Polyols with autocatalytic characteristics and polyurethane products made therefrom

Abstract

The present invention discloses a process for producing a polyurethane product with autocatalytic polyols. These autocatalytic polyols are based on an initiator that contains a tertiary amine. These autocatalytic polyols are reacted with a polyisocyanate in the presence of other additives and/or auxiliary agents known per se to produce polyurethane products.

1 . A process for the production of a flexible polyurethane foam by reaction of a mixture of 
 (a) at least one organic polyisocyanate with    (b) a polyol composition comprising    (b1) from 0 to 95 percent by weight of a polyol compound having a functionality of 2 to 8 and a hydroxyl number of from 20 to 100 and    (b2) from 5 to 100 percent by weight of at least one polyol compound having a functionality of 1 to 8 and a hydroxyl number of from 20 to 200,    wherein the weight percent is based on the total amount of polyol component (b), and (b2) is obtained by alkoxylation of at least one initiator molecule of (b2a), (b2b), (b2c) or (b2d) wherein    (b2a) is      H 2 N—(CH 2 ) n —N(R)—H  Formula (I)    where n is an integer from 2 to 12, and    R is a C 1  to C 3  alkyl group;    (b2b) is a compound which contains a dialkylylamino group pendant to a polyhydroxy or polyamino molecule of Formula II                          where R′ at each occurrence is independently a C 1  to C 3  alkyl group and R is as previously defined;    s is an integer from 1 to 3;    m is an integer from 1 to 12;    A is nitrogen or oxygen; and    p is 2 when A is nitrogen and is 1 when A is oxygen;    w is 0, 1 or 2;    (b2C) is a dimethylamino group pendant to a monohydroxy or monamino structure of Formula III      R 2 —(CH 2 ) y —CH (2-x) R x —AH p   (Formula III)    where    R 2  is NR′ 2  or a 5 substituted, 1-aza-3,7-dioxabicyclo[3.3.0] octane;    R, R′, A, and p, are as previously defined;    y is 0 or 1; and    x is 0, 1 or 2;    (b2d) is a bis-N-substituted piperazine wherein the substitution is an amino or hydroxy substituted C1 to C6 linear or branched alkyl;    (b2e) is a compound of Formula IV      R 3 —NH—R  (Formula IV)    with R 3  a C5 to C6 cycloalkyl group and R is as previously defined    (b2f) is a compound of formula V                          where R, R′, m, n, A, p and w are as previously defined;    x is 0, 1 or 2;    s is and integer from 1 to 3;    and q is an integer from 0 to 12;    or (b2) is a hydroxyl-tipped prepolymer obtained from the reaction of an excess of (b2 a), (b2b), (b2c), (b2d), (b2e) or (b2f) with a polyisocyanate;    or (b2) is (b2g) a blend selected from (b2a), (b2b) (b2c), (b2d), (b2e) (b2f) or hydroxyl-terminated prepolymers obtained from polyols based on initiators (b2a)-(b2f);    (c) optionally in the presence of a blowing agent; and    (d) optionally additives or auxiliary agents known per se for the production of polyurethane foams, elastomers and/or coatings.    
   
   
       2 . The process of  claim 1  wherein the initiator for (b2) is represented by Formula I wherein R is methyl.  
   
   
       3 . The process of  claim 2  wherein n is from 2 to 4.  
   
   
       4 . The process of  claim 2  wherein the initiator is N-methyl-1,2-ethanediamine or N-methyl-1,3,-propanediamine.  
   
   
       5 . The process of  claim 1  wherein the initiator for (b2) is represented by Formula II and R is methyl.  
   
   
       6 . The process of  claim 5  wherein R′ at each occurrence is methyl.  
   
   
       7 . The process of  claim 6  wherein A is oxygen.  
   
   
       8 . The process of  claim 6  wherein A is nitrogen.  
   
   
       9 . The process of  claim 8  wherein the initiator is N,N-dimethyl-tris(hydroxymethyl) aminomethane.  
   
   
       10 . The process of  claim 1  wherein the initiator for (b2) is represented by Formula III.  
   
   
       11 . The process of  claim 10  wherein R 2  is NR′ 2  where R′ is methyl.  
   
   
       12 . The process of  claim 10  wherein R 2  is 1-aza-3,7-dioxabicyclo octane.  
   
   
       13 . The process of  claim 10  wherein A is oxygen.  
   
   
       14 . The process of  claim 13  wherein the initiator is hydroxymethyl oxazolidine.  
   
   
       15 . The process of  claim 10  wherein A is nitrogen.  
   
   
       16 . The process of  claim 15  wherein the initiator is dimethylamino ethanolamine or N-methyl cyclohexylamine.  
   
   
       17 . The process of  claim 1  wherein the initiator for (b2b) is a bis-N-substituted piperazine.  
   
   
       18 . The process of  claim 17  wherein the initiator is N-bis(2-amino-isobutyl)-piperazine or N-methyl-dicyclohexylamine.  
   
   
       19 . The process  claim 1  wherein the initiator is represented by Formula IV.  
   
   
       20 . The process of  claim 19  wherein the initiator is N-methyl-cyclohexylamine.  
   
   
       21 . (canceled)  
   
   
       22 . (canceled)  
   
   
       23 . (canceled)  
   
   
       24 . (canceled)  
   
   
       25 . (canceled)  
   
   
       26 . The process of  claim 1  wherein the polyols (b1) and (b2) have an average functionality of 2 to 4 and an average hydroxyl number of 20 to 100.  
   
   
       27 . The process of  claim 26  wherein the blowing agent is water in an amount from 0.5 to 10 parts by weight of component (b).  
   
   
       28 . The process of  claim 27  wherein carbon dioxide is used either as a gas or as a liquid in the mixture to act as an auxiliary blowing agent.  
   
   
       29 . The process of  claim 26  wherein an acid is used in the mixture to act either as a delayed action additive or as a blowing agent in case of carboxylic acids.  
   
   
       30 . The process of  claim 26  wherein the polyisocyanate is toluene diisocyanate, polymethylene polyphenylene diisocyanate, isomers of diphenylmethylene diisocyanate or mixtures thereof.  
   
   
       31 . (canceled)  
   
   
       32 . (canceled)  
   
   
       33 . The process of  claim 1  wherein the polyisocyanate (a) contains at least one polyisocyanate that is a reaction product of an excess of polyisocyanate with a polyol which contains an initiator of (b2a), (b2b), (b2c), (b2d) or (b2e).  
   
   
       34 . The process of  claim 1  wherein the polyol (b) contains a polyol-terminated prepolymer obtained by the reaction of an excess of polyol with a polyisocyanate wherein the polyol is a polyol as defined by (b2) or is a mixture of (b2) with another polyol.  
   
   
       35 . (canceled)  
   
   
       36 . A flexible polyurethane product produced by the process of  claim 1 .  
   
   
       37 . (canceled)  
   
   
       38 . (canceled)  
   
   
       39 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator of Formula I  
       H 2 N—(CH 2 ) n —N(R)—H  Formula (I)  where n is an integer from 2 to 6, and    R is a C 1  to C 3  alkyl group.    
   
   
       40 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator of Formula II:  
     
       
         
         
             
             
         
       
       where R′ at each occurrence is independently a C 1  to C 3  alkyl group  
       R is a C 1  to C 3  alkyl group;  
       s is an integer from 1 to 3;  
       m is an integer from 2 to 6;  
       A is nitrogen or oxygen; and  
       p is 2 when A is nitrogen and is 1 when A is oxygen;  
       and w is 0, 1, or 2.  
     
   
   
       41 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator of Formula III:  
       R 2 —(CH 2 ) y —CH (2-x) R x —AH p   (Formula III)  
     where 
 R 2  is NR′ 2  or a 5 substituted, 1-aza-3,7-dioxabicyclo[3.3.0] octane;  
 R′ at each occurrence is independently a C 1  to C 3  alkyl group  
 R is a C 1  to C 3  alkyl group;  
 y is 0 or 1;  
 x is 0, 1 or 2;  
 A is nitrogen or oxygen; and  
 p is 2 when A is nitrogen and is 1 when A is oxygen.  
 
   
   
       42 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator that is a bis-N-substituted piperazine wherein the substitution is a hydroxy substituted C1 to C6 linear or branched alkyl.  
   
   
       43 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator of Formula IV  
       R 3 —NH—R  (Formula IV)  
     where 
 R 3  a C 5  to C 6  cycloalkyl group and  
 R is a C 1  to C 3  alkyl group.  
 
   
   
       44 . A prepolymer formed by reaction of an excess of polyisocyanate with a polyol as defined by (b2) of  claim 1  or a mixture thereof.  
   
   
       45 . A prepolymer formed by reaction of an excess of a polyol as defined by (b2) of  claim 1  or a mixture thereof with a polyisocyanate.  
   
   
       46 . The process of  claim 1  wherein the amount of (b2) is present in an amount so that the curing time is substantially equivalent to a similar reaction mixture containing standard polyurethane catalysts, where the reaction mixture with (b2) contains at least 10 percent by weight less of a standard polyurethane catalyst.  
   
   
       47 . An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator of Formula V  
     
       
         
         
             
             
         
       
       where,  
       x is 0, 1 or 2;  
       s is and integer from 1 to 3;  
       q is an integer from 0 to 12;  
       R′ at each occurrence is independently a C 1  to C 3  alkyl group;  
       R is a C 1  to C 3  alkyl group;  
       A is nitrogen or oxygen;  
       m, n and q are independently integers from 1 to 12;  
       p is 2 when A is nitrogen and 1 when A is oxygen;  
       w is 0, 1, or 2.