Use of low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates as flame retardants in polyurethane or polyisocyanurate foams

Abstract

The present invention relates to the use of low triphenyl phosphate, high phosphorous content aryl phosphates with high ortho alkylation as flame retardants in polyurethane or polyisocyanurate foams or polyurethane or polyisocyanurate foam formulations.

1 . (canceled) 
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . The polyurethane or polyisocyanurate foam formulation according to  claim 21  wherein said polyurethane or polyisocyanurate foam formulation is a flexible polyurethane foam formulation or a rigid polyurethane foam formulation. 
     
     
         5 . The polyurethane or polyisocyanurate foam formulation according to  claim 21  wherein said polyurethane or polyisocyanurate foam or polyurethane or polyisocyanurate foam formulation further contains at least one additional component selected from blowing agents, surfactants, antioxidants, diluents, and the like. 
     
     
         6 . The polyurethane or polyisocyanurate foam formulation according to  claim 5  wherein said alkylated triaryl phosphate ester has an organic phosphorous content in the range of from about 8 to about 8.4 wt %, based on the total weight of the alkylated triaryl phosphate ester. 
     
     
         7 . The polyurethane or polyisocyanurate foam formulation according to  claim 22  wherein said alkylated triaryl phosphate ester contains greater than about 90 wt % monalkylphenyl diphenyl phosphates, based on the total weight of the alkylated triaryl phosphate ester. 
     
     
         8 . The polyurethane or polyisocyanurate foam formulation according to  claim 21  wherein said alkylated triaryl phosphate ester contains less than about 0.5 wt % TPP based on the total weight of the alkylated triaryl phosphate ester. 
     
     
         9 . The polyurethane or polyisocyanurate foam formulation according to  claim 21  wherein said alkylated triaryl phosphate is made by a process comprising:
 a. reacting an alkylated phenol stream comprising less than about 1 mole % phenol and up to about 25 mole % dialkyl phenol, both based on the total weight of the alkylated phenol, with POCl3 in the presence of a first catalyst under first reaction conditions including temperatures ranging from about 80° C. to about 210° C. thereby producing a first reaction product comprising greater than about 75 mole % monoalkylated phenyl-dichloro phosphates, based on the total moles of the first reaction product; and 
 b. reacting the first reaction product with an alcohol selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst under second reaction conditions including temperatures ranging from about 90° C. to about 260° C. thereby producing' an alkylated triaryl phosphate ester; 
 or by a process comprising: 
 a. reacting an alkylated phenol stream comprising less than about 1 mole % phenol and up to about 25 mole % dialkyl phenol, both based on the total weight of the alkylated phenol, with POCl3 in the presence of a first catalyst under first reaction conditions including temperatures ranging from about 80° C. to about 210° C. thereby producing a first reaction product comprising greater than about 75 mole % monoalkylated phenyl-dichloro phosphates, based on the total moles of the first reaction product; and 
 b. sequentially reacting the first reaction product with more than one alcohol selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst under second reaction conditions including temperatures ranging from about 70° C. to about 260° C. thereby producing an alkylated triaryl phosphate ester. 
 
     
     
         10 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein the alkylated phenol stream comprises ortho-isopropylphenol (OIP), meta-isopropylphenol (MIP), and para-isopropylphenol (PIP. constituents. 
     
     
         11 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein the alkylated phenol stream comprises in the range of from about 64 to about 68 wt. % OIP, in the range of from about 0.5 to about 2.5 wt. % MIP, and in the range of from about 31 to about 35 wt. % PIP, all based on the total weight of the alkylated phenol. 
     
     
         12 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein excess POCl3 is stripped from the first reaction product prior to the first reaction product being reacted with the alcohol in the presence of the second catalyst. 
     
     
         13 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein said first reaction conditions include the substantial absence of oxygen. 
     
     
         14 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein a diluent selected from 1,4-dioxane and toluene is added along with the POCl3, first catalyst, and alkylated phenol. 
     
     
         15 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein the first reaction product comprises greater than about 75 mole % monoalkylated phenyl dichloro phosphates, based on the total moles of the first reaction product excluding unreacted POCl3, in the range of from about 70 to about 99.9 mole % monoalkylated phenyl-dichloro phosphates and in the range of from about 0.1 mole % but less than 30 mole %, bis-(monoalkylated. phenyl-chloro phosphates, both based on the total moles of the first reaction product excluding unreacted POCl3. 
     
     
         16 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein the alcohol is selected from decanol, dodecanol, monoisopropylated phenols, phenol, or mixtures thereof. 
     
     
         17 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein i. the alcohol is added to the first reaction product to which the second catalyst has already been introduced; or ii. a mixture of the second catalyst and alcohol are introduced into the first reaction product. 
     
     
         18 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein said process further comprises:
 a. adding to the alkylated aryl phosphate ester an additional amount of alcohol selected from monoisopropylated phenols, diisopropylated phenols, phenol, and mixtures thereof, and/or an additional amount of second catalyst to the alkylated triaryl phosphate ester thus producing an alcohol-rich alkylated phenyl phosphate product containing excess alcohol; 
 b. recovering said alcohol-rich alkylated phenyl phosphate product; and 
 c. removing at least a portion of the excess alcohol from the alcohol-rich alkylated phenyl phosphate ester product; 
 wherein the excess alcohol is removed by a method selected from phase separation stripping, distillation, and mixtures thereof. 
 
     
     
         19 . The polyurethane or polyisocyanurate foam formulation according to  claim 9  wherein said alkylated triaryl phosphate ester is an isopropylphenyl diphenyl phosphate ester selected from:
 a. isopropylphenyl diphenyl phosphate esters comprising in the range of from about 66 to 100 wt % 2-isopropylphenyl phosphate (2-IPP), in the range of from about 0.1 to 4 wt % 3-isopropylphenyl phosphate (3-IPP), and in the range of from about 0.1 to 40 wt % 4-isopropylphenyl phosphate (4-IPP); 
 b. isopropylphenyl diphenyl phosphate esters comprising in the range of about 63 to about 68 wt. % 2-IPP, in the range of from about 0.5 to about 2.5 wt. % 3-IPP and in the range of from about 30.5 to about 36.5 wt. % 4-IPP; or 
 c. isopropylphenyl diphenyl phosphate esters comprising about 66 wt. % 2-IPP, about 1 wt. % 3-IPP and about 33 wt. % 4-IPP, 
 wherein all wt. % are based on the total weight of the isopropylphenyl diphenyl phosphate ester. 
 
     
     
         20 . (canceled) 
     
     
         21 . A polyurethane or polyisocyanurate foam composition comprising at least one isocyanate, polyol, or combination thereof, and a flame retarding amount of an alkylated triaryl phosphate ester, wherein said alkylated triaryl phosphate ester contains at least one of (a) monoalkylphenyl diphenyl phosphates, (b. di-(alkylphenyl. phenyl phosphates, (c. dialkylphenyl diphenyl phosphates; (d. trialkylphenyl phosphates; (e. alkylphenyl dialkylphenyl pphenyl phosphates, and less than about 1 wt % triphenyl phosphate (“TPP”. and in the range of from about 5 to about 10 wt % organic phosphoous content, wherein the alkyl moieties of the alkylated phenyl phosphates and TPP are selected from methyl, ethyl, n-propopyl, isopropyl, isobutyl, tertiary-butyl, isoamyl and tertiary-amyl groups, all based on the total weight of the alkylated triaryl phosphate ester. 
     
     
         22 . The polyurethane or polyisocyanurate foam composition according to  claim 21  wherein the alkylated triaryl phosphate ester contains greater than about 75 wt % monalkylphenyl diphenyl phospates. 
     
     
         23 . A molded or extruded article comprising the polyurethane or polyisocyanurate foam composition of  claim 21 .