However, a problem generally encountered by this procedure was the premature reaction of the curing agent with the curable polymer during the mixing and formation operations. This problem was particularly acute in highly reactive systems such as in the curing of isocyanate terminated polyurethane prepolymers which necessitated the use of special low residence time mixers and selected diamine curing agents having reduced reactivity which generally limited the physical properties of the vulcanizates.
A class of widely used curing agents which have over-come many of the above-noted problems are the complexes of methylene dianiline and a salt which upon heating generally in excess of temperatures of 100C liberated the methylene dianiline from the complex and allowed it to commence curing of the poly-mers (U.S. Patent No. 3,755,261~. Although an improvement in the art, such class of curing agents still tended to be time consuming, required undesirable demolding time and thus tended to be uneconomical due to the number of molds re~uired. The only way to overcome these disadvantages was to increase the cure temperature which resulted, of course, in an increased cure rate. However, increased cure temperatures caused larger thermal expansion and subsequent shrinkage in the molded article which often led to strains and cracks in the product.
Accordingly, the presen~ invention proposes to provide ~ -1- ~
~ . ,.!

" 1065995 catalytic compounds for a methylene dianiline complex or a racemic

2,~3-di(4-aminophenyl) butane complex curing agent used in the curing of amine curable polymers or prepolymers, which catalytic compounds have a high dielectric constant and are relatively non-reactive with amines or isocyanates.
More particularly, the invention provides a catalyst cured polymer, comprising by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of (a) urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and haloformate groups and polymers containing anhydride groups which on reaction with diamines, yield amide-acide linkages, or (b) halogen containing hydrocarbon polymers, chlorosulfonated polymers and organo-poly-siloxanes an amine containing curing agent in an amount of 0.8 to 1.2 equivalents based upon the free active groups of the amine curable polymer or prepolymer of group (a), or of 0.0005 to about 0.05 equivalents based upon the active groups of the amine curable polymer or prepolymer of group (b), the curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, the salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, li.thium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of the dianiline or butane to the salt in the complex being about 3 moles per 1 mole and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate.

~3 `` ` 106599S

It has been found that the use of a specific catalyst in combination with a curing agent utilized for curing amine curable polymers or prepolymers generally results in increased cure rates, decreased curing temperatures or both. According to the present invention, the curing agent catalyst is selected from the group consisting of oleic acid benzaldehyde, adipo-nitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate.
A specific curing agent is a complex of 4,4'-methylène dianiline (MDA) and a salt. The preparation of the specific curing agent complex is set forth in U.S. Patent 3,755,261.
Generally, the complexes which are utilized as curing agents for amine curable polymers include the reaction product of 4,4'-methylene dianiline with the following salts at a ratio of about 3 moles of methylene dianiline to about 1 mole of salt;
sodium chloride, sodium bromide, sodium iodide, sodium nitrite, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide.
Another complex which can be used as a curing agent are the reaction products of racemic 2,3-di(4-aminophenyl) butane with the following salts in approximately a ratio of 3 moles of diamine to about 1 mole of salt; sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide. The complex of methylene dianiline and the salt are generally preferred with the preferred salt being sodium chloride or lithium chloride.
Utilization of the preferred curing agent in the curing of amine curable prepolymers or polymers upon heating to a temperature of approximately 100C causes methylene dianiline to be liberated from the complex and cure the polymers of prepolymers in a manner thought to be identical to that which occurs when free methylene dianiline is used as a curing agent.
The above-noted complexes can cure many amine curable prepolymers or polymers as noted and set forth in the above-noted ~ ~ - 3 -~.~

106S~9S

U.S. Patent No. 3,755,261. Generally, the preferred class of such prepolymers or polymers are the urethanes which are general-ly formed by the reaction of a diisocyanate and a glycol or diol having a molecular weight of generally 400 to 8,000 and preferably from 600 to 3,000. Such urethanes typically may be formed by the reaction of a polyether, a polyol, a polyester polyol, polybutadiene diols, and combinations thereof with an equivalent amount of slight excess of diisocyanate or triiso-cyanate to form a prepolymer having therminal isocyanate groups.
The present invention pertains to such formed urethanes as well as to other formed urethanes as fully apparent to those skilled in the art. Patents describing some general types of urethanes are 2,620,516, 2,777,831, 2,843,568, 2,866,774, 2,900,368, 2,929,800, 2,948,691, 2,948,707 and 3,141,735. Other groups of amine curable prepolymers or polymers set forth in U.S. Patent

3,755,261, are epoxy resins, polymers containing acid halide groups such as O
- C - Cl o and haloformate groups, such as - O - C- Cl polymers containing anhydride groups which on reaction with diamines yield amide-acid linkages, halogen containing hydrocarbon polymers such as chloroprene polymers, chlorinated butyl rubber and chlorinated polyethylene and polypropylene, chlorosulfonated polymers and organopolysiloxanes.
The specific catalyst when used in combination with the complex curing agents has been found to have a catalytic effect in the curing of polyurethane as well as the other noted amine curable polymers or prepolymers. That is, the use of the above selected catalysts causes the various polymers or pre-polymers to proceed at a more rapid cure rate or at a lowertemperature than otherwise possible with solely the use of the complex curing agents. Based upon 100 parts of polymer or pre-. .
. ~ ~ _4_ .. . _ _ ~, 1065S~9S
polymer, from 1.0 to approximately 35 parts of curing agentcatalyst ls utilized. A more preferred range extends from about 2 to about 10 parts with approximately 5 parts being high~
ly preferred. As should be apparent to one skilled in the art, the exact amount of catalyst may vary somewhat depending upon the amount of curing agent complex utilized, the amount of poly~ner or prepolymer active groups, curing temperature and the like.
The compounds which have a catalytic effect upon the curing of amine curable polymers or prepolymers according to the concepts of the present invention generally are high polar com-pounds, that is compounds which have a high dielectric constant, and which generally have relatively slow reaction rates with amines and free isocyanates. That is, it is desirable that the high dielectric constant catalytic compounds do not react with the amines of the curing agent or the isocyanates of the pre-polymer but rather have a catalytic effect upon the curing agent and are not deleterious to the prepolyrner or polymer. Hence, by the words "a relatively slow reaction rate" is meant a rate such that a substantial number of prepolymers or polymers are cured by the curing agents to produee cured polymers since the reac-tion rate with amines or diisocyanates ls sufficiently slow enough such that competitive reactions are substantially abated. There-fore, high dielectric constant compounds which react with amines such as strong acids and high dielectric constant compounds which react with isocyanates such as strong bases are not within the scope of the present invention. Generally, compounds having a high dielectric constant of 2.0 or above are preferred in the present invention. Of course, compounds having a high dielectric constant generally having a greater catalytic effect. General-ly, high dielectric catalytic compoùnds which are liquid during the curing temperature of the amine curable prepolymers or A ~ 5 , . _ 1 -` 1065g95 polymers, that is from about 80C to about 140C and even 170C
are desirable. It is generally thought that such liquid catalytic compounds can then wet the surface of the curing agent salts and thus sufficiently produce a catalytic effect.-Based upon 100 parts of polymer or prepolymer, from 0.1 to about 35 parts of the high dielectric catalyst compound is utilized. A preferred range extends from about 0.2 to about 10 parts. Of course, the exact amount of high dielectric constant catalytic compound will vary depending upon particula'r desirable curing temperature as well as the curing rates of the compounds which varies with different catalytic compounds which effect is clearly understood by one skilled in the art. Com-pounds which are preferred include those which generally give a demold time of less than 6.5 minutes when cured at a tempera-ture of 120C utilizing approximately 2.9 parts per 100 parts of polymer or prepolymer in accordance with the manner and test set forth in Example II, hereinbelow. Such preferred compounds include benzaldehyde, adiponitrile, acetic anhydride, poly-dimethylsiloxane and diethyl sulfate.
When the amine curable polymer or prepolymer is polyurethane, the amount of the curing agent complex will general-ly range from 0.8 to about 1.2 equivalents of the diamine in the curing agent to the free isocyanate groups in the polyurethane.
A more preferred range extends from 1.0 to about 1.1 equivalents.
These same ranges are applicable in situations wherein the polymer or prepolymer are the above-noted epoxy resins, polymers containing acid halide groups and haloformate groups(and halo-formate groups,) and polymers containing anhydride groups which on reaction with diamlnes yield amide-acid linkages~ That is, the amount of curing agent complex such as methylene dianiline and a salt will have the above-noted equivalent ranges which is based upon the number~of free active groups in the polymer or ~ ~ _ -6-.. ;
. ~

-"` 1065995 prepolymer which react with methylene dianiline.
Considering the remaining polymers or prepolymers, namely the halogen containing hydrocarbon polymers, the chloro-sulfonated polymers and the organopolysiloxanes, since they do not generally contain diamine reactive groups on the terminal portions of the chain, a much smaller equivalent ratio is desirable to cure these compounds such as through crosslinking.
Depending upon the desired final molecular weight of the polymers, and the average molecular weight of the prepolymers, the amount of curing agent complex can vary over a wide range.
Generally, such a range may extend from 0.0005 to about 0.05 equivalents of the reactive portion of the curing agent such as diamine to the active groups contained in the polymer or pre-polymer. A preferred range is from 0.005 to about 0.05 equivalents. As well known to one skilled in the art, the equivalent amount for obtaining a cured polymer having a desired average molecular weight or the like can be quickly and readily determined.
The composition according to the present invention can be prepared by blending the polymer or prepolymers with the curing agent complex at ambient or slightly elevated temperatures such as about 50C but below the curing temperature of the complexed curing agent which is generally about 90C or 100C.
Preferably, the catalyst is added just before the composition is cured such as prior to molding, extruding or the like. Since the various high dielectric constant catalytic compounds lower the cure initiation temperature of a curing agent, preferably the polymer or prepolymer mixture is below 80 or 90 at the incorporation or blending time of the catalytic compounds of the present invention to prevent, of course, premature cure.
Various conventional additives and compounds may be added to the composition of the present invention to impart ~ _ -7--`` 1065~95 various desirable characteristics or properties. These include antiforming agents or solid articles, pigments, light stabilizers, forming agents for foamed articles, fillers such as Hi Sil and the like. Additionally, in the production of polyurethanes, plasticizers are often added to increase the flexibility of the article. A conventional plasticizer often employed is dioctyl phthalate (DOP). The addition of DOP is also desirable in that since it is a liquid,it is used to disperse the powder during agent complexes.
The catalyzed amine curable polymers or prepolymers have been found to increase the cure rate, to decrease the cure time or both. Increased rate of cure, of course, allows the use of fewer molds since each mold can be cycled more rapidly.
Another important advantage of the use of the present catalyst cure systemps is that because possible lower temperature cures can be effected, less thermal expansion and subsequent shrinkage occurs in a molded article, Thus, the article contains less strain and is much less likely to develop any cracks or fissures.
Yet another obvious advantage is that due to the lower tempera-ture cure of the various catalysts, lower operating costs are obtained due to energy conservation.
~ he amine curable prepolymers or polymers made in accordance with the present invention can, of course, he used for the same normal applications. Concerning the preferred polyurethanes, they can be used for numerous applications such as automotive parts, bumpers, commercial and passenger tires, shoe soles, wearing apparrel, roller wheels and the like. Per-haps the most important application will lie in the manufacutre of tires.
The present invention will be more fully understood by reference to tne following examples concerning preparation and data.

. ..~, ~ 8-1065gg5 EXAMPLE I (COMPARATIVE) To a 3 neck flask fitted with a stirrer, thermometer and a vacuum takeoff was added 250 grams of DuPont's Adiprene LD784 (polytetramethylene ether glycol of about 1,000 molecular weight end capped with 2 molecules of Hylene TM, i.e. approxi-mately a 80/20 mixture the 2,4/2,6 position isomers of toluene diisocyanate) and 86.15 grams of a Caytur 21 (a complex of 4,4'-methylene dianiline and a salt) dispersion (50 % in DOP). Then 7.15 grams of tributyl phosphate was added to a flask. The mixture was seen to rapidly thicken and set up in the flask after 3 minutes of mixing at 50C. Cures prepared from this material were poor due to the partial cure which occurred in the flask. Since it appeared that TBP catalyzed the reaction of the Caytur 21 with the prepolymers, a series of various temperature cures were run to determine if the TBP was a true catalytic material. It was found that cure would occur at temperatures down to 80~ in the catalyzed system whereas in the uncatalyzed system, a cure temperature of at least 105C was necessary to initiate reasonable cure rates.
A series of runs were made utilizing different levels of TBP at various cure temperatures, the results of which are set forth in Fig. 1 wherein the demold time represents the time required for the molded articles to be sufficiently cured such that it maintained it:s structural integrity upon removal from .. ~
` `; 7~ - -9-...... ~, the mold. In the drawing,,line 1 represents the prior art composition of 100 parts of ~diprene LD784, 20 parts of DOP
and an equivalent ratio of 1.025 of the diamine to the free active isocyanate groups in the Adiprene prepolymer. The dotted portion of line 1 indicates that cures below a temperature of approxLmately 100C were difficult to achieve and gave poor properties. Lines 2, 3 and 4 represent mixtures of Adiprene prepolymers, DOP, TBP, and Caytur 21' curing agent in the amounts indicated.
As readily apparent from the drawing, the addition of TBP greatly reduced the cure time at a specific curing temperature and reduced the required curing temperature to cure in a specific amount of time. The commencement of lines 2, 3 and 4 at the lower temperatures generally represent the onset of initiation or cure whereas the termination of lines 2, 3 and 4 at higher tempexatures generally represent the upper desirable curing temperature, Of course, compositions containing more or les~
TBP will generally result in correspondingly located lines dependlng upon the amount of TBP, Moreover~ the equivalent ratio of the complex such as methylene dianiline to free active isocyanate groups can also be varied.
The effect of tributyl phosphate concentration on physical properties is set forth in Table I.

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i ~&i5~95 In general, as the amount of catalyst was increased, the physical properties such as tensile strength and crescent tear ~ere slightly reduced. Rowever, such reduction is generally well within the r~quirements of a particular application for the S cured polymer. Additionally, the 5% and 300~ modulus at ambient temperature (73F) were reduced thus indicatin~ a more resilient article is produced.
Table II shows the effect of prepolymers containing an increased amount of isocyanate content.

TABLE II
r EFFECT ~F NC~ CONTENT

COMPOSITION G H

Prepolymer %NCO 6.45 5~10 of Caytur Cure 102.5 102.5 Parts TBP 5 5 Parts DOP 17.2 14.0 Tensile Str. (PSI)2050 2100 300% Mod (PSI) 1530 1020 Crescent Tear (LB/IN) 276 291 Tensile Str. (PSI~4340 4400 5% Mod (PSI) 500 434 300% Mod (PSI) 1875 1275 Crescent Tear (LB/IN) 419 399 Tex-US Flex (2 low of 8) 10,000 126,000 In general, the properties remain relati~ely the same except that the 5% and 300% modulus of compound G containing lZ
!~A~ ,~
i 106~5 the higher amount of free isocyanate was much higher and the flex much lower indicating a stiffer or more brittle material.
Table III represents polyurethane compositions prepared from poly THF (Tetrahydrofuran).

TABLE II I
PREPOLYME~ TYI?ES
COMPOS ITION I J
Prepolymer type loo IPO1Y THF 100 ~Poly T~F
TDI type~Hylene TM ~Hylene T
% Caytur Cure102.5 102.5 Parts DOP 17.1 20 10 Parts TBP 2 . 9 5 Tensile Str. (PSI) 1970 1890 30096 Mod. (PSI) 1560 800 Crescent Tear (LB/IN) 274 137 Tensile Str. (PSI) 5375 2075 5% Mod. (PSI) 494 168 15 30096 Mod. (PSI) 2125 890 Crescent Tear (LB/IN)417 269 Additionally, the various catalytic high dielectric constant compounds according to the present invention other than tributyl phosphate also give reduced cure time at 20 a specific curing temperature or reduced the required curing temperature to cure in a specific amount of time. Moreover, the properties of the amine curable polymers or prepolymers according to the present invention wherein various high dielectric catalytic compounds were utilized generally are the 25 same as pol~mers or prepolymers cured without said high dielectric catalytic compounds.

~,~ . ,. _;
`~lj 13 -~06sg~5 EXAMPLE II
To a three neck flask fitted with a stirrer, thermo-meter and a vacuum takeoff was added 250 grams of DuPont's Adiprene LD784 (polytetramethylene ether glycol of about 1,000 molecular weight end capped with two molecules of Hylene TM, that is, approximately and 80/20 mixture of the 2,4/2,6 position isomers of toluene diisocyanate) and 86.15 grams of Caytur 21 (the complex of 4,4-methylene dianiline and a salt) dispersion (50 % in DOP). The mixture was heated to 50C and then 7.15 grams of various high dielectric constant catalytic compounds was added constant stirring. The mixture was then stirred more or less from about one half minute to a minute and a half depending upon the catalytic effect of a specific high dielectric constant compound. The mixture was then poured into a mold.
The time necessary for the material to become demoldable, that is maintain a structural integrity which would not lose its shape after separation from a mold, was compared to an un-catalyzed mixture to determine whether the specific compoun~
was a true catalyst. The following Table sets forth the results of a number of various types of high dielectric constant com-pounds which were tested as catalyst. It was found that the catalyzed systems could be cured as low as about 80C whereas in the absence of a catalyst, cure temperature of at least 105C was necessary to initiate reasonable cure rates.
Table IV sets forth the mold time of various catalysts wherein an amount of`2.9 grams per 100 grams of prepolymer were utilized and the mixture cured at a temperature of 120C.

.~ _ lO~S5~S
TABLE IV
DEMOLD
SAMPLE CATALYST MOLD TEMP (C) TIME (MIN
Control DOP 120 10.0 Oleic Acid 100 7.5 B Benzaldehyde 120 5.0 C Adiponitrile 120 3.0 D Acetic Anhydride 120 6.0 E Polydimethylsiloxane 120 5.5 F Diethyl sulfate 120 4.5 , Of course, increased concentrations of a specific catalyst will result in increased cure rates and thus shorter demold times and/or lower curing temperatures. Variation of concentrations, cure temperature and demold time of the catalysts of the present invention when plotted will result in a graph similar to Fig. 1.
Table V represents polyurethane compositions prepared from poly THF (Tetrahydrofuran).

TABLE V

Parts, Wt Compound 100 Polypropylene glycol hylene TM prepolymer (6.2~ NCO) 32.9 Caytur 21 Dispersion (49.5% in DOP) 2.9 Oleic Acid The composition of Table V when cured according to the same conditions as the compositions set forth in Table IV
gave a demold time of 4.0 minutes.

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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A catalyst cured polymer, comprising by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of (a) urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and halo-formate groups and polymers containing anhydride groups which on reaction with diamines, yield amide-acide linkages, or (b) halogen containing hydrocarbon polymers, chlorosulfonated polymers and organo-polysiloxanes; an amine containing curing agent in an amount of 0.8 to 1.2 equivalents based upon the free active groups of said amine curable polymer or prepolymer of group (a), or of 0.0005 to about 0.05 equivalents based upon the active groups of said amine curable polymer or prepolymer of group (b), said curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles per 1 mole; and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate.

2. A catalyst cured polymer, comprising by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and haloformate groups, and polymers containing anhydride groups which on reaction with diamines, yield amide-acid linkages, from 0.8 to 1.2 equivalents of an amine containing curing agent based upon the free active groups of said amine curable polymer or prepolymer, said curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles per 1 mole, and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate.

3. A catalyst cured polymer according to claim 2, wherein said equivalent ratio of said curing agent to said free active groups of said amine curable polymer or prepolymer ranges from 1.0 to about 1.2.

4. A catalyst cured polymer according to claims 2 or 3, wherein said amount of said catalyst ranges from about 0.2 to about 10 parts.

5. A catalyst cured polymer according to claim 2, wherein said amine curable polymer or prepolymer is a urethane polymer or prepolymer containing free isocyanate groups.

6. A catalyst cured polymer according to claim 2, wherein said curing agent is a complex of 4,4'-methylene dianiline and a salt.

7. A catalyst cured polymer according to claims 2 or 6, wherein said salt of said dianiline complex is selected from the group consisting of sodium chloride and lithium chloride.

8. A catalyst cured polymer according to claim 2, wherein said catalyst has a dielectric constant of 2.0 and greater.

9. A catalyst cured polymer, comprising by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of halogen containing hydrocarbon polymers, chloro-sulfonated polymers and organopolysiloxanes, from 0.0005 to about 0.05 equivalents of an amine containing curing agent based upon the active groups of said amine curable polymer or prepolymer, said curing agent selected from a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles to 1 mole, and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate.

10. A catalyst cured polymer according to claim 9, wherein the amount of said catalyst ranges from about 0.2 to about 10 parts.

11. A catalyst cured polymer according to claim 9, wherein said catalyst has a dielectric constant of 2.0 and greater.

12. A process for the catalytic curing of an amine curable polymer or prepolymer in a reaction vessel, comprising the steps of adding by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of (a) urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and haloformate groups and polymers containing anhydride groups which on reaction with diamines, yield amide-acide linkages, or (b) halogen containing hydrocarbon polymers, chlorosulfonated polymers and organo-polysiloxanes, adding an amine containing curing agent in an amount of 0.8 to 1.2 equivalents based upon the free active groups of said amine curable polymer or prepolymer of group (a), or of 0.0005 to about 0.05 equivalents based upon the active groups of said amine curable polymer or prepolymer of group (b), said curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles per 1 mole, and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate, and curing said polymer or prepolymer composition.

13. A process for the catalytic curing of an amine curable polymer or prepolymer in a reaction vessel, comprising the steps of adding by weight, 100 parts of an amine curable polymer or prepolymer selected from the group consisting of urethanes containing free isocyanate groups, epoxy resins, polymers containing acid halide and haloformate groups, and polymers containing anhydride groups which on reaction with diamines, yield amide-acide linkages, adding from 0.8 to 1.2 equivalents of an amine containing curing agent based upon the free active groups of said amine curable polymer or prepolymer, said curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt, said salt selected from the group consisting of sodium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles per 1 mole, and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethylsulfate, and curing said polymer or prepolymer composition.

14. A process according to claim 13, wherein said equivalent ratio of said curing agent to said free active groups of said amine curable polymer or prepolymer ranges from 1.0 to about 1.2.

15. A process according to claims 13 or 14, wherein the amount of said catalyst ranges from about 0.2 to about 10 parts.

16. A process according to claim 13, wherein said amine curable prepolymer or polymer is a urethane prepolymer or polymer containing free isocyanate groups.

17. A process according to claim 13, wherein said curing agent is a complex of 4,4'-methylene dianiline and a salt.

18. A process according to claims 13 or 17, wherein said salt of said dianiline complex is selected from the group consisting of sodium chloride and lithium chloride.

19. A process according to claim 13, wherein said curing is conducted at a temperature from about 80°C to about 140°C.

20. A process according to claim 13, wherein said catalyst has a dielectric constant of 2.0 and greater.

21. A process for the catalytic curing of an amine curable polymer or prepolymer in a reaction vessel, comprising the steps of adding by weight, 100 parts of an amine curable polymer or prepolymer which is selected from the group consisting of halogen containing hydrocarbon polymers, chlorosulfonated polymers and organopolysiloxanes, adding from 0.0005 to about 0.05 equivalents of an amine containing curing agent based upon the active groups of said amine curable polymer or prepolymer, said curing agent selected from the group consisting of a complex of 4,4'-methylene dianiline and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and a complex of racemic 2,3-di(4-aminophenyl) butane and a salt, said salt selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide, cesium chloride, cesium bromide and cesium iodide, the ratio of said dianiline or said butane to said salt in said complex being about 3 moles to 1 mole, and from 0.1 to about 35 parts of a curing agent catalyst selected from the group consisting of oleic acid, benzaldehyde, adiponitrile, acetic anhydride, polydimethylsiloxane and diethyl sulfate, and curing said polymer or prepolymer composition.

22. A process according to claim 21, wherein said curing is conducted at a temperature from about 80°C to about 130°C.

23. A process according to claim 21, wherein said catalyst has a dielectric constant of 2.0 and greater.

24. A process according to claim 21, wherein said equivalent ratio of said curing agent to said free active groups of said amine curable polymer or prepolymer ranges from 1.0 to about 1.2.

25. A process according to claims 21 or 24, wherein the amount of said catalyst ranges from about 0.2 to about 10 parts.

26. A process according to claim 21, wherein said amine curable prepolymer or polymer is a urethane prepolymer or polymer containing free isocyanate groups.

27. A process according to claim 21, wherein said curing agent is a complex of 4,4'-methylene dianiline and a salt.

28. A process according to claims 21 or 27, wherein said salt of said dianiline complex is selected from the group consisting of sodium chloride and lithium chloride.