Delayed action/enhanced curing catalysis in polyurethane systems

• US 4,582,861 A
• Filed: 11/13/1984
• Issued: 04/15/1986
• Est. Priority Date: 11/13/1984
• Status: Expired due to Term

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Andrew, Gary D., Galla, Edward A., Ricci, Robert L.
• Primary Examiner(s): Cockeram, Herbert S.
• Application Number:
  US06/670,705
• Time in Patent Office: 518 Days
• Field of Search: 528/49, 528/52, 521/118, 252/182
• US Class Current: 521/118
• CPC Class Codes: C08G 18/1875 containing ammonium salts or mixtures of secondary of tertiary amines and acids
• CPC Class Codes: C08G 18/2063 having two nitrogen atoms in the condensed ring system
• CPC Class Codes: Y10S 521/902 Cellular polymer containing an isocyanurate structure

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.

Claims

1. 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, R₁ and R₂ 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, R₁ and R₂ together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure;

R₃ 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

space="preserve" listing-type="equation">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 (CH₂)_d COOR₄ wherein d is equal to 0 to 4 and R₄ is hydrogen or an alkyl group of up to 20 carbon atoms.

2. The method of claim 1 in which the quaternary ammonium salt is 3-25 wt% of the tertiary amine.

3. The method of claim 1 in which the tertiary amine has the following general formula ##STR5## where R₅, R₆ and R₇ 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

R₅, R₆ and R₇ together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure.

4. The method of claim 1 in which the tertiary amine is triethylenediamine.

5. The method of claim 1 in which the tertiary amine comprises 5 to 8 parts dimethylethanolamine per part of bis(dimethylaminoethyl)ether.

6. The method of claim 1 in which the quaternary ammonium salt has the general formula:

##STR6## where R, R₁ and R₂ 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,

R₃ is hydrogen or methyl and R₈ is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH₂ CN.

7. 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.

8. 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.

9. 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.

10. 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.

11. 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.

12. 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 R₅, R₆ and R₇ 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

R₅, R₆ and R₇ 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, R₁ and R₂ 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,

R₃ is hydrogen or methyl and R₈ is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH₂ CN.

13. The method of claim 12 in which the quaternary ammonium salt is 3-25 wt% of the tertiary amine.

14. 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.

15. The method of claim 14 in which the polyol is a polyester polyol.

16. The method of claim 14 in which the polyol is a polyether polyol.

17. 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, R₁ and R₂ 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, R₁ and R₂ together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure;

R₃ 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

space="preserve" listing-type="equation">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 (CH₂)_d COOR₄ wherein d is equal to 0 to 4 and R₄ is hydrogen or an alkyl group of up to 20 carbon atoms.

18. The catalyst composition of claim 17 in which the tertiary amine has the following general formula:

##STR10## where R₅, R₆ and R₇ 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

R₅, R₆ and R₇ together with the nitrogen atom form an N-substituted heterocyclic 5-7 atom ring structure.

19. The catalyst composition of claim 18 in which a quaternary ammonium salt has the general formula:

##STR11## where R, R₁ and R₂ 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,

R₃ is hydrogen or methyl and R₈ is hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, benzyl or --CH₂ CN.

20. The catalyst composition of claim 19 in which the tertiary amine is triethylenediamine.

21. The catalyst composition of claim 19 in which the tertiary amine comprises 5 to 8 parts dimethylethanolamine per part of bis(dimethylaminoethyl)ether.

22. 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.

23. 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.

24. 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.

25. 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.

26. 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.

27. 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.

28. 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.

29. 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.

30. 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.

31. 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.

32. 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.

33. 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.

34. 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.

35. 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.

36. 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.

37. 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.

38. 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.