Method for producing polyurethane foam

Abstract

A method for producing polyurethane foams by reacting at least one organic isocyanate moiety, at least one polyol, a blowing agent consisting of halogen-containing (fluorine-containing) olefins and at least a siloxane of formula (I) R, R 1 , R 2 , R 4 , a, b, c, and d are defined herein, as well as compositions made by said method are described.

What is claimed is: 
     
         1 . A method for producing polyurethane foams comprising reacting at least one organic isocyanate containing two or more isocyanate functions, at least one polyol containing two or more isocyanate-reactive groups, and a blowing agent consisting of at least one halogenated olefin and at least one siloxane of formula (I): 
       
         
           
           
               
               
           
         
         wherein 
       
       
         
           
           
               
               
           
         
         a in each occurrence independently is from 0 to 500, 
         b in each occurrence independently is from 0 to 60, 
         c in each occurrence independently is from 0 to 10, 
         d in each occurrence independently is from 0 to 10, 
         with the proviso that, per molecule of formula (I), the average number Σd of T-units and the average number Σc of Q-units per molecule are neither greater than 50, the average number Σa of D-units per molecule is not greater than 2000 and the average number Σb of R 1 -bearing siloxy units per molecule is not greater than 100, 
         R is methyl, 
         the a/b ratio is not less than 7, 
         R 2  in each occurrence independently is R 1  or R, 
         R 1  is unlike R and in each occurrence independently is an organic moiety and/or a moiety selected from the group consisting of:
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″ 
 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″ 
 —CH 2 —R IV    
 —CH 2 —CH 2 —(O) x′ —R IV    
 —CH 2 —CH 2 —CH 2 —O—CH 2 —CH(OH)—CH 2 OH 
 
       
       
         
           
           
               
               
           
         
         and 
         —CH 2 —CH 2 —CH 2 —O—CH 2 —C(CH 2 OH) 2 —CH 2 —CH 3 , where 
         x is from 0 to 100, 
         x′ is 0 or 1, 
         Y is from 0 to 100, 
         z is from 0 to 100, 
         R′ in each occurrence independently is an alkyl or aryl group of 1 to 12 carbon atoms, wherein within an R 1  moiety and/or a molecule of formula I mutually different substituents R′ can be present, and 
         R″ in each occurrence independently is hydrogen or an alkyl group of 1 to 4 carbon atoms, a —C(O)—R′″ group where R′″=alkyl, a —CH 2 —O—R′ group, an alkylaryl group, or a —C(O)NH—R′ group, 
         R IV  is a linear, cyclic or branched, hydrocarbon moiety having 1 to 50 carbon atoms, 
         R 4  in each occurrence independently may be R, R 1  and/or a heteroatom-substituted, functionalized, organic, saturated or unsaturated moiety selected from the group consisting of alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloyloxyaryl, acryloyloxyalkyl, methacryloyloxyalkyl, methacryloyloxypropyl and vinyl, 
         with the proviso that at least one substituent from R 1 , R 2  and/or R 4  is other than R. 
       
     
     
         2 . The method according to  claim 1  wherein
 a in each occurrence independently is from 1 to 300, 
 b in each occurrence independently is from 1 to 50, 
 c in each occurrence independently is >0 to 4, 
 d in each occurrence independently is >0 to 4, 
 with the proviso that, per molecule of formula (I), the average number Σd of T-units and the average number Σc of Q-units per molecule are neither greater than 20, the average number Σa of D-units per molecule is not greater than 1500 and the average number Σb of R 1 -bearing siloxy units per molecule is not greater than 50. 
 
     
     
         3 . The method according to  claim 2  wherein
 R 1  in each occurrence independently is an organic moiety
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″ 
 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″, or 
 —CH 2 —R IV    
 where 
 x is from 0 to 100, 
 y is from 0 to 100, 
 R′ in each occurrence independently may be different and is methyl, ethyl and/or phenyl and, 
 R″ in each occurrence independently is hydrogen or an alkyl group of 1 to 4 carbon atoms, a —C(O)—R′″ group where R′″=alkyl, a —CH 2 —O—R′ group, an alkylaryl group, a —C(O)NH—R′ group, 
 R IV  is a linear, cyclic or branched, hydrocarbon moiety having 1 to 50 carbon atoms. 
 
 
     
     
         4 . The method according to  claim 3  wherein
 R 1  in each occurrence independently is an organic moiety selected from the group consisting of:
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″, 
 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″, 
 —CH 2 —R IV , and mixtures thereof 
 where 
 x is from 0 to 100, 
 y is from 0 to 100, 
 R′ is methyl and 
 R″ in each occurrence independently is hydrogen or an alkyl group of 1 to 4 carbon atoms, a —C(O)—R′″ group where R′″=alkyl, a —CH 2 —O—R′ group, an alkylaryl group, a —C(O)NH—R′ group, 
 wherein the molar fraction of oxyethylene units comprises at least 70% of the oxyalkylene units, or the molar fraction of oxyethylene units comprises at most 70% of the oxyalkylene units, and R″ is hydrogen. 
 
 
     
     
         5 . The method according to  claim 1  wherein R 1  consists of —CH 2 —R IV  to an extent of at least 20 mol %, wherein R IV  is a linear or branched hydrocarbon having 9 to 17 carbon atoms. 
     
     
         6 . The method according to  claim 1  wherein at least 10% of the R 2  moieties are equal to R 1 . 
     
     
         7 . The method according to  claim 1  wherein each siloxane of formula (I) is statistically on average at most 50%, of the entire average molecular weight of the one or more siloxanes of formula (I) and is accounted for by a summed molar mass of all R 1  moieties in the at least one siloxane of formula (I). 
     
     
         8 . The method according to  claim 1  wherein, in R 1 , y=0 and R″ is not hydrogen. 
     
     
         9 . The method according to  claim 1  wherein Σc+Σd is <1. 
     
     
         10 . The method according to  claim 1  wherein Σc+Σd is 1. 
     
     
         11 . A polyurethane foam obtained by a method according to  claim 1 . 
     
     
         12 . The polyurethane foam according to  claim 1 , wherein said polyurethane foam is closed-cell. 
     
     
         13 . The polyurethane foam according to  claim 12 , wherein the polyurethane foam is a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semirigid polyurethane foam, a thermoformable polyurethane foam or an integral foam. 
     
     
         14 . The method according to  claim 1 , wherein each siloxane of formula (I) is statistically on average at most 45% of the entire average molecular weight of the at least one siloxane of formula (I) and is accounted for by a summed molar mass of all R 1  moieties in the at least one siloxane of formula (I). 
     
     
         15 . The method according to  claim 1 , wherein each siloxane of formula (I) is statistically on average at most 40% of the entire average molecular weight of the at least one siloxane of formula (I) and is accounted for by a summed molar mass of all R 1  moieties in the at least one siloxane of formula (I). 
     
     
         16 . The polyurethane foam according to  claim 12 , wherein said polyurethane foam contains from 0.01% to 10% by weight of said at least one siloxane of formula (I). 
     
     
         17 . The polyurethane foam according to  claim 12  wherein said polyurethane foam contains from 0.1% to 3% by weight of said at least one siloxane of formula (I). 
     
     
         18 . A composition of matter, comprising a polyurethane foam and from 0.01% to 10% by weight of at least one siloxane of formula (I) 
       
         
           
           
               
               
           
         
         a in each occurrence independently is from 0 to 500, 
         b in each occurrence independently is from 0 to 60, 
         c in each occurrence independently is from 0 to 10, 
         d in each occurrence independently is from 0 to 10, 
         with the proviso that, per molecule of formula (I), the average number Σd of T-units and the average number Σc of Q-units per molecule are neither greater than 50, the average number Σa of D-units per molecule is not greater than 2000 and the average number Σb of R 1 -bearing siloxy units per molecule is not greater than 100, 
         R is methyl, 
         the a/b ratio is not less than 7, 
         R 2  in each occurrence independently is R 1  or R, 
         R 1  is unlike R and in each occurrence independently is an organic moiety and/or a moiety selected from the group consisting of:
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″ 
 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″ 
 —CH 2 —R IV    
 —CH 2 —CH 2 —(O) x ′—R IV    
 —CH 2 —CH 2 —CH 2 —O—CH 2 —CH(OH)—CH 2 OH 
 
       
       
         
           
           
               
               
           
         
         
            and 
           —CH 2 —CH 2 —CH 2 —O—CH 2 —C(CH 2 OH) 2 —CH 2 —CH 3 , where 
           x is from 0 to 100, 
           x′ is 0 or 1, 
           y is from 0 to 100, 
           z is from 0 to 100, 
           R′ in each occurrence independently is an alkyl or aryl group of 1 to 12 carbon atoms, wherein within an R 1  moiety and/or a molecule of formula I mutually different substituents R′ can be present, and 
           R″ in each occurrence independently is hydrogen or an alkyl group of 1 to 4 carbon atoms, a —C(O)—R′″ group where R′″=alkyl, a —CH 2 —O—R′ group, an alkylaryl group, or a —C(O)NH—R′ group, 
           R IV  is a linear, cyclic or branched, hydrocarbon moiety having 1 to 50 carbon atoms, 
           R 4  in each occurrence independently may be R, R 1  and/or a heteroatom-substituted, functionalized, organic, saturated or unsaturated moiety selected from the group consisting of alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloyloxyaryl, acryloyloxyalkyl, methacryloyloxyalkyl, methacryloyloxypropyl and vinyl, 
         
         with the proviso that at least one substituent from R 1 , R 2  and/or R 4  is other than R.