Hydroxy terminated polyethers are capped with toluene diisocyanate, and the amount of unreacted toluene diisocyanate substantially reduced. When cured with 4,4'-methylene-bis-(2-chloroaniline), the cured products have superior dynamic properties to the corresponding toluene diisocyanate capped polyethers with usual unreacted toluene diisocyanate content. The cured products are useful in fabricating industrial tires.
Description
BACKGROUND OF THE INVENTION This invention relates to the art of polyurethane chemistry particularly polyether polyols, toluene diisocyanate, 4,4'-methylene-bis-(2-chloroaniline) based polyurethanes, processes for their preparation and use and cured products formed therefrom. Industrial tires based on toluene diisocyanate (TDI) endcapped polyether polyols cured with 4,4'-methylene-bis-(2-chloroaniline) (MOCA) are known and in commercial use. Under heavy loads and long use, the internal structure of these tires degrades, a problem commonly attributed to internal heat buildup. It has been found surprisingly that comparable systems wherein the quantity of unreacted TDI from the endcapping reaction has been substantially reduced to below 0.45% free TDI prior to MOCA cure show longer times to internal breakdown under dynamic stress. Applicant knows of no art material to the patentability of this invention. SUMMARY OF THE INVENTION The invention provides a curable composition comprising: (a) a polyether polyol endcapped with toluene diisocyanate content of less than 0.45%; and (b) 4,4'-methylene-bis-(2-chloroaniline). The tangible embodiments of this composition aspect of the invention possess the inherent applied use characteristic of being curable to solid rubbery objects with extended dynamic stress failure times, thus evidencing their usefulness in the fabrication of solid industrial tires. The invention also provides a process for the preparation of a cast object which comprises: (a) treating of polyether polyol with an excess of a stoichiometric amount of toluene diisocyanate to prepare a toluene diisocyanate endcapped polyurethane prepolymer having an unreacted excess of toluene diisocyanate admixed therewith; (b) removing the excess unreacted toluene diisocyanate from the mixture of step (a) above to produce a toluene diisocyanate endcapped polyether polyol substantially free of toluene diisocyanate; (c) mixing the product of step (b) with a curing amount of 4,4'-methylene-bis-(2-chloroaniline); (d) placing the mixture of step (c) in a mold of the desired shape; and (e) subjecting the mold containing the mixture of step (c) prepared in step (d) to a curing temperature. The invention also provides a cured rubbery object comprising the reaction products of a toluene diisocyanate endcapped polyether polyol having a toluene diisocyanate content of less than 0.45% and 4,4'-methylene-bis-(2-chloroaniline). DESCRIPTION OF THE PREFERRED EMBODIMENT The manner of making and using the compositions of the invention will now be described with reference to a particular embodiment thereof, namely a curable composition based on a polyol polyether blend of 80% 1,000 molecular weight poly-(tetramethylene glycol) and 20% poly(oxypropylene) glycol of 1,000 molecular weight endcapped with HYLENE TM, an 80/20 blend of 2,4- and 2,6- toluene diisocyanate supplied by E. I. Du Pont de Nemours & Co. to a 6.00% NCO content which is then reduced in unreacted IDI to a total NCO content of 4.82% and unreacted isocyanate of about 0.22% (I) and 4,4'-methylene-bis-(2-chloroaniline). To prepare I, poly(tetramethylene) glycol of 1,000 molecular weight and poly(oxypropylene glycol) of 1,000 molecular weight are blended in conventional fashion and treated with toluene diisocyanate at 1.97 NCO/OH ratio in conventional fashion and at the close of the reaction priod the total NCO and unreacted NCO content determined by conventional techniques. The unreacted TDI may then be removed by conventional techniques to obtain I. Fractional distillation in a wiped film evaporator is a convenient method. I may then be blended at elevated temperature, conveniently about 100.degree. C., with MOCA in proportions known in the art, to obtain a 90 Shore A casting resin, a quantity of MOCA 90% of the amount required to theoretically combine with all the NCO content is a convenient amount. After addition of the MOCA and mixing in conventional fashion, the mixture so formed may be introduced into molds of the desired shape and subjected to elevated curing temperatures, preferably above room temperature, conveniently about 100.degree. C. until the desired degree of hardness on cooling is attained. One skilled in the art will recognize that various single polyether polyols or blends thereof may be employed as starting materials to prepare compositions of the invention comparable to I and that all starting materials are commercially available or preparable by well known techniques. The selection of a particular polyol or blend of polyols to obtain a particular range of properties or a particular cost range will be well within the level of skill of the art. Similarly, the tailoring of the ratio of isocyanate endcapping and of the proportions of MOCA curing agent will also be within the skill of the art. For example, as above, for a 90 Shore A hardness resin, the polyether polyols will have about 6.00% NCO content after TDI endcapping. Cure will be with MOCA at 90% stoichiometry after removal of unreacted TDI. Similarly, the cure time and temperature may also be varied by those skilled in the art to allow longer or shorter processing times and fine tuning of ultimate properties. When desired post cure heat conditioning may also be employed at the option of the skilled artisan. The following examples further illustrate the best mode contemplated by the inventor for the practice of his invention.
EXAMPLE 1 PREPARATION OF 90 Shore A Hardness Casting Resin A poly(tetramethylene) glycol of about 1,000 molecular weight and a poly(oxypropylene) glycol of about 1,000 molecular weight (the mixture then having equivalent weight of 500) is chain extended to about 6.00% NCO content at an NCO/OH ratio of about 1.9. To HYLENE TM (3.6 equivalents) is added a mixture of poly(tetramethylene) glycol (1.488 equivalents) and poly(oxypropylene) glycol (0.372 equivalents) is added slowly such that the temperature is kept below 55.degree. C. After addition is complete, the reaction is heated under an inert atmosphere at 80.degree. C. for two hours. Analysis for NCO Theoretical: 6.00% Found: 6.20% The reaction product is then passed through a wiped film molecular still at a jacket temperature of 150.degree. C. at a pressure of 0.5-0.8 mm Hg. to obtain a low unreacted TDI prepolymer. S.G. 1.074 (25.degree. C.). Analysis for NCO Found 4.96% Unreacted TDI (by gas phase chromatography)- 0.22% EXAMPLE 2 Preparation of 80 Shore A Hardness Casting Resin A polyoxy (tetramethylene) glycol (2,000 molecular weight)- poly(oxypropylene) glycol (2,000 molecular weight) 80%/20% blend is endcapped with TDI to 4.45% NCO at an NCO/OH ratio of 2.16. To HYLENE TM (2.16 equivalents) is added a blend of 2,000 molecular weight poly(tetramethylene) glycol (0.8 equivalents) and 2,000 molecular weight poly(oxypropylene) glycol (0.2 equivalents). The rate of addition is such that the reaction temperature is below 55.degree. C. After addition is complete, the reaction mixture is heated at 80.degree. C. under an inert atmosphere for 2 hours. Analysis for NCO Theoretical: 4.4% Found: 4.44% Unreacted TDI: 1.96% The product is then passed through a wiped film molecular still at a jacket temperature of 150.degree.-160.degree. C. and a pressure of 0.2 mm Hg. to give a prepolymer. Analysis for NCO Found: 3.20% Unreacted TDI: 0.05% EXAMPLE 3 Stress Strain Properties of Cured Sheets The prepolymer is conditioned in a metal can for 30 minutes at 100.degree. C. A desired curing amount of MOCA is melted in an aluminum weighing dish. The materials are mixed thoroughly and poured into a heated (100.degree. C.) mold and press cured 30 minutes at 100.degree. C. After demolding, the sheets are post cured 16 hours at 100.degree. C. Physical properties are determined by the following methods: ______________________________________Property ASTM Test Number______________________________________Stress-Strain D-412Shore Hardness D-2240Tear - Die C D-624Compression Set D-395 Method BBashore Rebound D-2632Compression Deflection D-575______________________________________ When tested in this fashion, 3 samples of 80 Shore A hardness resins (Example 2) with the actual NCO and free TDI (FTDI) percentages shown when cured with MOCA at 90% stoichiometry gave the following properties: ______________________________________% NCO 3.20 3.13 3.17% FTDI 0.11 0.08 0.06Tensile, psi 3225 3720 4450Elongation, % 610 630 610Shore A 83 84 78 100% Mod. 610 625 500 200% Mod. 800 800 675 300% Mod. 1000 1025 900 400% Mod. 1325 1380 1325 500% Mod. 1900 1950 2100Tear - Die C 358 361 313Bashore Rebound 53 55 54Compression Set 31 28.5 33 (22 hrs. 158.degree. F.) -- -- --Comp. Deflection -- -- -- 5% 158 175 128 10% 318 353 274 15% 412 448 385 20% 496 542 478 25% 592 647 583Pot Life, Min. (100.degree. C.) 71/2 8 71/2______________________________________ When tested in identical tests, 90 Shore A Hardness resins (Example 1) gave the following properties: ______________________________________Poly(tetramethylene)glycol, eq. % 100 90 80 70 60Poly(oxypropylene)glycol, eq. % 0 10 20 30 40NCO/OH 1.924 1.928 1.931 1.934 1.936Theo.% NCO-Undistilled 6.00 6.00 6.00 6.00 6.00Actual % NCO-Undistilled 5.99 6.07 6.15 6.19 6.13% Free 2.75 2.45 2.56 2.93 2.22% NCO - Distilled 4.97 5.00 4.96 4.99 4.97% Free TDI-Distilled 0.20 0.34 0.22 0.17 0.17Physical Properties - MOCA Cured - 90% Stoichiometry -Press Cured 30 min./212.degree. F. - Post Cured 16 hrs. 212.degree. F.Tensile 6750 4850 4260 5440 5080% Elongation 410 430 390 450 460Hardness - A/D 94/41 94/40 93.40 93.39 93.38Tensile Modulus at 100% Elong. 1610 1480 1450 1370 1340 at 200% Elong. 2150 1930 1880 1880 1770 at 300% Elong. 3180 2720 2640 2530 2400at 400% Elong. 6370 4740 -- 4220 4100Tear - Die C 477 473 456 433 409Bashore Rebound $ 47 45 42 43 39Compression Set % 26.0 29.2 30.5 34.6 34.6Compression Modulus at 5% Deflection 386 352 324 355 322 at 10% Deflection 727 665 618 671 600 at 15% Deflection 948 866 795 868 765 at 20% Deflection 1154 1050 963 1043 920 at 25% Deflection 1375 1251 1145 1238 1097Gel-Time min at 212.degree. F. 9 71/2 111/2 81/2 81/2*Evaluation of 2" .times. 6" Tire PlugsRolling resist. amps (5 min.) 4.0 3.5 3.5 4.0 4.0Time to destruction,min. 150 100 120 23 25 120 100 95 23 25______________________________________ *Industrial Research, August 1977, Prediction of Performance of Polyurethanes EXAMPLE 5 Comparison tests are performed on commercially available poly(tetramethylene) glycol based casting resins. ______________________________________Du Pont Adiprene "L" Series L-83 L-100 L-167 L-200 L-315______________________________________% Free NCO 3.2 4.2 6.3 7.5 9.45MOCA (95% theorybased on 100 g prep) 9.6 12.6 19.0 22.6 28.5Pot life at mix temp* 7.5 15 6 5 1Hardness: Shore A 83 90 95 -- -- Shore D -- 43 50 58 75Tensile, psi 4400 4500 5000 7800 11000100% Modulus, psi 700 1100 1800 300 4300300% Modulus, psi 1200 2100 3400 8300 --Elongation, % 550 450 400 315 270Tear Strength, Die C,pli 400 500 600 -- 725 Split, pli 75 75 150 135 116Resilience, Bashore, % 50 45 40 40 48Compression Set,Method "B", % 35 27 45 -- --______________________________________ *100.degree. C. Composition: L-83 not known L-100 1.67/1.0, NCO/OH ratio, 80/20 TDI/PTMEG**1000 L-167 2.0/1.0, NCO/OH ratio, 80/20 TDI/PTMEG 1000 L-200 55%/45% blend L167/L-315 L-315 2.0/1.0, NCO/OH ratio, 80/20 TDI/PTMEG 1000, 1,3 butanediol (.55/.45 eq.) blend **PTMEG = poly(tetramethylene) glycol ##STR1## ______________________________________UniroyalVibrathane Casting ResinsMOCA Cured B-600 B-601 B-602 B-614 B-615______________________________________% NCO 4.15 6.20 3.05 7.5 5.1Stoichiometry % 90 90 90 95 95Pot life, min/temp. .degree. F. 1-/212 55/160 10/212 3/160 8/180Hardness-Shore A 90 95 84 91Shore D 42 48 32 60 630Tensile, psi 5500 6500 5500 7250 6700100% Modulus, psi 1100 2100 800 3030 1500300% Modulus, psi 2200 4300 1470 6120 3300Elongation, % 430 380 490 330 410Tear Strength, pli 70 120 40 120 630 ASTM D-470 (Die C)Bashore Resilience, % 42 40 58 45 43Compression set Method B 25 30 20 30.5 30 22 hrs. 158.degree. F.______________________________________ EXAMPLE 6 Industrial tires are molded by standard techniques and tested on a tire tester as described in Industrial Research, August 1977, in an article entitled "Prediction of Performance of Polyurethane Prepolymers". The results of testing 3 samples from prepolymers prepared as in Example 1 and 3, samples prepared from a commercial tire prepolymer Uniroyal Vibrathane B-615 (a urethane casting resin with standard free TDI content based on 100% poly(tetramethylene) glycol. The results are shown. __________________________________________________________________________Evaluation of Urethane Industrial Tires (2) - 10 .times. 5 .times. 61/2in. XP9897 XP9897 XP9897 Vibra- ZL952 XL952 XL952 thane Vibrathane VibrathaneSample S2090A S2090A S2090A B-615 B-615 B-615__________________________________________________________________________% Stoichiometry 85 90 95 85 90 95Shore A Hardness 90 90 90 90 90 90Dyanamic Deflection (Inches at Stated Loads at 2 mph) 500 lbs. .028 .034 .037 .033 .038 .0471000 lbs. .067 .068 .072 .063 .067 .0771500 lbs. .096 .095 .096 .089 .099 .103Rolling Resistance (amps. at 100.degree. C.) 500 lbs. 3.5 3 3.3 3.5 3.5 42 mph 1000 lbs. 4 3.7 3.7 4 4.5 4.7 1500 lbs. 5 4.7 4.5 5 5.3 5 2000 lbs. 5.5 5.3 5.5 5.7 6.5 6.7 500 lbs. 3.5 3.5 3.3 4 4.7 4.34 mph 1000 lbs. 4 4.3 4.3 4.5 5 5 1500 lbs. 5 5 4.7 5.5 5.7 6 2000 lbs. 5.5 6 5.5 6.7 6.7 7 500 lbs. 4 4.3 4 4.3 4.5 4.56 mph 1000 lbs. 4.5 5 4.5 5.7 5 5.5 1500 lbs. 5.3 5.7 5.3 5 6 6 2000 lbs. 6.3 6.5 6 6.5 6.75 7Dynamic Destructive TestRolling Resistanceafter 15 min. 6.7 6 5.7 6 6.7 6.5after 30 min. 5.5 5.5 5.3 5.5 6 6Blow-Out time.sup.(1) (min) 662 615 660 428 335 235.sup.(3)__________________________________________________________________________ .sup.(1) Test cycle: 8 hours/5 mph/2000 lbs. 21/2 hours/5 mph/2500 lbs. ti destruction/6 mph/2500 lbs. .sup.(2) Values listed are average of two tires tested. .sup.(3) Value represents one test result. Second test blew out at 80 minutes and was discarded.
Claims
1. A curable composition comprising:
(a) a polyether polyol endcapped with toluene diisocyanate and having a free toluene diisocyanate content of less than 0.45%; and
(b) 4,4'-methylene-bis-(2-chloroaniline).
2. A curable composition as defined in claim 1 wherein the polyether polyol is based on poly(tetramethylene) glycol.
3. A curable composition as defined in claim 1 wherein the polyether polyol is based on an 80%/20% by weight mixture of poly(tetramethylene) glycol and poly(oxypropylene) glycol.
4. A curable composition as defined in claims 1, 2 or 3 wherein the toluene diisocyanate is an 80/20 ratio of the 2, 4 to 2, 6 isomers.
5. A curable composition as defined in claim 3 wherein the polyether polyol has an effective 500 equivalent weight.
6. A curable composition as defined in claim 4 wherein the polyether polyol has an effective equivalent weight of 500.
7. A process for the preparation of a cast object which comprises:
(a) treating a polyether polyol with an excess of a stoichiometric amount of toluene diisocyanate to prepare a toluene diisocyanate endcapped prepolymer having an unreacted excess of toluene diisocyanate admixed therein;
(b) removing the excess unreacted toluene diisocyanate from the mixture of step a) produce a toluene diisocyanate endcapped prepolymer substantially free of toluene diisocyanate;
(c) mixing the product of step b) with a curing amount of 4,4'-methylene-bis-(2-chloroaniline);
(d) placing the mixture of step c) in a mold of the desired shape; and
(e) treating the mold containing the mixture of step c) as prepared in step d) at a curing temperature.
8. A cured solid rubbery object comprising the reaction products of:
(a) a toluene diisocyanate endcapped polyether polyol having an unreacted toluene diisocyanate content of less than 0.45%; and
Patent Grant
4182825
