Source: http://www.google.com/patents/US4129670?dq=5,963,646
Timestamp: 2016-09-26 15:37:44
Document Index: 218686111

Matched Legal Cases: ['arts       100', 'arts       100', 'arts        24', 'arts          100', 'arts          100', 'arts          24', 'arts            100', 'arts            24', 'arts             5', 'arts          100', 'arts          100', 'arts           20', 'arts          100', 'arts          90', 'arts          12', 'arts          9', 'arts          100', 'arts          300', 'arts          24', 'arts          20', 'arts          100', 'arts          300', 'arts          24', 'arts           100', 'arts 300', 'arts           24', 'arts            100', 'arts   300', 'arts            24', 'arts              100', 'arts    500', 'arts              25', 'arts              500', 'arts              500', 'arts                100', 'arts      200']

Prior art teaches preparation of hydroxyl-terminated liquid polymers such as those described in U.S. Pat. Nos. 3,551,471 and 3,551,472, and carboxyl-terminated liquid polymers such as those described in U.S. Pat. No. 3,285,949. Such prior art polymers cure poorly with epoxy resins at room temperature and generally must be reacted at elevated temperatures in the presence of curing agents such as aliphatic or alicyclic amines. The carboxyl-terminated polymers form ester groups when they react with epoxy resins, and the reaction products are rather hydrolytically unstable. Moreover, use of larger amounts of carboxyl-terminated liquid polymers in epoxy resin compositions may require increasingly higher reaction temperatures, e.g., about 80�-180� C. when more than 50 parts carboxyl-terminated liquid polymer (Mn 2000-5000) is used per 100 parts epoxy resin (epoxy equivalent wt. 160-200). New liquid polymer compositions are desired which are room-temperature curable, castable, hydrolytically stable and which generally do not require a catalyst or curing agent.
The amine-terminated liquid polymers suitable for use in this invention have the formula ##STR1## wherein Y is a univalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two primary and/or secondary amine groups, and B is a polymeric backbone comprising carbon-carbon linkages. Generally the carbon-carbon linkages comprise at least about 90% by weight of total polymeric backbone weight, more preferably at least about 95% by weight of total polymeric backbone weight. The amine-terminated polymers contain an average from about 1.7 to about 3 primary and/or secondary amine groups per molecule, more preferably from about 1.7 to about 2.3 primary and/or secondary amine groups per molecule. The amine-terminated polymers may have Brookfield viscosities (measured using a Brookfield RVT viscometer at 27� C.) from about 500 cps to about 2,500,000 cps, more preferably from about 500 cps to about 500,000 cps.
The carboxyl-terminated liquid polymers can be esterified with an aliphatic monohydric alcohol by methods well known to the art in order to produce ester-terminated liquid polymers. For example, a carboxyl-terminated polymer and an aliphatic monohydric alcohol can be reacted in a distillation column or under reflux in the presence of a small amount of an acid catalyst. Suitable acid catalysts include organic acids containing 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as acetic acid, propionic acid, benzoic acid, monoesters and diesters of orthophosphoric acid, alkarylsulfonic acids such as p-toluene-sulfonic acid, and the like; inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like; and Lewis acids such as tetraisopropyl titanate and the like. The amount of acid catalyst used may be as little as about 0.01% up to about 5% by weight based upon total reactant weight. Suitable aliphatic monohydric alcohols for use in the esterification reaction contain from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms, and have boiling points below about 150� C., more preferably below about 100� C. Primary aliphatic monohydric alcohols are preferred. Examples of suitable aliphatic monohydric alcohols include alkanols containing from 1 to 6 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-hexanol, 3-hexanol, and the like. Other suitable aliphatic monohydric alcohols include 2-methoxyethanol, 2-ethoxyethanol and the like. Excellent results may be obtained using ethanol, 1-propanol or 1-butanol.
No catalyst is required, and many types of mixing apparatus can be used in the amine termination reaction. For example, simple mixers can be used, including turbine stirrers as well as propeller mixers. Reaction components can be combined in any order. The reaction mixture may be heated (or refluxed if a solvent is used) at a temperature from about 80� C. to about 150� C., typically for about 1 to 6 hours. The amine-terminated liquid polymer may be purified by vacuum distillation or by washing with a solvent such as a benzene-methanol mixture, followed by drying the polymer. Amine content of the amine-terminated liquid polymers can be analyzed qualitatively by infrared spectroscopy. Amine content can also be analyzed quantitatively following the procedure described by Siggia, Quantitative Organic Analysis via Functional Groups, N.Y., Wiley and Sons, Inc., 1963, pp. 452-456.
TABLE I__________________________________________________________________________Parts by Weight of     Compositional Properties3Amine-Terminated            ApproximateLiquid Polymer1 per               Approximate                       Ultimate100 Parts by Weight Tensile Elongationof Epoxy Resin2      Description               Strength, psi                       %__________________________________________________________________________About    1 -  20 Toughened Plastic               6000 -                   12000                       1 &#732;                           15About    20 -  100     Flexibilized Plastic               2500 -                   7000                       10 &#732;                           50About    100 -  250     Rigid Elastomer               2000 -                   4000                       40 &#732;                           150About    250 -  500     Elastomer 1000 -                   3000                       100 &#732;                           500About    500 -  1000     Soft Elastomer               100 -                   1000                       300 &#732;                           1000__________________________________________________________________________ 1 Amine equivalent weight per hundred parts (Ephr) of the polymer = 0.05 � 0.01. 2 Diglycidyl ether of bisphenol A epoxy resin having an epoxy equivalent weight of 175 - 200. 3 Composition contained 24 parts of bisphenol A chain extender per 100 parts by weight of epoxy resin.
Surprisingly and unexpectedly, all compositions summarized in Table I are curable at room temperature (about 20�-25� C.) with cure time increasing as the level of amine-terminated liquid polymer is decreased. The compositions are hydrolytically stable and generally do not require a catalyst or curing agent, although a catalyst or curing agent may be used.
Non-cycloaliphatic epoxy resins suitable for use in this invention together with amine-terminated liquid polymers contain at least an average of about 1.7 oxirane ##STR9## groups per molecule, more preferably from about 1.7 to about 3.0 oxirane groups per molecule, and even more preferably from about 1.7 to about 2.3 oxirane groups per molecule. The non-cycloaliphatic epoxy resins may be liquids or low-melting solids but are preferably liquids having a bulk viscosity from about 200 centipoises to about 2,000,000 centipoises (measured using a Brookfield RVT viscometer at 25� C.). The epoxy resins can have an epoxy equivalent weight (gram molecular weight per epoxy group) from about 70 to about 6,000, more preferably from about 70 to about 2,000. Suitable non-cycloaliphatic epoxy resins include epoxidized cyclic silane, epoxidized soybean oil, polyglycidyl esters of polycarboxylic acids, epoxidized polyolefins, and glycidyl ether resins, with glycidyl ether resins being preferred. Examples of suitable polyglycidyl esters of polycarboxylic acids include the diglycidyl ester of linoleic dimer acid, the triglycidyl ester of linoleic trimer acid and the like. Suitable glycidyl ether resins include polyallyl glycidyl ether; the diglycidyl ether of chlorendic diol; the diglycidyl ether of dioxanediol; the diglycidyl ether of endomethylene cyclohexanediol; epoxy novolac resins; alkanediol diglycidyl ethers; alkanetriol triglycidyl ethers; and the like.
In addition to the two essential components (an amine-terminated liquid polymer and an epoxy resin) and the two optional components (a chain extender or a curing agent) described heretofore, the composition of this invention may contain a broad range of other compounding ingredients. These ingredients are typical ingredients used in rubber and/or epoxy compounding. Standard levels of these ingredients are used, such levels being well known in the art. A preferred limitation placed on the levels of compounding ingredients is that the composition containing these ingredients should be flowable, i.e., castable at temperatures ranging from about 20� C. to about 100� C. This generally limits the amount of reinforcing fillers and other ingredients which thicken the liquid composition to low levels of up to about 50 parts by weight at room temperature based upon 100 parts by weight of the mixture of epoxy resin and amine-terminated liquid polymer. If a solvent such as kerosene or the like is used, even higher amounts of compounding ingredients can be used.
Heating the mixture up to about 100� C. may be helpful to obtain dissolution and uniform dispersion of the materials, but such heating causes the compositions to cure much more rapidly. The reaction mixture is generally castable before curing and can be centrifugally cast, roto-molded or poured into stationary trays or molds. The reaction mixture can also be used for liquid injection molding (LIM), also called reactive injection molding (RIM). The latter process is substantially more economical than conventional injection molding and is becoming well known, particularly in the automobile parts industry. The reaction mixtures cure at room temperature, with cure time being accelerated by increasing temperature, amount of curing agent (if used) and/or the amount of amine-terminated liquid polymer. With use of more than 100 parts by weight of amine-terminated liquid polymer per 100 parts by weight of non-cycloaliphatic epoxy resin, gelation of the mixture generally occurs in about 5 minutes to 3 hours. A tack-free state may be reached in about 2 to 5 hours at room temperature, while complete curing may require from 5 hours to 7 days. Use of a dihydric aromatic compound or a dimercaptan described heretofore may reduce the cure time and/or temperature, whereas a dibasic acid may increase the reaction time.
A cured composition of this invention containing up to about 500 parts by weight of amine-terminated liquid polymer per 100 parts by weight of epoxy resin can be characterized as a transparent to opaque solid having two phases, a continuous phase (matrix) and a particulate phase (domain). The size of particles making up the particulate phase may range from about 25� A. to about 5μ in diameter. The particles may vary in diameter according to a normal distribution curve or may have size ranges following a bimodal distribution curve or even a more multi-peaked distribution curve. A phase inversion point typically occurs at about 20-50 parts by weight of amine-terminated liquid polymer per 100 parts by weight of epoxy resin, depending upon the amount of chain extender and/or cross-linker used, epoxy resin molecular weight, and molecular weight and acrylonitrile content of amine-terminated liquid polymer.
A variety of methods may be used to apply a coating material described heretofore to a tire sidewall, preferably to a groove in the sidewall. The surface to be coated may be cleaned beforehand by wiping it with a solvent such as toluene or the like. Thereafter a coating may be extruded into a sidewall groove and allowed to flow by itself. Alternatively, the coating can be deposited in a sidewall groove and spread out with a squeegee-type tool. Still other methods involve brushing or spraying the coating onto the sidewall. The coating typically may have a thickness from about 1 mil to about 100 mils, more preferably from about 2 mils to about 60 or 70 mils. The coating material cures at room temperature but is preferably heated in order to hasten the cure using a heat lamp or heat gun to a temperature from about 150� F. to about 250� F. for about 30-60 minutes.
The novel vulcanizates were prepared following a general mixing procedure. All additives except a curing agent (if used) were mixed with an epoxy resin in a mixing kettle. A curing agent (if used) was mixed with an amine-terminated liquid polymer in a second mixing vessel. In each case mixing was done at about 40�-80� C. under vacuum (about 100 mmHg) in order to remove entrapped air. The two mixes were combined and stirred under vacuum at about the same temperature for about 5 minutes, and the final mixture was poured thereafter into a tensile sheet mold (or other suitable mold), or was molded centrifugally or painted as described hereinafter. Viscosity of the mixture before curing was typically less than 100,000 centipoises, and the mixture was readily castable in molds as described heretofore. The mold assembly was opened after curing and the vulcanizate removed for testing.
The amine-terminated liquid polymers used in the following examples were prepared readily by following the procedures described in detail heretofore using N-(2-aminoethyl)-piperazine in the amine-termination reaction. The amine-terminated liquid polymers identified as ATBN, were amine-terminated poly(butadiene/acrylonitrile) copolymers having a butadiene content of about 67.2% by weight of polymer, an acrylonitrile content of about 16.4% by weight of polymer unless otherwise noted hereafter, and an amine end group content of about 13.4% by weight of polymer. The ATBN polymers had a viscosity at 27� C. of about 270,000 and a molecular weight of about 3,550. The amine-terminated liquid polymers identified as ATB were amine-terminated polybutadienes having a viscosity at 27� C. of about 240,000 and a molecular weight of about 4200.
The non-cycloaliphatic epoxy resin most frequently used was a liquid diglycidyl ether of bisphenol A (DGEBA) having an epoxy equivalent weight of about 185 to 192 and a viscosity at 25� C. of about 10,000 to 16,000 cps. The DGEBA resin is sold under the trademark "Epon 828" by Shell Chemical Company. Another non-cycloaliphatic epoxy resin used was the triglycidyl ether of glycerol having an epoxy equivalent weight of about 140 to 160 and a viscosity at 25� C. of about 100-170, this resin being sold under the trademark "Epon 812" by Shell Chemical Company. Yet another non-cycloaliphatic epoxy resin used was 1,4-butanediol diglycidyl ether having an epoxy equivalent weight of about 136 and a viscosity at 25� C. of about 19 cps. The latter material is sold under the trademark "Araldite RD-2" by Ciba Products Co.
Physical testing of the compositions of this invention was performed according to the following procedures. Modulus, tensile strength and ultimate elongation of elastomeric materials were determined according to ASTM D412 using oval samples having a 4-inch mean perimeter except where noted; in the latter cases Die C dumbbells were used. Gehman freeze point was tested according to ASTM D1053. Compression set was measured according to ASTM D395B at 100� C. for 70 hours. Tear resistance was tested according to ASTM D624 using Die C. Pico abrasion resistance was measured according to ASTM D2228 using a 5.5 kg weight, a 60 rpm speed and 80 revolutions. Abrasion index was calculated according to Sec. 11.3 of the latter procedure. Durometer hardness was measured according to ASTM D676 using a Shore Type A durometer and a one-second indentation hardness time interval. Fracture surface energy was tested following the procedure cited in Riew etal, Rubber Toughened Thermosets, Symposium on Toughness and Brittleness of Plastics Chemistry, 168th A.C.S. National Meeting, Atlantic City, N.J., September 12, 1974. Gardner impact was measured using a Gardner impact tester and a dart having a 0.5-inch tip radius. Heat distortion temperature was tested according to ASTM D648. Tensile strength and elastic modulus of plastic materials in Table IV were tested according to ASTM D638.
Examples 1-18 demonstrate production of elastomeric compositions using a non-cycloaliphatic epoxy resin; an amine-terminated liquid polymer; optionally, isopropylidene bisphenol chain extender, and optionally, dioctyl phthalate plasticizer. Examples 1-12 demonstrate elastomeric compositions both with and without an isopropylidene bisphenol chain extender. Examples 11 and 12 illustrate the plasticizing effect of dioctyl phthalate together with use of isopropylidene bisphenol. Test results for examples 1-12 are set forth in Tabl II. Test samples for Examples 13-18 were molded centrifugally at about 500-1,000 rpm. Test samples were cured by spinning for about 50 min. at about 90� C. and thereafter placed in an oven for about 120 min. at about 120� C. Test results for Examples 13-18 are set forth in Table III.
TABLE II__________________________________________________________________________   Example  1   2   3    4    5    6   7   8   9   10  11* 12*__________________________________________________________________________ RecipeEpon 828, Wt. Parts       100 100 100  100  100  100 100 100 100 100 100 100ATBN, Wt. Parts       100 150 200  250  275  300 300 325 350 400 150 150Bisphenol, A, Wt. Parts        24  24  24   24   24   24 --   24  24  24  24  24Dioctyl Phthalate,Wt. Parts   --  --  --   --   --   --  --  --  --  --   10  20 Test DataCure Cycle, � C/Hrs.       120/21           120/21               120/19                    120/18                         120/21                              120/21                                  120/22                                      120/19                                          120/17                                              120/18                                                  120/16                                                      120/16100% Modulus, psi**       --  --  --   982  845  706 --  586 567 406 2086                                                      1784Tensile strength, psi**       2659           2023               1618 1283 1134 1044                                  695 963 941 802 2197                                                      1856Ultimate Elongation,%**       43  72  98   146  154  181 94  210 204 263 110 106Gehman Freeze Pt., � C       -72 -71 -63  -54  -55  -48 -49.5                                      -52 -57 -54.5                                                  --  --Compression Set, %       63.7           54.1               70.9 68.0 62.3 61.5                                  80.2                                      69.0                                          68.6                                              46.7                                                  61.1                                                      85.2Tear Resistance, lbs/in.       215 223 215  181  168  154.2                                  76  157 157.4                                              132 334.3                                                      295.8Pico Abrasion Index       31  34  40   28   27   26  --  --  19  --  23  21Durometer Hardness, Type A     98  97  97   91   90   87  73  83  83  81  --  --__________________________________________________________________________ *Tested using Die C dumbell samples **Tested at 25� C
TABLE III__________________________________________________________________________   Example     13*             14*                15*                   16* 17*                          18*__________________________________________________________________________ RecipeEpon 828, Wt. Parts          100             100                100                   100 100                          100ATBN, Wt. Parts          100             150                300                   450 450                          500Bisphenol A, Wt. Parts          24 24 24 24  24 24 Test Data100% Modulus, psi**          -- -- -- 194 218                          186100% Modulus, psi***          -- -- -- 52  59 48200% Modulus, psi**          -- -- -- 274 344                          251200% Modulus, psi***          -- -- -- 81  97 --Tensile Strength, psi**          2878             2260                1349                   459 486                          306Tensile Strength, psi***          707             553                273                   113 104                          69Ultimate Elongation, %**          9  95 170                   317 260                          240Ultimate Elongation, %***          100             113                130                   --  -- 165Gehman Freeze Point, � C          -- -80                -54                   -52.5                       -50                          -50.5Compression, Set,%          75.4             73 31.7                   84  68.3                          --Tear Resistance, lbs/In.          366             332                175                   120 128                          93Pico Abrasion Index          28 33 25 22  23 Cut ThroughDurometer Hardness, Type A          95 95 85 72  72 66__________________________________________________________________________ *Tested using Die C dumbbell samples **Tested at 25� C ***Tested at 80� C
Examples 21-24 demonstrate production of toughened compositions using a non-cycloaliphatic epoxy resin; an amine-terminated liquid polymer; an isopropylidene bisphenol (bisphenol A) chain extender; and a piperidine curing agent. Example 19 is a control experiment in which no amine-terminated liquid polymer was used. Example 20 is a comparison experiment using a carboxyl-terminated liquid polymer. The carboxyl-terminated polymer, identified as CTBN, is a carboxyl-terminated poly(butadiene/acrylonitrile) liquid polymer having an acrylonitrile content of about 17.5% by weight of polymer, a carboxyl content of about 2.3% by weight of polymer, a Brookfield viscosity at 27� C. of about 120,000 cps and a molecular weight of about 3,300. Compositions in examples 21-24 demonstrate toughness about the same as a composition containing a carboxyl-terminated liquid polymer in place of an amine-terminated liquid polymer (Example 20). Examples 21-24 also demonstrate that compositional toughness is increased substantially in comparison to Example 19, where no such liquid polymer was used. Thus the amine-terminated liquid polymers of this invention are shown to be effective tougheners of the non-cycloaliphatic epoxy resin compositions. Test results are set forth in Table IV.
TABLE IV__________________________________________________________________________   Example       19 20  21  22  23  24__________________________________________________________________________ RecipeEpon 828, Wt. Parts            100               100 100 100 100 100ATBN, Wt. Parts  -- --  2.5  5  7.5 10CTBN, Wt. Parts  --  5  --  --  --  --Bisphenol A, Wt. Parts            24 24  24  24  24  24Piperidine, Wt. Parts             5  5   5   5   5   5 Test DataElastic Modulus, kpsi            390               376 394 376 397 376Tensile Strength, psi            8900               9600                   9300                       8700                           9300                               8000Ultimate Elongation, %            4.0               8.8 4.8 5.4 4.5 4.9Fracture Energy in-lbs/in2            1  49  12  35  68  52Gardner Impact, in-lbs*            50 &gt;320                   &gt;320                       &gt;320                           &gt;320Heat Distortion Temperature, � C            82 82  88  82  82  82__________________________________________________________________________ *Specimen thickness is 1/4
TABLE V__________________________________________________________________________   Example     25  26  27  28  29  30  31  32  33__________________________________________________________________________ RecipeEpon 828, Wt. Parts          100 100 100 100 100 100 100 100 100ATBN, Wt. Parts          100 150 200 250 275 300 325 350 400Azelaic Acid, Wt. Parts           20  20  20  20  20  20  20  20  20 Test DataCure Cycle, � C/Hrs.          120/17              120/19                  120/20                      120/21                          120/21                              120/17                                  120/18                                      120/20                                          120/18100% Modulus, psi*          --  --  902 --  381 280 235 274 190Tensile Strength, psi*          1849              1131                  974 577 654 538 447 501 413Ultimate Elongation, %*          37  69  110 146 172 190 194 192 238Gehman Freeze Pt., � C          -71 -63 -56 -54.5                          -54.5                              -52.5                                  -52.5                                      -52.5                                          -53Compression Set, %          59.5              53.8                  58.1                      57.7                          59.0                              62.4                                  61.6                                      57.1                                          53.6Tear Resistance, lbs/in.          308.8              106.2                  73.9                      97.2                          98.2                              84.7                                  84.6                                      97.1                                          80.5Pico Abrasion Index          17  **  **  **  **  **  **  **  **Durometer Hardness, Type A          98  91  91  83  78  73  72  70  65__________________________________________________________________________ *Tested at 25� C **Cut through sample
TABLE VI__________________________________________________________________________   Example     34  35  36  37  38  39  40  41  42__________________________________________________________________________ RecipeEpon 828, Wt. Parts          100 100 100 100 100 100 100 100 100ATBN, Wt. Parts          90  100 100 250 300 400 100 200 300Bisphenol, A, Wt. Parts          12.7              12  12  12  12  12  24  24  24Azelaic Acid, Wt. Parts          9.6 10  9.8 10  10  10  20  20  20 Test DataCure Cycle, � C/Hrs.          120/16              120/16                  120/16                      120/16                          120/16                              120/16                                  120/16                                      120/16                                          120/16100% Modulus, psi*          --  --  1067                      285 300 145 --  500 266200% Modulus, psi*          --  --  --  --  566 220 --  617 356Tensile Strength, psi*          2793              2443                  1227                      505 585 404 2462                                      924 590Ultimate Elongation, %*          9   31  122 198 204 318 6   340 376Gehman Freeze Pt., � C          **  **  -55 -50.5                          -55 -53.5                                  **  -62 -52Compression Set, %          *** *** 57.1                      62.3                          52.5                              55.3                                  48.8                                      91.5                                          87.9Tear Resistance, lbs/in.          61.2              63.7                  190 111.4                          123.5                              75.4                                  486.2                                      231.3                                          176.8Pico Abrasion Index          64  58  72  ****                          ****                              ****                                  34  21  ****Durometer Hardness, Type A          99  99  93  86  80  65  98  85  86__________________________________________________________________________ *Tested at 25� C **Too stiff for measurement ***Sample was too brittle for testing ****Cut through sample
TABLE VII__________________________________________________________________________   Example     43  44  45  46  47__________________________________________________________________________ RecipeEpon 828, Wt. Parts          100 100 100 100 100ATBN, Wt. Parts          300 300 300 300 300Bisphenol A, Wt. Parts          24  24  24  24  241,4-Dibromobutane, Wt. Parts          20  15  10  5   0 Test DataCure Cycle, � C/Hrs.          120/16              120/16                  120/16                      120/16                          120/16100% Modulus, psi*          1110              1373                  --  790 924Tensile Strength, psi*          1252              1481                  1377                      1054                          1249Ultimate Elongation, %*          120 111 77  148 153Gehman Freeze Pt., � C          -49 -62 -62 -60 -60Compression Set, %          37  45  27  28  52Tear Resistance, lbs/in.          215 278 244 162 183Pico Abrasion Index          25  25  22  16  21Durometer Hardness, Type A          93  79  97  96  78__________________________________________________________________________ *Tested at 25� C
TABLE VIII__________________________________________________________________________EXAMPLES 48 - 57   Example     48*  49*  50*                       51* 52*__________________________________________________________________________ RecipeEpon 828, Wt. Parts          100  100  100                       100 100ATBN, Wt. Parts          300  300  300                       300 300Bisphenol A, Wt. Parts          24   24   24 24  24 Test DataWt. % Acrylonitrile in ATBN          0    10   10 10  17Cure Cycle, � C/Hrs          120/16.5               120/14.5                    ** 120/17                           120/15100% Modulus, psi***          897  789  454                       566 700100% Modulus, psi****          --   195  127                       153 155200% Modulus, psi***          1348 1191 673                       836 1117200% Modulus, psi****          --   --   -- --  252Tensile Strength, psi***          1680 1627 1229                       1125                           1844Tensile Strength, psi****          --   288  179                       239 282Ultimate Elongation, %***          249  271  365                       284 300Ultimate Elongation, %****          --   177  190                       197 220Gehman Freeze Pt., � C          -80  -76  -69                       -74 -58Compression Set, %          28.6 26.9 39.1                       --  28.8Tear Resistance, lbs/in.          190.9               199.4                    165.8                       191 211.9Pico Abrasion Index          26   29   22 29  24Durometer Hardness, Type A          92   91   81 90  90   Example      53* 54*  55* 56* 57*__________________________________________________________________________ RecipeEpon 828, Wt. Parts           100 100  100 100 100ATBN, Wt. Parts 300 300  300 300 300Bisphenol A, Wt. Parts           24  24   24  24  24 Test DataWt. % Acrylonitrile in ATBN           17  17.9 17.9                        18.2                            26.5Cure Cycle, � C/Hrs           **  120/18                    **  **  **100% Modulus, psi***           415 805  1020                        786 612100% Modulus, psi****           121 195  211 186 77200% Modulus, psi***           656 1272 --  1488                            957200% Modulus, psi****           193 --   --  --  126Tensile Strength, psi***           1281               1485 1512                        1463                            1521Tensile Strength, psi****           240 261  301 225 165Ultimate Elongation, %***           338 230  190 198 301Ultimate Elongation, %****           250 150  160 117 257Gehman Freeze Pt., � C           -54 -61  -59 -60 -45Compression Set, %           35.2               42.8 59.7                        23.5                            64.9Tear Resistance, lbs/in.           134.7               190.2                    209.0                        169.8                            205.4Pico Abrasion Index           24  21   23  *****                            19Duromater Hardness, Type A           80  92   94  89  90__________________________________________________________________________ *Tested using Die C dumbbell samples **Two-stage cure cycle in which the sample was cured first for 2 hours at 120� C and thereafter for 2 hours at 150� ***Tested at 25� C ****Tested at 80� C *****Cut through sample
TABLE IX______________________________________   Example       58*       59*     60*  61*______________________________________ RecipeEpon 828, Wt. Parts            100       100     100  100ATB, Wt. Parts   300       270     240  210Bisphenol A, Wt. Parts            24        24      24   24Diamine          --        30      60   90 Test DataCure Cycle, � C/Hrs.            120/16.5  **      **   **100% Modulus, psi***            897       793     761  310200% Modulus, psi***            1348      --      --   --Tensile Strength, psi***            1680      1239    1093 1176Ultimate Elongation, %***            249       188     143  351Gehman Freeze Pt. � C            -80       -84     -87  -16Compression Set, %            28.6      22.5    30.7 70.0Tear Resistance, lbs/in.            190.9     198.6   126.7                                   123.1Pico Abrasion Index            26        ****    **** ****Durometer Hardness, Type A            92        94      93   86______________________________________ *Tested using Die C dumbbell samples **Two-stage cure cycle in which the sample was cured first for 2 hours at 120� C and thereafter for 2 hours at 150� ***Tested at 25� C ****Cut through sample
Examples 62-64 demonstrate the utility of compositions of this invention in white tire sidewall paints having good to excellent flex crack resistance. Each sample was prepared by painting the convex side of a 1 in. � 6 in. � 1/4 in. strip of cured rubber tire sidewall composition, followed by curing the painted strip for 15 minutes in a circulating air oven at 180� F. All paints cured during that time to tough, glossy, tack-free rubbers. Flex crack resistance was measured using a Demattia flexometer according to ASTM D-430. Flex resistance was tested both after the initial cure and after further aging for 5 days at 180� F. Adhesion was found to be excellent even though the sidewall had not been buffed before painting. Test results are reported in Table X.
TABLE X______________________________________    Example        62      63      64______________________________________  RecipeEpon 812, Wt. Parts              100     100     100ATBN, Wt. Parts    500     625     833Bisphenol A, Wt. Parts              25      25      25Titanium Dioxide, Wt. Parts              500     625     833Kerosene, Wt. Parts              500     625     833 Test Data100% Flex Failure of 3 SamplesAfter Initial Cure, Cycles (1)              10,000  10,000  1,500,000*(2)                13,000  15,000  1,400,000*(3)                1,000   20,000  1,500,000*100% Flex Failure of 3 SamplesAfter Further 5 Day Cure at180� F (19  15,000  17,000  60,000   (2)             24,000  35,000  60,000   (3)             30,000  385,000 1,500,000*______________________________________ *Test was stopped at this point even though no flex failure had occurred
Examples 65-66 demonstrate production of elastomeric compositions of this invention by curing a mixture of an amine-terminated liquid polymer and 1,4-butanediol diglycidyl ether, the latter having an epoxy equivalent weight of about 136 and a viscosity at 25� C. of about 19 cps. The latter material is sold under the trademark "Araldite RD-2" by Ciba Products Company. Test data is summarized in Table XI.
TABLE XI______________________________________   Example           65*       66*______________________________________ RecipeAraldite Rd-2, Wt. Parts                100       100ATBN, Wt. Parts      200       300 Test DataCure Cycle, � C/Hrs.                120/21    120/19100% Modulus at 25� C, psi                --        --100% Modulus at 80� C, psi                --        --Tensile Strength at 25� C, psi                225       284Tensile Strength at 80� C, psi                166       171Ultimate Elongation at 25� C, %                60        116Ultimate Elongation at 80� C, %                37        50Gehman Freeze Pt., � C                -39       -48.5Compression Set, %   39.4      30.9Tear Resistance, lbs/in.                37        31Pico Abrasion Index  **        **Durometer Hardness, Type A                64        58______________________________________ *Tested using Die C dumbbell samples **Cut through sample