Abstract:
A class of Mannich condensates containing phosphorus prepared by reacting a phenol with formaldehyde and a primay amine, and then reacting the product with formaldehyde and a dialkyl phosphite. Useful applications include use as a fire retardant additive in polyurethane foams.

Description:
FIELD OF THE INVENTION 
     This invention pertains to the introduction of phosphorus into aromatic amino polyols by the Mannich reaction and its use as a fire retardant additive in polyurethane foams. 
     DESCRIPTION OF THE RELATED ART 
     The Mannich reaction involves the reaction of an acidic hydrogen with formaldehyde and an amino base. U.S. Pat. No. 4,310,592 to Schmitz illustrates the manner in which the Mannich reaction can be used to prepare useful products. The patent teaches that when an aliphatic amine and formaldehyde are reacted with phenol, the reaction yields predominantly an ortho substituted Mannich base. According to the patent, the reaction proceeds by the following general equation: ##STR1## wherein R is an alkyl radical containing from about 12 to 22 carbon atoms. 
     U.S. Pat. No. 3,076,010 discloses that when instead of a phenol, a dialkyl phosphite is reacted with an aldehyde or ketone and a dialkanolamine, a compound is formed which may be represented by the formula: ##STR2## in which R and R&#39; may be the same or different alkyl or haloalkyl radicals, R 2  and R 3  may be the same or different lower alkylene radicals and R 4  is hydrogen or an alkyl radical. U.S. Pat. No. 3,076,010 instructs that these compounds may be made according to the general reaction: ##STR3## wherein R, R&#39;, R 2 , R 3  and R 4  are defined as above. 
     U.S. Pat. No. 4,052,487 represents an improvement on the teachings of U.S. Pat. No. 3,076,010 by disclosing the development of a diol phosphonate having the general formula: ##STR4## in which R is an alkyl group with 1 to 4 carbon atoms, R 2  is hydrogen, a methyl or an ethyl group, and R&#39; is --CH 2  --CH 2  --CH 2  -- or ##STR5## This diol-phosphonate was found useful as a flame-proofing additive in polyurethane foams. 
     The invention disclosed herein combines elements of the two reactions disclosed in U.S. Pat. Nos. 4,310,592 and 3,076,010 to produce a new class of Mannich condensates. 
     SUMMARY OF THE INVENTION 
     The invention is a compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR6## in which R is hydrogen, an alkyl, alkanol or polyoxyalkylene group, and R&#39; is an alkyl group. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The Mannich reaction involves the reaction of an acidic hydrogen with formaldehyde and an amino base. The phosphorus-hydrogen bond is acidic in dialkyl phosphites and will undergo the Mannich reaction with an N--H bond in the presence of formaldehyde. When phosphorus is introduced into aromatic amino polyols by the Mannich reaction, the resulting products have a variety of uses; for example, fire retardants for rigid urethane foams and epoxy plastics, lubricating additives, gasoline wear-inhibiting additives, corrosion inhibitors and surfactants, and may also be propoxylated to other useful polyols for urethanes. 
     These compounds may be prepared by a Mannich reaction between a phenol, formaldehyde, a primary amine and a dialkyl phosphite as illustrated by the following reaction sequence: ##STR7## in which R is hydrogen, an alkyl, alkanol or polyoxyalkylene group, and R&#39; is an alkyl group. It is preferred that R is an alkanol group. Especially preferred is --CH 2  --CH 2  OH. A preferred compound may be represented by the following structure: ##STR8## Some useful phenols include phenol, nonylphenol, isopropylphenol, cresol, dodecylphenol or Bisphenol A. It is preferred that the phosphite used be dimethyl phosphite or diethyl phosphite. 
     The conditions within which this invention is useful include a temperature range of 15° to 150° C. and a pressure range of 1 to 200 atmospheres. It is preferred that the reaction be run at a pressure of 1 atmosphere. 
    
    
     Though the products of this invention have a number of applications, of particular interest is their application as fire retarding agents for plastics. Those products which contain several hydroxy groups are especially suitable as fire retardants for urethane foams. This invention and its application as a fire retardant for urethane foams will be further illustrated by the following non-limiting examples. 
     EXAMPLE 1 
     To a 1 liter, three-necked flask equipped with a stirrer, thermometer and dropping funnel were added 220 g of nonylphenol (1.0 moles) and 61 g of monoethanolamine. The mixture was cooled to 15° C. and 81.1 g of formalin (1.0 moles) were added slowly while keeping the temperature at 15°-20° C. After all the formalin was added, the mixture was stirred for 30 minutes and then heated to 90° C. and held at this temperature under about 20 mm pressure for two hours. The product weighed 291.5 g and analysis indicated 50% of ortho hydrogens on nonylphenol underwent the Mannich reaction. 
     To 100 g of the product described above was added 47.13 g of diethyl phosphite (0.341 moles). Then 27.65 g of formalin (0.341 moles) was added and the temperature allowed to rise to 55° C. The contents were heated to 90° C. and held at 90°-108° C. for five hours at full water aspirator reduced pressure while removing water. The final product weighed 142.2 g and was a thick, light brown liquid. It had a hydroxyl number of 78 and a total amine content of 1.85 meq/g. 
     The procedure described above illustrates in general the technique used in this work. Specific examples are described in Tables I and II using nonylphenol, phenol and Bisphenol A. A wide variety of amines were used. Diethyl phosphite was used in all runs shown except 11 of Table I in which dimethyl phosphite was used. 
     
                                           TABLE I__________________________________________________________________________REACTIONS OF DIETHYL PHOSPHITE, AMINES,FORMALDEHYDE AND NONYLPHENOLNonyl-               Analysis Reaction                                 Reaction   phenol,  Amines,        CH.sub.2 O,            DEP,                Total                    Hydroxyl                         Stage #1                                 Stage #2Ex.   Moles  Moles Moles            Moles                Amine                    Number                         Hrs-Temp., °C.                                 Hrs-Temp., °C.__________________________________________________________________________1  0.34  MEA   0.34            0.34                1.85                    78   2   110 5   100  0.342  0.52  DGA   0.50            0.5 1.81                    236  1   110 4   110  0.53  0.14  M-600 0.28            0.28                1.12                    57   --  --  3   100  0.284  0.07  M-1000        0.13            0.13                0.56                    23   --  --  3   110  0.135  0.17  M-300 0.33            0.33                1.62                    34   3   110 3   110  0.336  0.25  D-400 0.50            0.50                2.49                    150  4   110 4   110  0.57  0.25  D-400 0.50            0.50                2.14                    119  4   110 4   110  0.58  0.25  ED-600        0.50            0.50                2.01                    123  8   110 4   110  0.59  0.07  T.sub.3 EDMA        0.13            0.13                2.30                    207  3   110 4   110  0.1310 0.1 T.sub.4 EGMA        0.20            0.20                5.22                    192  3   110 3   110  0.2011 0.14  M-600 0.28            DMP 1.05                    61   2   110 2   110  0.28      0.2812 0.5 DGA   0.93            0.93                2.50                    200  3   110 3   110  1.013 0.5 MEA   0.92            0.92                2.23                    169  3   110 3   110  1.014 0.5 M-360 0.97            0.97                1.36                    80   3   110 3   110  1.0__________________________________________________________________________ Monoethanolamine (MEA) = NH.sub.2 CH.sub.2 CH.sub.2 OH DIGLYCOLAMINE ® Agent = NH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH ##STR9## ##STR10## ##STR11## ##STR12## ##STR13## T.sub.3 EGMA = NH.sub.2(CH.sub.2 CH.sub.2 O).sub.3 H T.sub.4 EGMA = NH.sub.2(CH.sub.2 CH.sub.2 O).sub.4 H ##STR14## All amines obtained from Texaco Chemical Company. 
    
     
                                           TABLE II__________________________________________________________________________REACTIONS OF DIETHYL PHOSPHITE, AMINES,FORMALDEHYDE AND PHENOL                         Reaction                               Reaction                Analysis Stage #1                               Stage #2   Phenol,   Amines,        CH.sub.2 O,            DEP,                Total                    Hydroxyl                         Hrs-Temp.,                               Hrs-Temp.,Ex.   Moles   Moles        Moles            Moles                Amine                    Number                         °C.                               °C.__________________________________________________________________________1  1.0  M-300        0.33            0.33                1.86                    105  3  110                               5  110   0.332  0.5  M-300        1.0 1.0 2.0 128  3  110                               5  110   1.03  0.5  M-1000        0.5 0.5 0.75                     48  4  110                               5  110   0.54  0.5  M-600        1.0 1.0 1.18                     83  4  110                               4  110   1.05  1.0  M-600        1.0 1.0 1.17                     83  3  110                               4  110   1.06  0.25 M-1000        0.5 0.5 0.71                     36  9  110                               6  110   0.57  0.25 ED-600        0.5 0.5 2.13                    132  8  110                               5  110   0.58  0.5  MEA  1.5 1.5 3.15                    176  3  110                               3  110   1.59  0.25 D-400        0.46            0.46                2.78                    171  3  110                               4  110   0.5__________________________________________________________________________ 
    
     
                                           TABLE III__________________________________________________________________________REACTIONS OF DIETHYL PHOSPHITE, AMINES,FORMALDEHYDE AND BISPHENOL A                          Reaction                                Reaction                 Analysis Stage #1                                Stage #2   BPA,  Amines,         CH.sub.2 O,             DEP,                 Total                     Hydroxyl                          Hrs-Temp.,                                Hrs-Temp.,Ex.   Moles  Moles  Moles             Moles                 Amine                     Number                          °C.                                °C.__________________________________________________________________________1  0.16  M-300  0.33             0.33                 1.85                     30   3  110                                3  110  0.332  0.17  M-600  0.33             0.33                 1.14                     80   3  110                                3  110  0.333  0.25  ED-600 0.5 0.5 --  --   5  110                                Polymer  0.54  0.03  M-1000 0.06             0.06                 --  --   3  110                                Liquid 50° C.  0.03  M-300 (0.03)__________________________________________________________________________ 
    
     EXAMPLE 2 
     Several of the products prepared in this invention were tested in rigid polyurethane and polyurethane-isocyanurate foam formulations. The foams were prepared by standard one-shot, free-rise techniques. Formulation components were mixed at 2700 rpm and poured into an 8&#34;×8&#34;×12&#34; (600 g pour) open mold and allowed to rise. The resulting foams were allowed to stand at ambient conditions for at least three days before determination of physical properties. 
     It was found that the use of the products of this invention adds fire retardant properties to the foams, improves both insulation values (K-factor) and compression strength, and results in higher heat distortion temperatures. The improvement of foam physical properties also occurs in isocyanurate foams, and, in addition, the friability of the foams is improved. It was found that foams made using DIGLYCOLAMINE® (DGA) agent were easiest to work with and were conveniently prepared. 
     Formulations, reaction profiles and foam physical properties are detailed in the following table for various comparative and inventive examples. 
     
         __________________________________________________________________________EXPERIMENTAL FIRE RETARDANT EVALUATIONS__________________________________________________________________________                                             Nonylphenol/                                Nonylphenol/MEA Based                                             DGA Based                                (See Table I)                                             (See Table I)             Comparative Examples                                Ex. Ex.  Ex. Ex.                                                Ex.Fire Retardant    --  AB-80.sup.1                     -- AB-80                            AB-80                                1   13   13  2  2__________________________________________________________________________Formulation, pbwTHANOL ® R-350-X.sup.2 (OH = 526)             37.3                 35.1                     24.6                        23.2                            --  34.7                                    34.3 22.7                                             34.0                                                22.5TERATE ® 203.sup.3 (OH = 309)             --  --  16.4                        15.4                            --  --  --   15.0                                             -- 14.9R-440.sup.4 (OH = 258)             --  --  -- --  --  --  --   --  -- --R-440.sup.4 (OH = 252)             --  --  -- --  28.9                                --  --   --Fire Retardant    --  5.0 -- 5.0 5.0 5.0 4.9  4.9 4.8                                                4.8DC-193.sup.5      0.5 0.5 0.5                        0.5 0.5 0.5 0.5  0.5 0.5                                                0.5R-11A.sup.6       13.0                 13.0                     13.0                        13.0                            12.0                                13.0                                    13.0 13.0                                             13.0                                                13.0Water             --  --  0.3                        0.3 --  --  --   0.3 -- 0.3FOMREZ ® UL-32.sup.7             --  --  0.01                        0.01                            --  --  --   0.01                                             -- 0.01T-45.sup.8        --  --  -- --  1.5 --  --   --  -- --MONDUR ® MR.sup.9             49.2                 46.4                     45.2                        42.6                            52.1                                --  --   --PAPI ® 27.sup.10             --  --  -- --  --  46.8                                    47.3 43.6                                             47.7                                                44.0Index             1.05                 1.05                     1.05                        1.05                            3.0 1.05                                    1.05 1.05                                             1.05                                                1.05Reaction ProfileTimes (sec), mixing             15  15  12 12  3   15  15   12  15 12Times (sec), cream             25  24  17 20  8   28  28   21  25 21Times (sec), gel  78  86  52 70  21  99  98   71  92 73Times (sec), tack free             106 110 81 94  32  117 124  113 108                                                102Times (sec), rise 187 186 139                        153 64  199 210  180 251                                                198Initial Surface Fri-             None                 None                     Yes                        None                            Yes None                                    None Yes None                                                NoneabilityFoam appearance   Good                 Good                     Fair                        Good                            Good                                Good                                    Good Good                                             Good                                                GoodPhysical PropertiesDensity, pcf      1.96                 1.99                     1.65                        1.72                            1.86                                1.85                                    1.92 1.63                                             1.97                                                1.68K-factor          0.118                 0.119                     0.112                        0.128                            0.117                                0.111                                    0.115                                         0.112                                             0.111                                                0.112Compressive strength,psi, with rise    47.57                 41.92                     40.81                        38.31                            38.41                                46.89                                    48.61                                         37.39                                             41.79                                                31.66against rise      16.58                 14.90                     10.54                        10.51                            11.05                                15.82                                    14.89                                         10.15                                             12.52                                                7.36Heat distortion, °C.             158 144 136                        115 191 137 142  131 154                                                136Closed cells, %   92.25                 91.51                     92.55                        91.43                            91.30                                91.10                                    93.07                                         92.21                                             92.59                                                92.94Friability, % wt. 6.63                 5.88                     2.07                        2.43                            24.90                                5.64                                    7.62 4.93                                             6.27                                                3.73loss, 10 minASTM 1692 Burn,   2.57                 1.64                     2.27                        1.82                            1.19                                3.07                                    2.06 2.86                                             1.86                                                1.76in/min (BHA)Butler Chimney TestFlame height, in. &gt;11 &gt;11 &gt;11                        &gt;11 4.33                                &gt;11 &gt;11  &gt;11 &gt;11                                                &gt;11Sec. to extinguish             26  20  25 14  12.33                                24  19   17  23 16% wt. retained    20.1                 64.3                     31.4                        68.7                            93.2                                36.2                                    52.0 54.7                                             43.3                                                58.0Dimensional Stability158° F., 100% R-H1 weekΔV     +2.7                 +8.4                     +2.9                        +16.5                            +5.3                                +2.9                                    +3.2 +4.1                                             +4.3                                                +4.1ΔW     -0.3                 -0.7                     -0.6                        -1.0                            -1.9                                +0.3                                    +0.2 +0.1                                             -0.4                                                -0.6ΔL     +1.8                 +5.4                     +2.2                        +11.9                            +3.4                                +2.5                                    +2.2 +3.3                                             +2.5                                                +2.44 weeksΔV     +5.4                 +16.8                     +7.7                        +42.5                            +9.8                                +5.4                                    +6.1 +7.7                                             +8.4                                                +10.3ΔW     -0.3                 -1.2                     -0.6                        -2.8                            -3.1                                +0.4                                    +0.2 0.0 0.0                                                -0.1ΔL     +3.4                 +9.9                     +5.1                        +23.0                            +5.9                                +4.6                                    +4.0 +5.7                                             +5.0                                                +5.9__________________________________________________________________________             Nonylphenol/DGA                         Nonylphenol/M-300 Based                                       Bispenol A/M-300 Based             Based (See Table I)                         (See Table I) (See Table II)             Ex. Ex. Ex  Ex.  Ex.  Ex. Ex. Ex.  Ex.Fire Retardant    12  12  12  5    5    5   1   1    1__________________________________________________________________________Formulation, pbwTHANOL ® R-350-X.sup.2 (OH = 526)             34.1                 22.5                     --  34.9 23.1 --  35.0                                           23.1 --TERATE ® 203.sup.3 (OH = 309)             --  15.0                     --  --   15.3 --  --  15.3 --R-440.sup.4 (OH = 258)             --  --  26.4                         --   --   28.2                                       --  --   28.3R-440.sup.4 (OH = 252)Fire Retardant    4.9 4.9 4.6 5.0  5.0  4.9 5.0 5.0  4.9DC-193.sup.5      0.5 0.5 0.5 0.5  0.5  0.5 0.5 0.5  0.5R-11A.sup.6       13.0                 13.0                     12.0                         13.0 13.0 12.0                                       13.0                                           13.0 12.0Water             --  0.3 --  --   0.3  --  --  0.3  --FOMREZ ® UL-32.sup.7             --  0.01                     --  --   0.01 --  --  0.01 --T-45.sup.8        --  --  1.0 --   --   1.0 --  --   1.0MONDUR ® MR.sup.9PAPI ® 27.sup.10             47.5                 43.8                     55.5                         46.6 42.8 53.4                                       46.5                                           42.8 53.3Index             1.05                 1.05                     3.0 1.05 1.05 3.0 1.05                                           1.05 3.0Reaction ProfileTimes (sec), mixing             15  12  6   15   12   6   15  12   6Times (sec), cream             27  21  14  25   17   13  26  17   15Times (sec), gel  92  71  46  97   69   49  97  65   49Times (sec), tack free             112 91  56  128  95   93  123 99   77Times (sec), rise 223 202 134 211  165  152 219 166  156Initial Surface Fri-             None                 None                     None                         None None Yes None                                           None YesabilityFoam appearance   Good                 Good                     Good                         Good Good Good                                       Good                                           Good GoodPhysical PropertiesDensity, pcf      1.97                 1.70                     1.84                         2.01 1.68 1.96                                       2.00                                           1.68 1.99K-factor          0.114                 0.110                     0.110                         0.121                              0.118                                   0.122                                       0.118                                           0.117                                                0.119Compressive strength,psi, with rise    43.80                 34.47                     33.12                         41.46                              30.69                                   35.03                                       44.26                                           35.26                                                40.64against rise      12.52                 8.25                     9.64                         14.93                              10.33                                   13.68                                       15.18                                           10.59                                                15.27Heat distortion, °C.             145 127 207 144  124  212 153 123  204Closed cells,     93.24                 93.22                     93.17                         92.14                              93.10                                   92.67                                       92.10                                           93.27                                                91.88Friability, % wt. 5.38                 4.24                     4.46                         5.79 2.32 6.42                                       7.43                                           2.30 11.88loss, 10 minASTM 1692 Burn,   1.87                 2.14                     1.81                         1.83 2.15 1.33                                       2.20                                           2.64 1.79in/min (BHA)Butler Chimney TestFlame height, in. &gt;11 &gt;11 7.67                         &gt;11  &gt;11  9.0 &gt;11 &gt;11  9.75Sec. to extinguish             21  14  12  32   24   12  23  25   11.75% wt. retained    55.4                 64.8                     84.4                         49.5 50.9 84.6                                       47.8                                           51.5 88.8Dimensional Stability158° F., 100% R-H1 weekΔV     +3.6                +7.0 +4.6                        +7.7 +16.7                                  +5.0                                      +5.6 +10.3                                                +3.7ΔW     -0.3                -0.4 -1.9                        -0.9 -1.0 -1.4                                      -0.6 -0.2 -1.8ΔL     +2.4                +4.6 +3.2                        +4.7 +10.1                                  +3.4                                      +3.4 +7.1 +3.54 weeksΔV     +7.7                +17.5                     +8.7                        +14.1                             +35.5                                  +8.4                                      +10.6                                           +24.8                                                +6.9ΔW     -0.2                0.0  -2.0                        -1.3 -2.0 -2.0                                      -0.7 -0.7 -2.6ΔL     +4.7                +10.3                     +5.9                        +8.6 +18.0                                  +5.6                                      +6.4 +15.0                                                +5.7__________________________________________________________________________                              Phenol/M-300 Based                              (See Table II)                              Ex. Ex. Ex.                                         Ex. Ex. Ex.            Fire Retardant    1   1   1  2   2   2__________________________________________________________________________            Formulation, pbw            THANOL ® R-350-X.sup.2 (OH = 526)                              34.6                                  22.9                                      -- 34.5                                             22.8                                                 --            TERATE ® 203.sup.3 (OH = 309)                              --  15.2                                      -- --  15.1                                                 --            R-440.sup.4 (OH = 258)                              --  --  27.4                                         --  --  27.2            R-440.sup.4 (OH = 252)            Fire Retardant    4.9 4.9 4.8                                         4.9 4.9 4.7            DC-193.sup.5      0.5 0.5 0.5                                         0.5 0.5 0.5            R-11A.sup.6       13.0                                  13.0                                      12.0                                         13.0                                             13.0                                                 12.0            Water             --  0.3 -- --  0.3 --            FOMREZ ® UL-32.sup.7                              --  0.01                                      -- --  0.01                                                 --            T-45.sup.8        --  --  1.0                                         --  --  1.0            MONDUR ® MR.sup.9            PAPI ® 27.sup.10                              47.0                                  43.2                                      54.3                                         47.1                                             43.4                                                 54.6            Index             1.05                                  1.05                                      3.0                                         1.05                                             1.05                                                 3.0            Reaction Profile            Times (sec), mixing                              15  12  6  15  12  6            Times (sec), cream                              27  18  15 18  13  14            Times (sec), gel  100 74  72 87  68  64            Times (sec), tack free                              137 104 98 106 98  108            Times (sec), rise 216 162 150                                         184 149 155            Initial Surface Fri-                              None                                  None                                      Yes                                         None                                             None                                                 Yes            ability            Foam appearance   Good                                  Good                                      Fair                                         Good                                             Good                                                 Good            Physical Properties            Density, pcf      2.04                                  1.69                                      2.04                                         2.00                                             1.65                                                 2.00            K-factor          0.111                                  0.113                                      0.114                                         0.112                                             0.113                                                 0.114            Compressive strength,            psi, with rise    46.12                                  34.98                                      34.64                                         45.20                                             33.29                                                 34.51            against rise      16.67                                  10.89                                      15.09                                         15.92                                             10.05                                                 13.94            Heat distortion, °C.                              148 119 210                                         148 122 209            Closed cells,     91.89                                  92.81                                      92.60                                         91.98                                             93.01                                                 92.70            Friability, % wt. 16.03                                  3.07                                      7.57                                         6.67                                             1.98                                                 5.03            loss, 10 min            ASTM 1692 Burn,   2.05                                  2.41                                      1.79                                         1.87                                             2.57                                                 1.75            in/min (BHA)            Butler Chimney Test            Flame height, in. &gt;11 &gt;11 10.0                                         &gt;11 &gt;11 &gt;11            Sec. to extinguish                              28  13  13 28  22  12            % wt. retained    45.3                                  65.2                                      85.6                                         44.2                                             53.6                                                 83.3            Dimensional Stability            158° F., 100% R-H            1 week                 ΔV     +4.4                                  +13.6                                      +5.8                                         +4.6                                             +10.8                                                 +4.9                 ΔW     +0.2                                  -0.3                                      -1.8                                         +0.1                                             -0.4                                                 -1.5                 ΔL     +2.7                                  +8.9                                      +5.6                                         +3.0                                             +7.2                                                 +4.2            4 weeks                 ΔV     +10.1                                  +34.0                                      +9.4                                         +11.1                                             +30.0                                                 +8.7                 Δ W    +0.1                                  -0.9                                      -2.4                                         0.0 -0.9                                                 -2.2                 ΔL     +5.9                                  +18.7                                      +8.1                                         +6.7                                             +17.3                                                 +6.6__________________________________________________________________________ .sup.1 ANTIBLAZE ® 80  Tris(2-chloropropyl phosphate) fire retardant made by Mobil Chemical Co. .sup.2 Aromatic amino polyol sold by Texaco Chemical Co. .sup.3 Aromatic polyester polyol sold by Hercules, Inc. .sup.4 Experimental aromatic polyester polyol made by Texaco Chemical Co. .sup.5 Silicone surfactant sold by Dow-Corning. .sup.6 Trichlorofluoromethane sold by E. I. duPont de Nemours &amp; Co. .sup.7 Organic tin catalyst sold by Witco Chemical Corp. .sup.8 Potassium octoate in glycol sold by M&amp;T Chemical Co. .sup.9 Polymeric isocyanate sold by Mobay Chemical Corp. .sup.10 Polymeric isocyanate sold by Upjohn Co.