Phosphorus containing aromatic amino polyols

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' may be the same or different alkyl or haloalkyl radicals, R.sup.2 and R.sup.3 may be the same or different lower alkylene radicals and R.sub.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', R.sup.2, R.sup.3 and R.sup.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.sup.2 is hydrogen, a methyl or an ethyl group, and R' is --CH.sub.2 --CH.sub.2 --CH.sub.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' 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' is an alkyl group. It is preferred that R is an alkanol group. Especially preferred is --CH.sub.2 --CH.sub.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.degree. to 150.degree. 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.degree. C. and 81.1 g of formalin (1.0 moles) were added slowly while keeping the temperature at 15.degree.-20.degree. C. After all the formalin was added, the mixture was stirred for 30 minutes and then heated to 90.degree. 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.degree. C. The contents were heated to 90.degree. C. and held at 90.degree.-108.degree. 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., .degree.C. Hrs-Temp., .degree.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 .RTM. 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 .degree.C. .degree.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 .degree.C. .degree.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.degree. 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".times.8".times.12" (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.RTM. (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 .RTM. 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 .RTM. 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 .RTM. UL-32.sup.7 -- -- 0.01 0.01 -- -- -- 0.01 -- 0.01T-45.sup.8 -- -- -- -- 1.5 -- -- -- -- --MONDUR .RTM. MR.sup.9 49.2 46.4 45.2 42.6 52.1 -- -- --PAPI .RTM. 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, .degree.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. >11 >11 >11 >11 4.33 >11 >11 >11 >11 >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.degree. F., 100% R-H1 week .DELTA.V +2.7 +8.4 +2.9 +16.5 +5.3 +2.9 +3.2 +4.1 +4.3 +4.1 .DELTA.W -0.3 -0.7 -0.6 -1.0 -1.9 +0.3 +0.2 +0.1 -0.4 -0.6 .DELTA.L +1.8 +5.4 +2.2 +11.9 +3.4 +2.5 +2.2 +3.3 +2.5 +2.44 weeks .DELTA.V +5.4 +16.8 +7.7 +42.5 +9.8 +5.4 +6.1 +7.7 +8.4 +10.3 .DELTA.W -0.3 -1.2 -0.6 -2.8 -3.1 +0.4 +0.2 0.0 0.0 -0.1 .DELTA.L +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 .RTM. R-350-X.sup.2 (OH = 526) 34.1 22.5 -- 34.9 23.1 -- 35.0 23.1 --TERATE .RTM. 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 .RTM. UL-32.sup.7 -- 0.01 -- -- 0.01 -- -- 0.01 --T-45.sup.8 -- -- 1.0 -- -- 1.0 -- -- 1.0MONDUR .RTM. MR.sup.9PAPI .RTM. 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, .degree.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. >11 >11 7.67 >11 >11 9.0 >11 >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.degree. F., 100% R-H1 week .DELTA.V +3.6 +7.0 +4.6 +7.7 +16.7 +5.0 +5.6 +10.3 +3.7 .DELTA.W -0.3 -0.4 -1.9 -0.9 -1.0 -1.4 -0.6 -0.2 -1.8 .DELTA.L +2.4 +4.6 +3.2 +4.7 +10.1 +3.4 +3.4 +7.1 +3.54 weeks .DELTA.V +7.7 +17.5 +8.7 +14.1 +35.5 +8.4 +10.6 +24.8 +6.9 .DELTA.W -0.2 0.0 -2.0 -1.3 -2.0 -2.0 -0.7 -0.7 -2.6 .DELTA.L +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 .RTM. R-350-X.sup.2 (OH = 526) 34.6 22.9 -- 34.5 22.8 -- TERATE .RTM. 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 .RTM. UL-32.sup.7 -- 0.01 -- -- 0.01 -- T-45.sup.8 -- -- 1.0 -- -- 1.0 MONDUR .RTM. MR.sup.9 PAPI .RTM. 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, .degree.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. >11 >11 10.0 >11 >11 >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.degree. F., 100% R-H 1 week .DELTA.V +4.4 +13.6 +5.8 +4.6 +10.8 +4.9 .DELTA.W +0.2 -0.3 -1.8 +0.1 -0.4 -1.5 .DELTA.L +2.7 +8.9 +5.6 +3.0 +7.2 +4.2 4 weeks .DELTA.V +10.1 +34.0 +9.4 +11.1 +30.0 +8.7 .DELTA. W +0.1 -0.9 -2.4 0.0 -0.9 -2.2 .DELTA.L +5.9 +18.7 +8.1 +6.7 +17.3 +6.6__________________________________________________________________________ .sup.1 ANTIBLAZE .RTM. 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 & Co. .sup.7 Organic tin catalyst sold by Witco Chemical Corp. .sup.8 Potassium octoate in glycol sold by M&T Chemical Co. .sup.9 Polymeric isocyanate sold by Mobay Chemical Corp. .sup.10 Polymeric isocyanate sold by Upjohn Co.

Claims

1. A compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR15## in which R is an alkanol or polyoxyalkylene group, and R' is an alkyl group, said compound being a polyol.

2. The compound of claim 1 in which the phenol is nonylphenol, phenol, isopropyl phenol, a cresol, dodecylphenol or Bisphenol A.

3. The compound of claim 1 as the product of a Mannich reaction.

4. A compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR16## in which R is an alkanol or polyoxypropylene group, and R' is a methyl or ethyl group, said compound being a polyol.

5. The compound of claim 4 in which the phenol is nonylphenol, phenol, isopropyl phenol, a cresol, dodecylphenol or Bisphenol A.

6. The compound of claim 4 as the product of a Mannich reaction.

7. A compound having the formula: ##STR17##