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US4582861A Expired / Lapsed US ⏱️ 0.0 years remaining

Delayed action/enhanced curing catalysis in polyurethane systems

Assignee: Air Products and Chemicals Inc
•
Filing: 1984-11-13
•
Granted: 1986-04-15
•
Expires: 2004-11-13
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Abstract

Abstract A method for preparing polyurethane product by the reaction of an organic polyisocyanate with a polyester or polyether polyol in the presence of a catalytically effective amount of a catalyst system consisting essentially of a tertiary amine and 1 to 35 wt %, based on the tertiary amine, of an N-hydroxyalkyl quaternary ammonium carbonylate salt. The use of such catalyst system advantageously improves the cure time of the urethane reaction, when compared to a system containing solely a tertiary amine, while maintaining the same initiation of the reaction. This advantage can be transferred to a delay in the initiation time while maintaining or shortening the cure time by adjustments in the total amount of the catalyst system used.

Inventors

  • 👤 Edward A. Galla
  • 👤 Robert L. Ricci
  • 👤 Gary D. Andrew

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-25 15:11
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/16; C08G18/18; C08G18/20; C08G18/2045; C08G18/2063; C08G18/1875; Y; Y10; Y10S; Y10S521/00; Y10S521/902

Claims Analysis

Total Claims: 41
Claim 1
Independent Claim 346 words
In a method for the preparation of a polyurethane product by reacting a polyisocyanate with a polyester or a polyether polyol in the presence of a tertiary amine catalyst, the improvement which comprises employing a catalytically effective amount of a mixture consisting essentially of a tertiary amine and 1 to 35 weight percent, based on the tertiary amine, of an organic acid salt of a quaternary ammonium compound of the formula: ##STR4## wherein a is 0 or 1, R, R 1 and R 2 are independently alkyl or hydroxyalky groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl (e.g. benzyl), aryl (e.g. phenyl), alkenyl of 2 to 20 carbon atoms, or alkynyl of 2 to 6 carbon atoms, or R, R 1 and R 2 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure; R 3 is hydrogen, phenyl, an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, alkynyl group of 2 to 6 carbon atoms, a hydroxyalkyl group of 1 to 9 carbon atoms, a ketoalkyl group having a total of 3 to 15 carbon atoms, or an alkoxy alkyl group having a total of 2 to 20 carbon atoms; Y is hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, phenyl, an alkylphenyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the phenyl ring, benzyl, an alkylbenzyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the benzene ring, or a CH.sub.(3-b) Z.sub.(b) group wherein b is 1 to 3 and Z is --OH, --CN, --Cl, an alkoxy group of 1 to 5 carbon atoms, a phenyl group or methoxyphenyl group, or Z is (CH 2 ) d COOR 4 wherein d is equal to 0 to 4 and R 4 is hydrogen or an alkyl group of up to 20 carbon atoms.
Claim 2
Dependent Claim 346 words
In a method for the preparation of a polyurethane product by reacting a polyisocyanate with a polyester or a polyether polyol in the presence of a tertiary amine catalyst, the improvement which comprises employing a catalytically effective amount of a mixture consisting essentially of a tertiary amine and 1 to 35 weight percent, based on the tertiary amine, of an organic acid salt of a quaternary ammonium compound of the formula: ##STR4## wherein a is 0 or 1, R, R 1 and R 2 are independently alkyl or hydroxyalky groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl (e.g. benzyl), aryl (e.g. phenyl), alkenyl of 2 to 20 carbon atoms, or alkynyl of 2 to 6 carbon atoms, or R, R 1 and R 2 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure; R 3 is hydrogen, phenyl, an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, alkynyl group of 2 to 6 carbon atoms, a hydroxyalkyl group of 1 to 9 carbon atoms, a ketoalkyl group having a total of 3 to 15 carbon atoms, or an alkoxy alkyl group having a total of 2 to 20 carbon atoms; Y is hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, phenyl, an alkylphenyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the phenyl ring, benzyl, an alkylbenzyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the benzene ring, or a CH.sub.(3-b) Z.sub.(b) group wherein b is 1 to 3 and Z is --OH, --CN, --Cl, an alkoxy group of 1 to 5 carbon atoms, a phenyl group or methoxyphenyl group, or Z is (CH 2 ) d COOR 4 wherein d is equal to 0 to 4 and R 4 is hydrogen or an alkyl group of up to 20 carbon atoms.
Claim 3
Dependent Claim 18 words
The method of claim 1 in which the quaternary ammonium salt is 3-25 wt% of the tertiary amine.
Claim 4
Dependent Claim 84 words
The method of claim 1 in which the tertiary amine has the following general formula ##STR5## where R 5 , R 6 and R 7 are independently alkyl or hydroxyalkyl groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl, aryl, alkenyl of 2 to 20 carbon atoms or alkynyl 2 to 6 carbon atoms, or R 5 , R 6 and R 7 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure.
Claim 5
Dependent Claim 12 words
The method of claim 1 in which the tertiary amine is triethylenediamine.
Claim 6
Dependent Claim 20 words
The method of claim 1 in which the tertiary amine comprises 5 to 8 parts dimethylethanolamine per part of bis(dimethylaminoethyl)ether.
Claim 7
Dependent Claim 83 words
The method of claim 1 in which the quaternary ammonium salt has the general formula: ##STR6## where R, R 1 and R 2 are independently alkyl or hydroxyalkyl groups of 1 to 4 carbon atoms, or together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure, R 3 is hydrogen or methyl and R 8 is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH 2 CN.
Claim 8
Dependent Claim 21 words
The method of claim 1 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine.
Claim 9
Dependent Claim 21 words
The method of claim 1 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of dimethyl-N-hydroxyethyl-N-2-hydroxypropyl quaternary amine.
Claim 10
Dependent Claim 21 words
The method of claim 1 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of trimethyl-N-2-hydroxypropyl quaternary amine.
Claim 11
Dependent Claim 24 words
The method of claim 1 in which the quaternary amine salt is the cyanoacetic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine or dimethyl-N-hydroxyethyl-N-2-hydroxypropyl quaternary amine.
Claim 12
Dependent Claim 27 words
The method of claim 1 in which the quaternary ammonium salt is the formic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine; dimethyl-N-hydroxyethyl-N-2-hydroxypropyl quaternary amine or trimethyl-N-2-hydroxypropyl quaternary amine.
Claim 13
Dependent Claim 214 words
In a method for the preparation of a polyurethane product by the reaction of a polyisocyanate with a polyester or polyether polyol in the presence of a tertiary amine catalyst, the improvement which comprises employing a catalytically effective amount of a composition consisting essentially of a tertiary amine of the following general formula: ##STR7## where R 5 , R 6 and R 7 are independently alkyl or hydroxyalkyl groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl, aryl, alkenyl of 2 to 20 carbon atoms or alkynyl 2 to 6 carbon atoms, or R 5 , R 6 and R 7 together with the nitrogen atom form an N-substituted heterocyclic 5 to 7 atom ring, and 1 to 35 wt%, based on tertiary amine, of an organic acid salt of a quaternary ammonium compound of the general formula: ##STR8## where R, R 1 and R 2 are independently alkyl or hydroxyalkyl groups of 1 to 4 carbon atoms, or together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure, R 3 is hydrogen or methyl and R 8 is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH 2 CN.
Claim 14
Dependent Claim 214 words
In a method for the preparation of a polyurethane product by the reaction of a polyisocyanate with a polyester or polyether polyol in the presence of a tertiary amine catalyst, the improvement which comprises employing a catalytically effective amount of a composition consisting essentially of a tertiary amine of the following general formula: ##STR7## where R 5 , R 6 and R 7 are independently alkyl or hydroxyalkyl groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl, aryl, alkenyl of 2 to 20 carbon atoms or alkynyl 2 to 6 carbon atoms, or R 5 , R 6 and R 7 together with the nitrogen atom form an N-substituted heterocyclic 5 to 7 atom ring, and 1 to 35 wt%, based on tertiary amine, of an organic acid salt of a quaternary ammonium compound of the general formula: ##STR8## where R, R 1 and R 2 are independently alkyl or hydroxyalkyl groups of 1 to 4 carbon atoms, or together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure, R 3 is hydrogen or methyl and R 8 is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH 2 CN.
Claim 15
Dependent Claim 18 words
The method of claim 12 in which the quaternary ammonium salt is 3-25 wt% of the tertiary amine.
Claim 16
Dependent Claim 24 words
The method of claim 12 in which the catalyst composition is present in an amount from 0.1 to 3 parts per 100 parts polyol.
Claim 17
Dependent Claim 13 words
The method of claim 14 in which the polyol is a polyester polyol.
Claim 18
Dependent Claim 13 words
The method of claim 14 in which the polyol is a polyether polyol.
Claim 19
Dependent Claim 316 words
A catalyst composition for the catalysis of the isocyanate/polyol reaction consisting essentially of a tertiary amine and 1 to 35 weight percent, based on the tertiary amine, of an organic acid salt of a quaternary ammonium compound of the formula: ##STR9## where a is 0 or 1, R, R 1 and R 2 are independently alkyl or hydroxyalky groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl (e.g. benzyl), aryl (e.g. phenyl), alkenyl of 2 to 20 carbon atoms, or alkynyl of 2 to 6 carbon atoms, or R, R 1 and R 2 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure; R 3 is hydrogen, phenyl, an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, a hydroxyalkyl group of 1 to 9 carbon atoms, a ketoalkyl group having a total of 3 to 15 carbon atoms, or an alkoxy alkyl group having a total of 2 to 20 carbon atoms; Y is hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, phenyl, an alkylphenyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the phenyl ring, benzyl, an alkylbenzyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the benzene ring, or a CH.sub.(3-b) Z.sub.(b) group wherein b is 1 to 3 and Z is --OH, --CN, --Cl, an alkoxy group of 1 to 5 carbon atoms, a phenyl group or methoxyphenyl group, or Z is (CH 2 ) d COOR 4 wherein d is equal to 0 to 4 and R 4 is hydrogen or an alkyl group of up to 20 carbon atoms.
Claim 20
Dependent Claim 316 words
A catalyst composition for the catalysis of the isocyanate/polyol reaction consisting essentially of a tertiary amine and 1 to 35 weight percent, based on the tertiary amine, of an organic acid salt of a quaternary ammonium compound of the formula: ##STR9## where a is 0 or 1, R, R 1 and R 2 are independently alkyl or hydroxyalky groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl (e.g. benzyl), aryl (e.g. phenyl), alkenyl of 2 to 20 carbon atoms, or alkynyl of 2 to 6 carbon atoms, or R, R 1 and R 2 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure; R 3 is hydrogen, phenyl, an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, a hydroxyalkyl group of 1 to 9 carbon atoms, a ketoalkyl group having a total of 3 to 15 carbon atoms, or an alkoxy alkyl group having a total of 2 to 20 carbon atoms; Y is hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, phenyl, an alkylphenyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the phenyl ring, benzyl, an alkylbenzyl having 1 to 9 carbon atoms in the alkyl group or groups attached to the benzene ring, or a CH.sub.(3-b) Z.sub.(b) group wherein b is 1 to 3 and Z is --OH, --CN, --Cl, an alkoxy group of 1 to 5 carbon atoms, a phenyl group or methoxyphenyl group, or Z is (CH 2 ) d COOR 4 wherein d is equal to 0 to 4 and R 4 is hydrogen or an alkyl group of up to 20 carbon atoms.
Claim 21
Dependent Claim 85 words
The catalyst composition of claim 17 in which the tertiary amine has the following general formula: ##STR10## where R 5 , R 6 and R 7 are independently alkyl or hydroxyalkyl groups of 1 to 20 carbon atoms, or cycloalkyl groups of 3 to 8 carbon atoms, aralkyl, aryl, alkenyl of 2 to 20 carbon atoms or alkynyl 2 to 6 carbon atoms, or R 5 , R 6 and R 7 together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure.
Claim 22
Dependent Claim 84 words
The catalyst composition of claim 18 in which a quaternary ammonium salt has the general formula: ##STR11## where R, R 1 and R 2 are independently alkyl or hydroxyalkyl groups of 1 to 4 carbon atoms, or together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure, R 3 is hydrogen or methyl and R 8 is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH 2 CN.
Claim 23
Dependent Claim 13 words
The catalyst composition of claim 19 in which the tertiary amine is triethylenediamine.
Claim 24
Dependent Claim 21 words
The catalyst composition of claim 19 in which the tertiary amine comprises 5 to 8 parts dimethylethanolamine per part of bis(dimethylaminoethyl)ether.
Claim 25
Dependent Claim 22 words
The catalyst composition of claim 19 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine.
Claim 26
Dependent Claim 22 words
The catalyst composition of claim 19 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of dimethyl-N-hydroxyethyl-N-2-hydroxypropyl quaternary amine.
Claim 27
Dependent Claim 22 words
The catalyst composition of claim 19 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of trimethyl-N-2-hydroxypropyl quaternary amine.
Claim 28
Dependent Claim 22 words
The catalyst composition of claim 20 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine.
Claim 29
Dependent Claim 22 words
The catalyst composition of claim 21 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of triethylenediamine-N-2-hydroxypropyl quaternary amine.
Claim 30
Dependent Claim 22 words
The catalyst composition of claim 20 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of dimethyl-N-hydroxyethyl-N-2-hydroxypropyl quaternary amine.
Claim 31
Dependent Claim 22 words
The catalyst composition of claim 20 in which the quaternary ammonium salt is the 2-ethyl hexanoic acid salt of trimethyl-N-2-hydroxypropyl quaternary amine.
Claim 32
Dependent Claim 55 words
A polyurethane composition comprising the following components in parts by weight: Polyether Polyol--100, Crosslinker--5-15, Water--0-0.4, Cell Stabilizer--0-0.3, Halocarbon Blowing Agent--2-8, Organometallic Catalyst--0-0.1, Isocyanate Prepolymer, free NCO%--98-105 Index, 18-22%, and the catalyst composition of claim 19 in which the tertiary amine is 0.3-0.6 parts by weight and the quaternary ammonium salt is 0.03-0.12 parts by weight.
Claim 33
Dependent Claim 55 words
A polyurethane composition comprising the following components in parts by weight: Polyether Polyol--100, Crosslinker--5-15, Water--0-0.4, Cell Stabilizer--0-0.3, Halocarbon Blowing Agent--2-8, Organometallic Catalyst--0-0.1, Isocyanate Prepolymer, free NCO%--98-105 Index, 18-22%, and the catalyst composition of claim 20 in which the tertiary amine is 0.3-0.6 parts by weight and the quaternary ammonium salt is 0.03-0.12 parts by weight.
Claim 34
Dependent Claim 55 words
The polyurethane composition comprising the following components in parts by weight Polyether Polyol--100, Crosslinker--5-15, Water--0-0.4, Cell Stabilizer--0-0.3, Halocarbon Blowing Agent--2-8, Organometallic Catalyst--0-0.1, Isocyanate Prepolymer, free NCO%--98-105 Index, 18-22%, and the catalyst composition of claim 25 in which the tertiary amine is 0.3-0.6 parts by weight and the quaternary ammonium salt is 0.03-0.12 parts by weight.
Claim 35
Dependent Claim 56 words
A polyurethane composition comprising the following components in parts by weight: Polyester Polyol--100, Crosslinker (ethylene glycol)--5-15, Water--0-0.5, Cell Stabilizer--0-1, Isocyanate prepolymer, free NCO%--96-104 Index, 18-22%, and the catalyst composition of claim 17 in which the tertiary amine is present at 0.3-0.6 parts by weight and the quaternary ammonium salt is present at 0.03-0.25 parts by weight.
Claim 36
Dependent Claim 56 words
A polyurethane composition comprising the following components in parts by weight: Polyester Polyol--100, Crosslinker (ethylene glycol)--5-15, Water--0-0.5, Cell Stabilizer--0-1, Isocyanate prepolymer, free NCO%--96-104 Index, 18-22%, and the catalyst composition of claim 20 in which the tertiary amine is present at 0.3-0.6 parts by weight and the quaternary ammonium salt is present at 0.03-0.25 parts by weight.
Claim 37
Dependent Claim 56 words
A polyurethane composition comprising the following components in parts by weight: Polyester Polyol--100, Crosslinker (ethylene glycol)--5-15, Water--0-0.5, Cell Stabilizer--0-1, Isocyanate prepolymer, free NCO%--96-104 Index, 18-22%, and the catalyst composition of claim 25 in which the tertiary amine is present at 0.3-0.6 parts by weight and the quaternary ammonium salt is present at 0.03-0.25 parts by weight.
Claim 38
Dependent Claim 56 words
The polyurethane composition comprising the following components in parts by weight: Polyester Polyol--100, Crosslinker (ethylene glycol)--5-15, Water--0-0.5, Cell Stabilizer--0-1, Isocyanate prepolymer, free NCO%--96-104 Index, 18-22%, and the catalyst composition of claim 27 in which the tertiary amine is present at 0.3-0.6 parts by weight and the quaternary ammonium salt is present at 0.03-0.25 parts by weight.
Claim 39
Dependent Claim 51 words
A polyurethane composition comprising the following components in parts by weight: Polyol--100, Water--0-2, Cell Stabilizer--0.7-2, Halocarbon Blowing Agent--20-55, Isocyanate--100-110 Index, and the catalyst composition of claim 17 in which the tertiary amine is present at 1-3 parts by weight and the quaternary ammonium salt is present at 0.04-0.2 parts by weight.
Claim 40
Dependent Claim 51 words
The polyurethane composition comprising the following components in parts by weight: Polyol--100, Water--0-2, Cell Stabilizer--0.7-2, Halocarbon Blowing Agent--20-55, Isocyanate--100-110 Index, and the catalyst composition of claim 21 in which the tertiary amine is present at 1-3 parts by weight and the quaternary ammonium salt is present at 0.04-0.2 parts by weight.
Claim 41
Dependent Claim 51 words
The polyurethane composition comprising the following components in parts by weight: Polyol--100, Water--0-2, Cell Stabilizer--0.7-2, Halocarbon Blowing Agent--20-55, Isocyanate--100-110 Index, and the catalyst composition of claim 26 in which the tertiary amine is present at 1-3 parts by weight and the quaternary ammonium salt is present at 0.04-0.2 parts by weight.

References Cited (Backward Citations)

US3087912A Cited
US3010963A Cited
US3050477A Cited
US3476933A Cited
US3824199A Cited
US3892687A Cited
US3993652A Cited
US4116879A Cited
US4040992A Cited
US4136240A Cited
US4186255A Cited
US4365025A Cited

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