Abstract:
Hydroxy terminated polyethers are capped with toluene diisocyanate, and the amount of unreacted toluene diisocyanate substantially reduced. When cured with 4,4&#39;-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&#39;-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&#39;-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&#39;-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&#39;-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&#39;-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 &amp; 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&#39;-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° 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° 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° C. After addition is complete, the reaction is heated under an inert atmosphere at 80° 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° C. at a pressure of 0.5-0.8 mm Hg. to obtain a low unreacted TDI prepolymer. S.G. 1.074 (25° 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° C. After addition is complete, the reaction mixture is heated at 80° 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°-160° 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° 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° C.) mold and press cured 30 minutes at 100° C. After demolding, the sheets are post cured 16 hours at 100° 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° 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° 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° F. - Post Cured 16 hrs. 212° 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° F.           9     71/2    111/2                              81/2 81/2*Evaluation of 2&#34; × 6&#34; 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 &#34;L&#34; 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  --     725Split, pli          75     75      150   135   116Resilience, Bashore, %          50     45      40    40    48Compression Set,Method &#34;B&#34;, %  35     27      45   --    --______________________________________ *100° 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. ° 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° 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 &#34;Prediction of Performance of Polyurethane Prepolymers&#34;. 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 × 5 × 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° 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.