DE2621923A1 - CURED POLYMERS AND MANUFACTURING METHODS - Google Patents

Description

The present invention relates to the catalysis and plasticization of amine curable polymers, and more particularly Polyurethane polymers with a specific class of compounds together with methylenedianiline complexes or racemic 2,3-di- (4-aminophenyl) -butane complexes reduced curing times and reasonably low Temperatures used to produce polymers that have unexpectedly improved life.

Heretofore, when curing amine curable polymers or prepolymers, such as epoxy resins, one has grindable halogen-containing Hydrocarbon polymers, and particularly isocyanate-terminated polyurethane prepolymers, in general Amine curing agent mixed in, the resulting mixture in brought into a usable shape and heated to complete the curing reaction. However, one encountered in general in this procedure on the problem of the premature reaction of the curing agent with the curable polymer the mixing and shaping processes. This problem was particularly

609850/0924

this is acute in highly reactive systems, e.g. when curing polyurethane prepolymers with isocyanate end groups, so that the use of special mixers with short residence times and selected diamine hardeners with reduced Activity was required, which generally limited the physical properties of the vulcanizate.

Among the class of widely used curing agents which overcome many of the problems noted above are the complexes of methylenedianiline and a salt, which on heating (generally above of temperatures of 100 C) release methylenedianiline from the complexes, so that the curing of the polymers began (U.S. Patent 3,755,261). Although it is a Technological improvement acted, this class of hardening agents still lost time and led to undesirable demolding times, which is due to the number required forms was uneconomical. The only way to overcome these tile parts was to control the curing temperature to increase, which of course led to an increased hardening rate. However, increased curing temperatures caused greater thermal expansion and subsequent shrinkage of the molded article, often resulting in stresses and cracks in the molded article Product led.

In recent times, various hardening complexes, e.g. that of methylenedianiline, have been used with very different polar Materials as well as with compounds containing hydroxyl groups have been catalyzed. Although generally an improvement the curing time and a lowering of the curing temperature has been achieved, these various connections present several undesirable aspects. E.g. multiple connections tended to to cure too quickly, so that uniform curing of a molded article was difficult. There was another problem in that they acted as solvents in automatic metering and mixing devices and, in fact, various seals of the fixtures. That was another problem

609850/0924

Degassing as the catalyzed compounds tended to cure the polymers before the gas was released from the molded article could escape. Other catalysts have tended to provide a viscous polymer which, in addition to the problem of degassing, required excessive time to load a mold. On the other hand, many compounds provided a composition with too low a viscosity and caused Problems in accurately metering the various components due to errors in the metering pumps. From the point of view of In terms of physical properties, none of the catalysts resulted in improved properties.

Accordingly, it is an object of the present invention to provide plasticizer compounds to be provided as hardening agent for methylenedianiline complexes or racemic 2,3 ~ di- (4-aminophenyl) -butane complexes, used in curing amine curable polymers or prepolymers.

Further, it is an object of the present invention to provide a plasticizer for the above-mentioned curing agents which are used in the Herstellur% of polyurethane polymers.

A further object of the present invention is to provide plasticizers for the hardening agents specified above, which are used as Catalyst act and increase the curing rate and the initial curing temperature reduce.

It is also an object of the present invention to provide plasticizers for the above hardening agents which have the Reduce demolding time and molding costs.

A further object of the present invention is to provide plasticizers for hardeners that are used in the hardening of with Amine curable polymers or prepolymers are used, which allow rapid polymerization when justifiable cause low temperatures and temperatures that are lower than is usually the case «

'' 6098 5 0 / 092A

A further object of the present invention is to provide plasticizers for the hardening agents specified above, which are to lead to an improved elastomer service life.

A further object of the present invention is to provide plasticizers for the above-mentioned hardening agents which contain a enable precise measurement of the components and do not damage the seals of the various devices.

It is also an object of the present invention to provide plasticizers for the above hardening agents which have a allow uniform curing and satisfactory demolding time and eliminate the degassing problems.

It is also an object of the present invention to provide plasticizers for the aforesaid curing agents to provide useful cast tire blanks.

A further object of the present invention is to provide plasticizers for the hardening agents specified above, with which cast tire body stock can be obtained with greater elasticity and service life.

The object of the present invention is explained below, various embodiments being described in detail without attempting to discuss all the possible variations.

Generally, a polymer cured with a catalyst comprises on a weight basis 100 parts of one with an amine curable polymers or prepolymers made from urethanes with free isocyanate groups, epoxy resins, polymers with acid halide and haloformate groups and polymers with anhydride groups which, when reacted with diamines, form amide-acid bonds provide, formed group, 0.8 to 1.2 equivalents of a curing agent based on the free active Groups of the amine-curable polymer or prepolymer, the curing agent being selected from the complexes of 4,4'-methylenedianiline with a salt obtained from the sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, Lithium bromide, lithium iodide, lithium nitrate and

609850/0924

Sodium cyanide is selected, and complexes of the racemic 2,3-di- (4-aminophenyl) -butane with a salt is selected, the salt being selected from the group formed by 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 is selected and the ratio of dianiline and butane to the complex is about 3 mol to 1 mol, and about 1.0 part to about 15? 0 parts of an ester of the formula (R -GO-O) _x -Ry, where r ' ^{1 is} a polyglycol radical having 2 to 5 carbon atoms and R is an aliphatic radical having 4 to 9 carbon atoms and X is 1 or 2 and Y is an integer from 1 to 5.

Also includes a polymer composition cured with a catalyst on a weight basis 100 parts of an amine curable polymer or prepolymer from the through halogen-containing hydrocarbon polymers, chlorosulfonated polymers and organopolysiloxanes and about 0.0005 to about 0.05 equivalents of a curing agent based on the active groups of the amine-curable polymer, wherein the hardening agent is the hardening agent specified above and the composition is further contains about 1.0 to about 15? 0 parts of the ester.

In accordance with the present invention, it has been found that the Use of various specific ester plasticizers in combination with a hardener that is used to harden amine curable polymers or prepolymers are used, generally at increased cure rates, decreased cure temperatures or both together with good demolding times, a solution to the degassing problem and a unexpected improvement of the physical lifespan, especially in the case of cast urethane elastomers, which are preferably used as green tires.

A special and preferred curing agent is a complex of 4-, 4'-methylenedianiline (MDA) and a salt.

6098 5 0/0 924

The preparation of the specific hardener complex is described in US Pat. No. 3,755,261, which is hereby incorporated by reference is taken, particularly with regard to the various complexes of 4,4'-methylenedianiline with a salt and their formation. In general, the complexes used as curing agents for amine curable polymers include Reaction products of 4,4'-methylenedianiline with the following Salts at a ratio of about 3 moles of methylenedianiline 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. Sodium chloride is the most most preferred salt.

Another complex that can be used as a hardening agent is the reaction product of racemic 2,3-di (4-aminophenyl ·) butane with any of the following salts in about 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. That the most preferred salt is sodium chloride. The preparation of the hardener is also described in US Pat. No. 3,755,261 which are fully incorporated herein by reference.

The use of the preferred curing agent (MDA) or butane complex upon curing of the curable amine prepolymers or polymers upon heating to a temperature of about 100 ⁰ C causes methylenedianiline is released from the complex and the polymers or copolymers cured in a manner which is believed to be identical to that using free methylenedianiline or butane as the curing agent.

The complexes listed above can be many amine curable "^ polymers or cure polymers as in the above U.S. Patent No. 3,755,261 cited, which is also referred to herein for the general and specific type of

609850/0924

with amine curable prepolymers or polymers are fully referred to will. In general, the preferred class of such prepolymers or polymers is Urethanes, generally obtained by reacting a diisocyanate and a glycol or diol with a molecular weight generally from 400 to 8000 and preferably from 600 to 3000. Such urethanes can typically through the conversion of polyalkylene diols, polyalkylene ether diols, Polyester polyols, polybutadiene diols and their combinations in an equivalent amount or a slight amount Excess diisocyanates or triisocyanates formed to form an isocyanate-terminated prepolymer will. The present invention relates to urethanes formed in this way as well as urethanes formed in other ways, such as one skilled in the art can easily see. The following US patents describe some general types of urethanes: 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 3,114,735. Regarding particularly preferred special ones Diols include polypropylene ether dxol and polytetramethylene ether diol. Other preferred diols include, for example Polyethylene ether diol, polytrimethylene ether diol and polyhexamethylene ether diol.

Other groups of amine-curable prepolymers and polymers of US Pat. No. 3,755,261 are epoxy resins, polymers with acid halide groups, e.g. -CO-Cl- and haloformate groups, for example -O-CO-Cl groups, polymers with anhydride groups, which, when reacted with diamines, yield amide-acid bonds, halogen-containing hydrocarbon polymers, such as chloroprene polymers, chlorinated butyl rubbers and chlorinated polyethylenes and chlorosulfonated polypropylene polymers (polypropylene chlorosulfonated polymers) and organopolysiloxanes.

It has surprisingly been found that the specific ester plasticizers of the present invention, when used in combination with the complex curing agents listed above

6098 50/09 24

agents are used, act as accelerators or have a catalytic effect on the curing of the polyurethane as also exercise on other listed amine curable polymers or prepolymers. In addition, it was also found that that when different polymers are in a heated form, for example in the manufacture of cast tire blanks hardened, the problems of degassing, premature hardening, non-uniform hardening, the slow feed rates to the mold due to the high viscosity of the composition and dimensional problems (often due to particularly low viscosities), which is often the case with other catalysts for the complex curing agents listed above encountered are generally avoided.

Based on 100 parts by weight of a polymer or prepolymer For example, about 1.0 to about 15.0 parts of an ester according to the invention are desirable. A preferred range is from about 2.0 to about 10.0 parts. Of course, the exact amount of the respective polyglycol depends on the respective curing temperature, the particular amine-curable polymer and the particular catalyst according to the invention.

The esters of the present invention have the formula

1 1

(R-CO-O) -R .. In general, R can be any polyglycol

^x y
radical, e.g. a glycol radical with 2 to 5 carbon atoms, or various such radicals, χ is 1 or 2 and y is 1 to 5 · Preferably χ = 2 and y = 4. Specific examples of polyglycols include tetraethylene glycol, tetrapropylene glycol, tetrabutylene glycol , Tetrapentylene glycol, di-ethylene dipropylene glycol and propylene triethylene glycol. Preferred polyglycol compounds include tetraethylene glycol and tetrapropylene glycol, with tetraethylene glycol being particularly preferred.

In general, R is an aliphatic radical with h to 9 carbon atoms, preferably an alkane radical. Specific examples include the butyl, pentyl, hexyl, heptyl,

60985 0./0924

Octyl, nonyl and 2-ethylhexyl radical, the 2-ethylhexyl radical being particularly preferred. As indicated above, a particularly preferred class of esters relates to complexes of the formula (R-CO-O) ₂ - (R ¹ ) ^. Tetraethylene glycol di (2-ethylhexoate) is a particularly preferred compound. His

Formula looks like this:

0 0

C ^ H ₉ (C ₂ H ₅ ) CH-C-OCH ₂ - (CH ₂ -O-CH ₂ J ₃ -CH ₂ OC-CH (C ₂ H ₅ JC ₁₁ H _g

Tetraethylene glycol di (-2-ethylhexoate) can be sold as Flexon 4GO and is manufactured by Union Carbide. The formulas of other polyglycol esters of 2-ethylhexanoic acid are of course identical, with only the section of the molecule in the brackets differing. As stated above this group of special plasticizers gives good practical results in the processing and curing of various amine curable polymers. This fact is quite surprising since - as from the above chemical Formula of a typical compound shows - the plasticizers are not highly polar and no free hydroxyl compounds contain like the known compounds, but are high molecular weight esters in which the polar groups are considerable are sterically hindered.

Further preferred compounds are the half esters in which x = 1 and y = 1. Examples include methyl M-butyrate, Ethyl M-butyrate, ethyl isobutyrate, ethyl valerate, ethyl caproate, Ethyl heptoate, ethyl capryate, ethyl pelargonate including propyl, butyl and amyl derivatives.

The plasticizers of the present invention are also the extent desired, as they C (424 ⁰ F) possess at 5 Torr in the case of Tetraäthylenglykoldi- £ ethyl hexoate) is generally a high boiling point of, for example 218 ^0; thus very little plasticizer is lost on curing compared to the prior art volatile catalysts which resulted in exceptional mold shrinkage. Further, the viscosities of the various plasticizers, for example, 12 cPoise at 40 ⁰ C in the case of Tetraäthylenglykoldi- are (2-ethylhexoate) for

609850/0324

- ίο -

accurate metering of the plasticizer component, ie suitable without error of the metering pump; When the plasticizers are mixed with the amine-curable polymers and other components, for example other plasticizers, they are very compatible and allow rapid injection times as well as a suitable escape time for the gases formed. In this way, the disadvantages of uneven curing and degassing are easily avoided. Furthermore, the plasticizers of the present invention do not act as solvents; they also do not destroy the various rings and seals of the dispensing equipment. Further, the plasticizer, in the Hartung temperature range of about 80 to about 170 are ⁰ C liquid. A preferred curing temperature for most presently available polymer systems, including the urethane is about 100 to about 140 ⁰ C, particularly preferred temperatures are at about 115 to about 125 ⁰ C.

If it is the amine curable polymer or prepolymer If polyurethane is concerned, the amount of the 2 curing agent complexes listed above is generally in the range from about 0.8 to about 1.2 equivalents of the diamine in the hardening agent with respect to the free isocyanate groups of the polyurethane. A more preferred range is from about 0.9 to about 1.05 Equivalents, a ratio of 1.025 being particularly preferred. Ratios above and below the latitude range lead to a noticeable rate in the manufacture of the particularly preferred product in cast urethane tire blanks

Variation both in terms of the curing process of the product and its physical properties. The above Areas cited can also be applied to compositions which contain the epoxy resins and polymers cited above Acid halide groups and haloformate groups as well as polymers with anhydride groups that are involved in the reaction with diamines provide amide-acid bonds. That is, the amount of the curing agent complex of, for example, methylenedianiline and a salt, for example sodium chloride,

609850/0924

is in the range of equivalents given above based on the number of free active groups in the polymer or prepolymer which reacts with the methylenedianiline.

Considering the remaining polymers and prepolymers, i.e. the halogen-containing hydrocarbon polymers, the chlorosulfonated polymers and the organopolysiloxanes, which generally do not have isocyanate groups in their end sections of the chain, there is a much smaller equivalent ratio for curing these compounds than for crosslinking necessary. Depending on the desired molecular weight of the polymers and the molecular weight of the prepolymers the amount of the amine curing agent can vary over a wide range. In general, such an area can be found from about 0.0005 to about 0.05 equivalents of the reactive component of the curing agent, e.g., the diam'ine, to the active Extend group in the polymer or prepolymer. A preferred range is 0.0005 to about 0.05 equivalents. the Amount of the ester plasticizer of the present invention used for the remaining polymers or prepolymers, is generally as large as indicated above for the urethane compounds, prepolymers, or polymers.

In accordance with conventional art in the art of molding and curing amine curable polymers or Customary additives or compounds to the composition according to the invention can be added to prepolymers in order to achieve desired To confer properties or characteristics. These include common antifoam agents, common pigments, a desired one give an aesthetic appearance, common foaming agents for foam bodies and common fillers, e.g. Hi SiI. Naturally other additives may be added depending on the desired use of the product, e.g., flame retardants.

In the production of polyurethanes it is often desirable to use additional customary plasticizers to increase flexibility

'609850/0924

to admit the object. The addition of such common plasticizers is particularly useful in the manufacture of urethanes preferred in terms of their use for green tires. About special preferred plasticizers used in manufacture Urethanes used include dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), and diisodecyl phthalate (DIDP) Dinonyl phthalate (DNP). DOP is particularly preferred. It was surprisingly found that the use of a conventional Plasticizer as well as the ester plasticizer according to the invention in addition to an increased flexibility of the cured Imparts improved viability to the final product, as can be seen in Examples I and II below. Although the exact reason for this effect is not fully understood, it is believed that the use of a common plasticizer with an ester plasticizer according to the invention additionally the effect of an unforeseeable curing catalyst brings about and brings about a synergistic and unexpected result. A suitable range of the common plasticizer can be from about 4 to about 20 parts per 100 parts of the amine curable polymer, and preferably from about 12 to be about 17 parts. Since the various ester plasticizers, e.g. the polyglycol ester of 2-ethylhexanoic acid, with the preferred Plasticizers are completely compatible, e.g. with DOP, and are less volatile than the plasticizers, that is The end result is a less volatile plasticizer system, which avoids the problems of degassing and also large ones Amounts of the preferred plasticizer remain in the cured elastomer system. It was also found that the use from two plasticizers to greater elasticity of the cured polymer, especially at low temperatures leads. The usual plasticizer is preferably added as a mixture with the amine hardener.

Light stabilizers can also be used, particularly for the manufacture of polyurethanes for cured tires. A preferred light stabilizer is carbon black in an amount of from about 0.3 to about 3.0 parts ¹ per 100 parts of the with

609850/0924

Amine curable polymers. Quantities in excess of 3 parts can lead to a very viscous polymer composition, which leads to difficulties in terms of a short or practicable mold filling time and, accordingly, uneven hardening and brings bad qualities with it. Since soot with larger particle sizes tends to crack more easily, a fine particle size preferred. Typically, particles no larger than 1 micron are preferred. Of course you can any conventional carbon black which meets this requirement can be used, for example REGAL 400R from Cabot. Further leads the carbon black also contributes to the characteristic black color of the tires, which because of its aesthetics attracts potential buyers.

Other light stabilizers include both common inorganic ones as well as conventional organic dyes or pigments in an amount of about 0.3 to about 1.5 parts per 100 parts of the Polymers. The dyes can either completely contain carbon black or partially replace. Although carbon black is generally preferred over dyes, dyes are nonetheless commonly used because they have a very small particle size, much smaller than a micron. To specific examples of dyes include Thermoplast NSP (American Ugine organic dye) and Nigrosine SSB (organic dye the American Cyanamid). Of course, other usual organic ones can be used or inorganic dyes or pigments can also be used, for example

The curable prepolymers and polymers made according to the invention can be used for many purposes will. For example, polyurethane can be used for shoe soles, utility clothing, roller wheels, automotive parts and Motor vehicle bumpers are used. As mentioned above, there is a very important and technical application in the production of green tires that can be provided with conventional tread rubber, for example with polybutadiene / styrene.

609850/0924

The composition according to the invention can be prepared by reacting the polymers or prepolymers with a Härtungsmittelkomplex at room temperature or slightly elevated temperature, for example at etiva 50 ⁰ C, but mixed below the curing temperature of the Komplexhärtungsmittels, generally at about 90 to 100 ⁰ C. The various additives, fillers, etc. can also be added and mixed. When the curing agent is the preferred methylenedianiline complex with sodium chloride, it usually contains a protective colloid suspending agent such as lecithin. Since lecithin is also a good foam stabilizer, an antifoam agent such as a compounded silicone compound (Dow Corning Paint Additive No. 7) can be added. In general, it has been found that when a centrifugal mold is used, for example in the manufacture of green tires, if the overall viscosity is low and the molding speed is high at the same time, no antifoam agent has to be used. It should also be noted that DOP can be used as a carrier for the MDA curing agent; accordingly, the amount of the preferred plasticizer added can be decreased by a corresponding amount. In any case, the various esters, for example the various polyglycol esters of 2-ethylhexanoic acid, are added to the casting mold and mixed immediately before being charged (dispensing). Since short molding cycles are desired to reduce operating costs, the viscosity of the urethane composition is preferably below 150 poise. Such a low viscosity also allows the various components to be mixed quickly. A viscosity of 50 poise or less is preferred. The mold is then filled and the composition cured. Compositions according to the invention using urethane polymers for green tires can generally be cured sufficiently in 5 minutes after filling the mold so that the tire has sufficient strength to be immediately mechanically demolded without damage to the tire.

609850/0924

The invention thus relates to amine curable polymers and Prepolymers of, for example, urethane formed using a methylenedianiline complex or a complex of the racemic 2,3-di - (^ - aminophenyl) butane, in the presence a catalytic plasticizer compound, with increased curing rates, lower curing temperatures and improved lifetimes can be achieved.

Table I lists various physical properties of cast polyurethanes made in accordance with the invention were manufactured.

As can readily be seen from Examples I and II, the cured polyurethanes performed according to the invention to significantly longer lifetimes than the comparison as well as to an unexpected increase in the hardening rate and Reduction of the hardening time.

609850/0924

CD O CO co cn ο

(X) FO

Table I.

(All samples measured 15 χ 15 x 0.018 cm = 6 χ 6 χ 0.075 "and were under Pressure hardened in 5 min = LAB SAMPLES)

IA IB 2A 2B 3A 3B 4a

Post-curing (oven) 0 45 'at O 45' at O 45 'at

■ ⁿ C 140 ° C 140 ° C

L.SM. 5 ff (0.07 kg / cm ²
= PSI) 465 ) 1184 515 515 535 510 510 510 I. N? Module (0.07 kg / cm ² = PSI 1634 CT3 100 % 1585 1550 1550 1515 I525 158Ο I. 1923 200 % 2085 2070 2010 1955 I960 2055 I. 300 % 2000 2475 2625 2515 2535 2690 400 % 1990 4080 4140 3690 3430 34 80 3640 500 % 300 5170 4895 Break (BRK) 5295 4770 5245 3690 4935 3425 Elongation at break (ff) 1335 490 455 510 440 510 400 Module at 100 ⁰ C (212 ° F-
0.07 kg / cm ² = PSI) 1890 100 % 1925 1300 1365 1310 1330 1235 1350 300 ff 320 1815 2060 1825 2,000 1720 2025 Fracture . 2020 2150 2670 2000 2390 2100 Elongation at break (%) 330 320 . 480 300 480 320

Table I (continued)

Shore "A" at 23 ^U C

(73 ° F) 92 89

crescent-shaped hiss

(crescent tear);

(0.07 kg / cm ² = PSI)

at 100 ⁰ C (212 ° F) 254 301

Caytur 21,% of the theoretical value

Caytur 21 PHP Flexol 4G0 PHP

Adriprene L-367 rate no./min

Caytur rate no./min

Flexol 4G0 rate no./min

10.74 at 10.74

54 ⁰ C

(130 ⁰ F)

3.65 at

49 ⁰ C

(12O ⁰ F)

3.65

91

261

307

10.74

10.74 10.74

0.16 at 0.16 at 0.21 38 ° C 38 ⁰ C (100 ⁰ F) (100 ⁰ F)

Oil (DOP + 4G0) PHP 18.35 18.35 19.17 Pouring rate nr / min 19.50 19.50 14.261

3.65

0.21

19.17
14.61

3.65

0.34

19.99
14.72

3.65

0.34

19.99 14.72

90

265

101.0 101.0 101.0 101.0 101.0 101.0 101.0 34.0 34.0 34.0 34.0 34.0 34.0 34.0 1.52 1.52 2.34 2.34 3.16 3.16 4.67

10.74

3.65

0.43

21.5 K>

14.83

CO N) Ca)

Table I (port setting)

sample

5A

5B

6A

6B

oo cn ο

Ver Polymeg 5.0 PHP / TBP equals 620

Hardened press

Post-curing (oven) 45 'at
14O ° C 0 45 'at
14O ° C 0 60 'at
14O ° C 60 'bej
120 ⁰ C 420 445 ■ N) LSM 5 % (0.07 kg /
cnr = PSI) 505 515 485 500 500 500 I. 0 Module (0.07 kg / cm ² =
PSI) IO85 1125 CO
I. ISJ 100 % 1530 1545 1495 1520 1520 1410 1540 1535 I. CO
Kj 200 % 1980 2070 I960 I99O 1940 1915 2205 2080 300 % 2570 2830 2600 2615 2735 2590 3405 3025 400 % 3570 3675 3445 3905 3755 500 % 4055 43OO fracture 4400 2930 3900 3300 4935 5425 450 485 Elongation at break {%) 485 340 450 400 495 485 Module at 100 ⁰ C (212 ⁰ P;
0.07 kg / cBT = PSI) 740 825 100 % 1245 1310 1200 1345 1275 880 1350 300 % 1725 I75O 2030 I87O 1430 1265 1425 fracture 1905 1475 2000 2005 2365 1950 265 305 Elongation at break {%) 360 160 370 290 420 420 87 87 Shore "A" at 23 ° C (73 ° P ) 89 90 90 91 89 91

Table I (port setting)

semicircular crack (0.07 kg / cm = PSI at 100 ⁰ C = 212 ° P)

cn
ο Adiprene L-367 at 54
(130 ⁰ F) 253 283 263 278 272 212 253 1
(-Λ ΓΟ ·. CD
m Rate no./min 101.0 10.74
C. 10.74 10.74 10.74 10.74 10.74 10.74 VO
I. CT5 ) / 0 S ί Caytur 21 % of theory 34.0 101.0 101.0 102.5 102.5 102.9 102.5 102.5 CD
K)
CO * - ■ - *
CO
ro Caytur 21-PHP ' 4.67 34.0 34.0 34.52 34.52 34.65 31.13 34.61 Flexol 4GO 3.65
at
49 ° C
(120 ° F) 5.45 5.45 3.08 3.08 3.16 3.10
Polymeg
620 5.00 TBP Caytur 21 no. / Min 3.65
at
49 ⁰ C
(120 ⁰ F) 3.65
at
(120 ⁰ F) 3.65
at
49 ° C
(120 ⁰ F) 3.65
at
49 ⁰ C
(120 ° F) 3.72
at
49 ° C
(120 ⁰ F) 3.34
at
52 ° C
(125 ° F) 3.72
at
49 ° C
(12O ⁰ F) 0.43
at
38 ⁰ C
(100 ⁰ F) Polymeg
620 5/0 php /
TBP Plexol 4GO No./min. 21.5 0.54
at
38 ⁰ C _n
(100 ⁰ F) 0.54
at
38 ⁰ C ₀
(100 ⁰ P) 0.33
at
38 ⁰ C _n
(100 ⁰ F) 0.33
at
38 ⁰ C
(100 ⁰ F) 0.34
at
38 ° C
(100 ⁰ P) 0.03
at
43 ⁰ C
(110 ⁰ F) 0.54
at
32 ° C
(90 ⁰ F) Oil (DOP catalyst) PHP 14.83 22.28 22.28 20.17 20.17 20.31 21.29 22.13 Casting rate no./min 14.93 14.93 14.72 14.72 14.80 14.72 15.0

2521923

- 20 Example I.

Three tires (size 145-13) were centrifugally cast from catalyzed elastomer feedstock that had been measured, mixed and machined on a three component Admiral elastomer processing machine. Each of the three tires was ^{cured for 1 hour at 120 °} C. and then tested for its service life with an indoor wheel in accordance with the US Department of Transportation regulations. Test specimens 0.19 cm (0.075 ") thick were cured along with each tire to determine physical properties. In addition, test panels (15 × 15 × 0.19 cm or 6 × 6 × 0.075") were made of additional. liquid elastomer that was left after filling the tire mold prepared by curing in a Kompressionspreßform, which had been heated to 120 ⁰ C. Two groups of these plates were demolded after a pressing time of only 5 minutes and then post-cured in an oven with air circulation for the specified time and at the specified temperature in order to compare the physical properties with plates which had been cured together with the tires.

According to the D.O.T. criteria, the specified minimum driving distance until it is unusable is 2735 km (1700 miles) below strict conditions, with the test tires after 4868 km (3025 miles), 4828 km (3000 miles) or 5303 km (3295 miles) were useless. The D.O.T. life test for tires (145-13) requires operation at a nominal load at the beginning and a nominal tube filling (304 kg or 6701lbs / tire at 1.68 kg / cm or 24 PSI) with gradually increased load (as indicated below), with a speed 80 km / h (50 MPH) is continuously maintained; 4 h (322 km or 200 miles) under 304 kg (67Ο lbs), after that Increase the load to 338 kg (745 lbs) and 6 hours longer Operation (483 km or 300 miles) under 338 kg (745 lbs), after that Increase the load to 363 kg (800 lbs) and 24 hours longer

6 0 9 8 5 0/0924

282 19

Operation (1930 km or 1200 miles) under 363 kg (800 lbs) without failure.

After completing the required 2735 km (17OO miles) the tested test tires were subjected to the following loads until they were unusable:

Tire 1: After 2735 km (17OO miles) the load had increased to 395 kg (870 lbs) and it was tested at this load for 8 hours (644 km or 400 miles), after which the load increased to 442 kg (975 lbs) 8 hours (644 km or 400 miles), after which the load was increased to 487 kg (1075 lbs) for 8 hours (644 km or 400 miles), after which the load was increased to 532 kg (II75 lbs) . This tire was then tested 201 km (125 miles; 4868 km total or 3025 miles) under 532 kg (1175 lbs) before becoming unusable.

Tire 2: It was subject to identical load and speed conditions like tire 1 and was after 16 miles (100 miles; 4828 km in total or 3000 miles) unusable with a load of 532 kg (1175 lbs).

Tire 3: It was subjected to the same stresses as Tire and Tire 2, but 179 km (395 miles; 5303 km) total or 3295 miles) tested under a load of 532 kg (II75 lbs) before becoming unusable.

In contrast, numerous comparison tires were tested for an overall average of 8 hours with a load of 442 kg unusable, (975 lbs; corresponding to a total of 4023 km or 25OO miles). The approach for the comparison tires was the same as for tires 1, 2 and 3 except that they did not contain Plexol 4GO. So it is clear to see that a great increase in service life has been achieved.

609850/0924

2021923

Tire 1: 4868 km (3025 miles) run under increased D.O.T.load

Plate hardening with tires 60 ' Press/ Press/ Press 120 ⁰ C oven oven Curing time not applicable 5 ' 5 ' 60 ' Hart ung s t emp e r at ur - 120 ⁰ C 120 ⁰ C 120 ° C Post-curing time 45 ' 45 ' not applicable Post-curing temperature 145 ° C 120 ° c - tested at 23 ° C: 470 5 % module (0 _} 07 kg / cm ² 1315 = PSI) 1650 440 435 45O 100 % module " 2120 1380 1475 1455 200ί module " 2905 1740 1885 1835 300 % module " 4320 2230 2440 2350 400 % module " 452O 3025 3400 318O 500 % module " 515 4290 - 456O Final pull (0.07 kg / cm ² = PSI) 4735 5OO5 4625 Final elongation ( % ) 436 530 495 505 semicircular crack 90 (0.07 kg / cm ² = PSI) 486 495 487 Shore hardness A 90 90 90 tested at 100 ⁰ C: 940 100 % modulus (0.07 kg / cm ² = I35O PSI) I78O 1000 1010 1020 300 % module " 410 1405 143.0 1450 Final pull (0.07 kg / cm ² = PSI) I87O 1800 1715 Final elongation ( % ) 445 390 360 semicircular crack

(0.07 kg / cnT = PSI)

306

392

386

377

609850/092 4

Approach: Adiprene L-367

Caytur 21 (102nd, 5 %) Flexol 4GO
DC-7

Total plasticizer machine casting council e

100 parts 33.92 parts 4.50 parts 0.25 parts 21.3 parts / 100 parts polymer (phP) 15.0 no./min

Adiprene L-367 is manufactured by DuPont and is polytetramethylene ether glycol with a molecular weight of about 1000 and two terminal molecules from Hylene ™, ie a mixture (about 80/20) of the 2,4 / 2,6-IsOmCrOn of toluene diisocyanate. Caytur 21 is a complex of 4,4'-methylenedianiline with sodium chloride in the form of a dispersion in 50 % DOP.

609850/0924

Tire 2: 4828 km (3000 miles) run under increased D.O.T.load

Plate hardening

Curing time Curing temperature Post-curing time Post-curing temperature

tested at 23 ° C:

5 % module (0.07 kg / cm ² = PSI)

100 % module "200 % module" 300 % module "400 % module" 500 % module "

Final tensile (0.07 kg / cm ² = PSI) final elongation ( % ) semicircular tear

(0.07 kg / cm ² = PSI) Shore hardness A tested at 100 ⁰ C:

100 % module (0.07 kg / cm ² - PSI)

300 % module "

Ultimate tensile (0.07 kg / cm ² = PSI) ultimate elongation {%) semicircular tear

(0.07 kg / cm ² = PSI) with tire press / oven

pressure

60 ' 5 ¹ 60 ' 120 ⁰ C 120 ⁰ C 120 ⁰ C not applicable 30 ' not applicable * I. λ Ο π

425 395 425 1245 1175 1300 1560 1505 1670 2035 1915 2165 2780 2545 2985 4035 3370 ^ 235 4205 3700 4275 515 505 505 524 538 539 91 92 92

930

915

990

1285 1195 ■ 1345 1930 1760 2370 480 530 580

368 399

396

609850/0924

Approach: Adiprene L-367 100 parts

Caytur 21 (102.5 %) 33.92 parts

Plexol 4GO 6.0 parts

DC-7 0.25 parts

Total plasticizer 22.8 parts / 100 parts polymer

(phP)

Machine pour rate 15.0 nr / min

609850/0924

Tire 3: ran 5303 km (3295 miles) under increased D.O.T.load

Plate hardening

Curing time
Curing temperature
Post-curing time with tire press

Press

Post-curing temperature tested at 23 ° C:

5 % module (0.07 kg / cm ² = PSI) 100% module "200 % module ⁿ 300 % module" 400% module "500 % module"

Final tension (0.07 kg / cm ² = PSI) final elongation (%)

semi-circular crack

(0.07 kg / cm ² = PSI) Shore hardness A

tested at 100 ⁰ C:

100 % module (0.0? Kg / cm ² = PSI) 300 Jg module "

Final tension (0.07 kg / cm ² = PSI) final elongation (%)

semi-circular crack

(0.07 kg / cm ² = PSI)

60 « 5 ¹ 60 · 120 ⁰ C 120 ⁰ C 120 ⁰ C not applicable Broken
at Ent
to shape
from the
Press

425
1140
I5IO
1980
2750
4075
443O

525

481
90

945
1325
2400

575
356

460

1275 I670 2155 2990 4400 4750 520

521 93

990 1420 2130

475

389

609850/0924

Approach: Adiprene L-367 100 parts

Caytur 21 (102.5 %) 33.92 parts

Flexol 4GO 3.0 parts

DC-7 0.15 parts

Total plasticizer 19.8 parts / 100 parts polymer

(phP)

Machine pour rate 15.0 nr / min

Example II

In addition, two tires (145-13) were made as in Example I for testing according to the DOT high speed regulation which requires a minimum fitness for 0.5 hours at 137 km / h (85 MPH). Again, plaques (0.19 cm or 0.075 ") were prepared to determine physical properties under various curing conditions. Particularly noteworthy are the excellent physical properties obtained at elevated temperature when testing the plaques which were demolded after a 5 minute press cure vjurden and then post-cured for 60 minutes at 120 ⁰ C in a fully relaxed state.

The specified high speed D.O.T. test for Tire (145-13) requires a tube filling of 1.68 kg / cm (24 PSI), a load of 304 kg per tire and the following run times and speeds;

2.0 h warm-up at 80 km / h (50 MPH); then increase the speed to 121 km / h (75 MPH) and a 0.5 hour long Run at 121 km / h (75 mph); then increase the speed to 129 km / h (80 MPH) and a 0.5 h run 129 km / h (80 MPH) and increasing the speed to 137 km / h (85 MPH). The tire then had to travel at I37 km / h for 0.5 hours (85 MPH) run with no errors to pass the test.

609850/0924

In the case of test tires 4 and 5, the test was continued above 137 km / h (85 MPH) until it was unusable as follows;

0.5 h at 145 km / h (90 MPH), 0.5 h at 153 km / h (95 after increasing the speed to 161 km / h (100 MPH), both tires failed after 12 minutes at 161 km / h (100 MPH).

In contrast, numerous comparison tires were average Unusable for 0.2 hours at 153 km / h (95 MPH). The comparative tires had the same composition as that Tires 5 and 6 except that they did not contain Plexol 4G0.

609850/092 4

Tire 4: Run 0.2 h at 161 km / h (100 MPH) with increased D.O.T. high-speed test

Plate hardening

Curing time Curing temperature Post-curing time Post-curing temperature

tested at 23 ° C:

5 % module (0.07 kg / cm ² = PSI) 100 % module "200 % module" 300 % module "400 % module" 500 % module "

Ultimate tensile (0.07 kg / cm ² = PSI) ultimate elongation {%) semicircular tear

(0.07 kg / cm ² = PSI) Shore hardness A tested at 100 ⁰ C:

ICO % module (0.07 kg / cm ² = PSI) 300 % module. "

Ultimate tensile (0.07 kg / cm ² = PSI) ultimate elongation {%) semicircular tear

(0.07 kg / cm ² = PSI)

with tires Press/ Press oven 60 ' VJl 60 ' 120 ⁰ C 12O ⁰ C 12O ⁰ C not applicable 30 « not applicable - 14O ⁰ C - 415 430 410 1215 1205 1170 1600 1580 1525 2110 2070 1965 1935 2945 2755 - - 4005 3835 4250 4430 460 490 530 474 497 491 92 88 90 980 1035 1005 1440 1450 1425 1710 2240 2175 380 500 500 385

357

381

609850/0924

Approach: Adiprene L-367 100 parts

Caytur 21 (102.50 %) 33.92 parts

Flexol 4GO 3.0 parts

DC-7 0.15 parts

Total plasticizer 19, & parts / 100 parts polymer (phP)

Machine pour rate 15.0 nr / min

609850/0924

Tire 5: Run 0.2 h at 16 l km / h (100 MPH) with increased D.O.T. high-speed test

Plate hardening

Curing time Curing temperature Post-curing time Post-curing temperature

tested at 23 ° C:

5 % module (0.07 kg / cm ² = PSI)

100 % module "200 % module" 300 % module "400 % module" 500 % module "

Final tensile (0.07 kg / cm ² = PSI) final elongation ( % ) semicircular tear

(0.07 kg / cm ² = PSI) Shore hardness A tested at 100 ⁰ C:

100 % module (0.07 kg / cm ² = PSI)

300 % module "

Final tensile (0.07 kg / cm ² = PSI) final elongation ( % ) semicircular tear

(0.07- kg / cm ² = PSI)

with tires Press/ Press/ Press oven oven 60 · VJl 5 ' 60 ' 12O ⁰ C 12O ⁰ C 120 ° C 12O ⁰ C not applicable 30 ' 60 » not applicable 14O ° C 120 ⁰ C

420

400

420

325

1295 1345 1340 1315 1585 1600 1635 1595 1935 1915 1990 1930 2480 2370 2550 2415 3320 3070 3500 3210 4245 3695 4490 4265 575 575 500 595 505 512 90 91 92 91 90 91 935 940 950 950 1300 1160 1265 1260 1565 1375 2090 1970 385 430 590 590

365

372

376

378 '

609850/0924

Approach: Adiprene L-367 100 parts

Caytur 21 (102.5 %) 33.92 parts

Flexol 4GO 9.0 parts

DC-7 0.35 parts

Total plasticizer 25.8 parts / 100 parts polymer (phP)

Machine pouring rate 15.0 no./min

609850/0924

Claims (1)

Claims 1. Cured polymer, characterized by (on a weight basis) 100 parts of an amine-curable polymer or prepolymers made of the by urethanes with free isocyanate groups, epoxy resins, polymers with acid halide and haloformate groups and polymers with anhydride groups, which when reacted with diamines amide-acid -Bonds form, formed group, 0.8 to about 1.2 equivalents of a curing agent based on the free active groups of the amine-curable polymer or prepolymer, the curing agent from the complexes of ² 1,4'-methylenedianiline with a Salt selected from the group formed by sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide, and complexes of racemic 2,3-di- (iJ-aminophenyD-butane with a salt) is, the salt being made up 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 is selected and the ratio of the dianiline or butane to the salt in the complex is about 3 moles to 1 mole, and about 1.0 to about 15.0 parts of a Esters of the formula (R-CO-O) _x -R 'where R ^{1 is} a polyglycol radical with a total of 2 to 5 carbon atoms or various such polyglycol radicals, R is an aliphatic radical with 4 to 9 carbon atoms, χ = 1 or 2 and y is a whole Number from 1 to 5 is. 2. Cured polymer according to claim 1, characterized by a curing agent range of about 0.9 to about 1.05. 3. Cured polymer according to claim 1, characterized in that χ = 2 and y = 4. 609850/092 4 _ 34 - 4. Cured polymer according to claim 3, characterized by tetraäthylenglykoldi- (2-ethylhexoate) as an ester and a curing agent complex of 4,4'-methylenedianiline and Sodium chloride. 5. Cured polymer according to claim 1, characterized in that that the amine curable polymer or prepolymer is a urethane with free isocyanate groups acts. 6. Cured polymer according to claim 5, characterized by a 4,4'-methylenedianiline complex with sodium chloride as a curing agent. 7. Cured polymer according to claim 6, characterized by a curing agent range from about 0.9 to about 1.05 8. Cured polymer according to claim 6, characterized by an ester with an x value of 2 and a y value of 4th 9. Cured polymer according to claim 8, characterized in that the radical R ^{1 is selected} from the group formed by tetraethylene glycol, tetrapropylene glycol, tetrabutylene glycol, tetrapentylene glycol, diethylene dipropylene glycol and propylene triethylene glycol radicals, and that the radical R is selected from the group formed by butyl Pentyl, hexyl, heptyl, octyl, nonyl and 2-ethylhexyl radicals is selected. 10. Cured polymer according to claim 8, characterized in that the ester from the tetraethylene glycol di (2-ethylhexoate), Tetrapropylene glycol di (2-ethylhexoate), tetrabutylene glycol di (2-ethylhexoate), tetrapentylene glycol di (2-ethylhexoate), Diethylenedipropylene glycol di (2-ethylhexoate) and propylene triethylene glycol di (2-ethylhexoate) is selected. 609850/0924 11. Cured polymer according to claim 8, characterized by tetraethylene glycol di (2-ethylhexoate) as the ester. 12. Cured polymer according to claim 8, characterized by a range of the ester from about 2 to about 10 parts. 13. Cured polymer according to claim 10, characterized by an amount of ester in the range of about 2.0 to about 10.0 parts and an amount of hardener in the range of about 0.9 to about 1.05 parts. 14. Cured polymer according to claim 11, characterized by an amount of ester in the range from about 3.0 to about 9.0 Parts and an amount of hardener in the range of about 0.9 ^ is about 1.05 equivalents. 15. Cured polymer according to claim 10, characterized in that that the urethane compounds from diols from the by Polyäthylenätherdiol, Polytrxmethylenätherdiol, Polyhexamethylenätherdiol, Polypropylene ether diol and polytetramethylene ether diol formed group have been established. 16. Cured polymer according to claim 8, characterized by a content of plasticizers, which from the by dioctyl phthalate, Diisooctyl phthalate, diisodecyl phthalate and dinonyl phthalate are selected and their amounts in the Range from about 4 to about> 20 parts. 17. Cured polymer according to claim 16, characterized in that χ = 1 and y = 1. 18. Cured polymer according to claim 8, characterized by a content of about 0.3 to about 3.0 parts of a light stabilizer . 19. Cured polymer according to claim 17, characterized by a light stabilizer from the carbon black, organic 609850/0924 Dyes and inorganic dyes formed group, the light stabilizer having an average particle size of 1 micron or less. 20. Cured polymer, characterized by (on a weight basis) 100 parts of an amine curable polymer or prepolymer from the group formed by halogen-containing hydrocarbon polymers, chlorosulfonated polymers and organopolysiloxanes, about 0.0005 to about 0.05 equivalents of a curing agent based on the active groups of the amine-curable polymer or prepolymer, the curing agent consisting of the complexes of 4,4'-methylenedianiline with a salt, the salt being composed of the sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide is selected, and complexes of the racemic 2,3-di- (4-aminophenyl) -butane with a salt is selected, the salt being selected from the group formed by 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 formed group is selected and the ratio of the dianiline or the butane to the salt in the complex is about 3 mol to 1 mol, and about 1.0 to about 5.0 parts of an ester of the formula (R-CO-O) -R ^f , where R ^{f is} a polyglycol radical with a total of 2 to 5 carbon atoms or various such radicals, R is an aliphatic radical with H to 9 carbon atoms, x = 1 or 2 and y is an integer from 1 to 5. 21. Cured polymer according to claim 20, characterized by a curing agent equivalent in the range of about 0.005 to about 0.05 parts. 22. Cured polymer according to claim 20, characterized by an ester with an x value of 2 and a y value of 609850/0924 23 · Cured polymer according to claim 22, characterized by a hardener complex of 4,4'-methylenedianiline and sodium chloride. 24. Cured polymer according to claim 23, characterized by an ester of the tetraethylene glycol di (2-ethylhexoate), Tetrapropylene glycol di (2-ethylhexoate), tetrabutylene glycol di (2-ethylhexoate), Tetrapentylene glycol di (2-ethylhexoate), diethylene dipropylene glycol (2-ethylhexoate) and Propylene triethylene glycol di (2-ethylhexoate) formed group. 25. Cured polymer according to claim 24, characterized by tetraethylene glycol di (2-ethylhexoate) as a catalyst. 26. A method for producing a cured polymer according to any one of the preceding claims, characterized in that that an amine-curable polymer or prepolymer is cured in a reaction vessel and in addition in the form of stages on a weight basis 100 parts of the amine-curable polymer or prepolymer from the urethane with free isocyanate groups, Epoxy resins, polymers with acid halide and haloformate groups, polymers with anhydride groups that are involved in the reaction with diamine to form amine-acid bonds, 0.8 to 1.2 equivalents of a curing agent based on the free active Groups of the amine-curable polymer or prepolymer, the curing agent being selected from the complexes of 4,4'-methylenedianiline with a salt, the salt being selected from the sodium chloride, sodium bromide, sodium iodide, sodium nitrate, Lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium cyanide is selected, and complexes of the racemic 2,3-di- (4-aminophenyl) -butane with a salt group formed is selected, the salt from the group formed by sodium chloride, sodium bromide, sodium iodide, potassium chloride, Potassium bromide, potassium iodide, rubidium chloride, rubidium iodide, Rubidium bromide, cesium chloride, cesium bromide, and cesium iodide formed group is selected, the ratio of the dianiline or the butane to the salt and to the complex about 3 mol to 1 mole and about 1.0 to about 15.0 parts of an ester 609850/092 4 of the formula (R-CO-O) _x -R 'is added, where R' is a polyglycol radical with a total of 2 to 5 carbon atoms or various such radicals, R is an aliphatic radical with 4 to 9 carbon atoms, χ = 1 or 2 and y is one is an integer from 1 to 5. 27. The method according to claim 26, characterized by a hardener complex of 4,4'-methylenedianiline and Sodium chloride. 28. The method according to claim 26, characterized by an ester with an x value of 2 and a y value of 4. 29. The method according to claim 28, characterized by a hardener complex of 4,4'-methylenedianiline and Sodium chloride. 30. The method according to claim 29, characterized by a urethane with free isocyanate groups as the curable polymer . 31. The method according to claim 30, characterized in that the urethanes from diols from the polyethylene ether diol, Polytrimethylene ether diol, Polyhexamethylene ether diol, polypropylene ether diol and polytetramethylene ether diol formed group are produced. 32. The method according to claim 30, characterized in that the ester from the tetraethylene glycol di (2-ethylhexoate), tetrapropylene glycol di (2 riethylhexoate), tetrabutylene glycol di (2-ethyl hexoate), tetrapentylene glycol di (2-dipyl hexoate), -äthylhexoat) and propylenetriathylenglykoldi- (2-ethylhexoate) formed group is selected. 33 · The method of claim 32, characterized in that (2-ethylhexoate) as esters Tetraäthylenglykoldi- 609850/0924 used. 3 ¹ I. The method according to claim 28, characterized in that hardening is carried out at a temperature of about 90 to about 170 ^° C. 35. The method according to claim 3 ^, characterized in that that the ester is used in an amount in the range from 2.0 to about 10.0 parts and the hardener in an amount in the range from about 0.9 to about 1.05 equivalents used. 36. A method for producing a cured polymer according to any one of the preceding claims, characterized in that an amine-curable polymer or prepolymer is cured in a reaction vessel and, for this purpose, 100 parts of the amine-curable polymer or prepolymer from the in the form of stages on a weight basis group formed by halogen-containing hydrocarbon polymers, chlorosulfonated polymers and organopolysiloxanes, about 0.00005 to about 0.05 equivalents of a hardening agent based on the active groups of the amine-hardenable polymer or prepolymer, the hardening agent consisting of the complexes of 4,4 '-Methylenedianiline with a salt, the salt being selected from the group formed by sodium chloride, sodium bromide, sodium iodide, sodium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate and sodium yanide, and complexes of the raceic 2,3'-di- ( ⁱ l- aminophenyl) butane is selected with a salt formed group, the Sal z is selected from the group formed by 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, and the ratio of dianiline or butane to the salt in the complex is about 3 mol to 1 Moles, and about 1.0 to about 15.0 parts of an ester of the formula (R-CO-O) -R ^{1 is} added, where R ^{1 is} a polyglycol radical with a total of χ y including 2 to 5 carbon atoms or various such radicals, R is an aliphatic radical with 4 to 9 carbon atoms, x = 1 or 2 and y is an integer from 1 to 5 _iBt> 609850/0924 37. The method according to claim 36, characterized by an ester with an x value of 4 and a y value of 2. 38. The method according to claim 37, characterized by a curing agent complex of 4,4'-methylenedianiline and Sodium chloride. 39. A method according to claim 38, characterized in that the compounds are cured at a temperature of about 90 to about 170 ⁰ C. 40. The method according to claim 39 , characterized in that an ester is prepared from the tetraethylene glycol di (2-ethylhexoate), tetrapropylene glycol di (2-ethylhexoate), tetrabutylene glycol di (2-ethylhexoate), tetrapentylene glycol di (2-ethylhexylene) glycol (2-ethylhexoate) and propylene triethylene glycol di (2-ethylhexoate) formed group used. 41. The method according to claim 40, characterized in that that one used as ester Tetraät hy lenglykoldi- (2-ethylhexoate). 609850/0924