Polyisocyanate Trimerization Catalyst Composition

• US 20150031527A1
• Filed: 03/12/2013
• Published: 01/29/2015
• Est. Priority Date: 03/29/2012
• Status: Abandoned Application

• Current Assignee: Huntsman International LLC (Huntsman Corporation)
• Original Assignee: Huntsman Internatio9nal LLC
• Inventors: Esbelin, Christian, Verbeke, Hugo, Verbeke, Hans Godelieve Guido
• Application Number:
  US14/382,020
• Publication Number:
  US 20150031527A1
• Time in Patent Office: Days
• US Class Current: 502/167
• CPC Class Codes: B01J 31/0247 Imides, amides or imidates (R-C=NR(OR))
• CPC Class Codes: B01J 31/04 containing carboxylic acids or their salts B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226
• CPC Class Codes: C08G 18/092 oligomerisation to isocyanurate groups
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/225 of alkali or alkaline earth metals
• CPC Class Codes: C08G 18/285 Nitrogen containing compounds
• CPC Class Codes: C08G 18/3829 containing ureum groups
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/58 Epoxy resins C08G18/42, C08G18/48 take precedence; reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen C08G18/6407, with at least equivalent amounts of amines C08G18/6415; polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen C08G18/003
• CPC Class Codes: C08G 18/725 Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• CPC Class Codes: C08G 18/7664 containing alkylene polyphenyl groups
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group
• CPC Class Codes: C08G 18/794 formed by oligomerisation of aromatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/797 containing carbodiimide and/or uretone-imine groups
• CPC Class Codes: C08G 2115/02 to isocyanurate groups
• CPC Class Codes: C08K 5/21 Urea; Derivatives thereof, e.g. biuret

Abstract

A trimerization catalyst composition comprising a trimerization catalyst compound selected from one or more organic metal salt, preferably alkali or earth alkali metal salts, and one or more compounds selected from compounds which comprise a carboxamide group having the structure —CO—NH₂ and/or from compounds which comprise a group having the structure —CO—NH—CO— is disclosed. Further a stable polyisocyanate composition comprising the catalyst composition and a process for making the polyisocyanate composition is disclosed. A curable polyisocyanate composition is obtained comprising the catalyst composition, a polyisocyanate composition, an epoxy resin and optionally a polyol/monool composition and a polyisocyanurate comprising material made by allowing the curable composition to react at elevated temperature and a process for making the polyisocyanurate comprising material.

Claims

1. A trimerization catalyst composition comprising:

a trimerization catalyst compound selected from one or more organic metal salts, selected from alkali or earth alkali metal salts, and

one or more compounds selected from compounds which comprise a carboxamide group having the structure —

CO—

NH₂ and/or from compounds which comprise a group having the structure —

CO—

NH—

CO—

.

2. The catalyst composition according to claim 1 wherein the number of equivalents of compounds which comprise a group having the structure —

CO—

NH—

CO—

is greater than the number of trimerization catalyst equivalents.

3. The catalyst composition according to claim 1 wherein the number of equivalents of compounds which comprise a carboxamide group having the structure —

CO—

NH₂ is greater than the number of trimerization catalyst equivalents, preferably greater than 4 times the number of trimerization catalyst equivalents.

4. The catalyst composition according to claim 1 wherein the organic metal salt is a carboxylate or alkoxide and is preferably selected from one or more of potassium acetate, potassium hexanoate, potassium ethylhexanoate, potassium octanoate, potassium lactate, sodium ethoxide, sodium formate, potassium formate, sodium acetate, potassium benzoate and mixtures thereof.

5. The catalyst composition according to claim 1 wherein the compound comprising a group having the structure —

CO—

NH—

CO—

comprises the structure R₁—

CO—

NH—

CO—

R₂ wherein R₁ and R₂ each independently from each other are selected from

     1) hydrogen (—

H),

     2) —

NR₃R₄,

     3) hydrocarbyl having 1-100 carbon atoms and optionally comprising hydroxy, ether, halogen, carboxyl, oxygen, isocyanate and/or amine groups wherein R₃ and R₄ independently from each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups which hydrocarbyl groups have 1-20 carbon atoms and optionally comprise hydroxy, ether, halogen, carboxyl, isocyanate and/or amine groups, wherein R₁ and R₂ may be linked to each other essentially forming a ring structure including the —

CO—

NH—

CO—

group, and wherein the hydrocarbyl groups in the compounds corresponding to the formula R₁—

CO—

NH—

CO—

R₂ may be a combination of linear, branched, saturated, unsaturated, cyclic and/or non-cyclic aliphatic, aromatic or araliphatic hydrocarbyls and mixtures of such compounds.

6. The catalyst composition according to claim 1 wherein the compound comprising a group having the structure —

CO—

NH—

CO—

comprises the structure R₁—

CO—

NH—

CO—

R₂ wherein R₁ and R₂ together with the —

CO—

NH—

CO—

group form a 4 to 12 membered ring structure including the —

CO—

NH—

CO—

group.

7. The catalyst composition according to claim 1 wherein the compound comprising the —

CO—

NH—

CO—

group corresponds to a compound comprising a —

CO—

NH—

CO—

NH—

group and is a reaction product of a compound comprising a carboxamide group having the structure —

CO—

NH₂ and a polyisocyanate compound comprising a reactive NCO group.

8. The catalyst composition according to claim 7 wherein the compound comprising a —

CO—

NH—

CO—

NH—

group corresponds to R₆—

CO—

NH—

CO—

NH—

R₇ and wherein;

the compound comprising a carboxamide group corresponds to NH₂—

CO—

R₆ and wherein R₆ is

     1) hydrogen (—

H),

     2) —

NR₈R₉,

     3) hydrocarbyl having 1-20 carbon atoms and optionally comprising hydroxy, ether, halogen and/or amine groups, or

     4) —

R₁₀—

CO—

NH₂, wherein R₈ and R₉, independently from each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups which hydrocarbyl groups have 1-10 carbon atoms and optionally comprise hydroxy, ether, halogen and/or amine groups and wherein R₁₀ is a bivalent hydrocarbon radical having up to 8 carbon atoms and mixtures of these carboxamides, and

the compound comprising a reactive NCO group corresponds to R₇—

NCO and wherein R₇ is selected from hydrogen and hydrocarbyl groups which hydrocarbyl groups have 1-20 carbon atoms and optionally comprise hydroxy, ether, halogen, carboxyl, isocyanate and/or amine groups and wherein said hydrocarbyl groups may be a combination of linear, branched, saturated, unsaturated, cyclic and/or non-cyclic aliphatic, aromatic or araliphatic hydrocarbyls and mixtures of such compounds.

9. The catalyst composition according to claim 8 wherein R₆ is selected from 1) —

NR₈R₉,

     2) alkyl having 1-10 carbon atoms and optionally comprising 1-3 hydroxy and/or ether groups,

     3) phenyl or

     4) tolyl wherein R₈ and R₉, independently from each other, are selected from hydrogen, hydroxy, phenyl, tolyl and alkyl having 1-6 carbon atoms and optionally comprising an hydroxy and/or an ether and mixtures of such compounds.

10. A monool or polyol composition comprising at least one of the compounds of the catalyst composition according to claim 1 and wherein the polyol/monool composition preferably comprises polyester and/or polyether polyols having an average molecular weight of 32-6000 and an average nominal functionality of 1-8.

11. A stable polyisocyanate composition comprising the catalyst composition according to claim 1 and a polyisocyanate composition in such an amount that the number of equivalents of compounds which comprise a group having the structure —

CO—

NH—

CO—

is greater than the number of trimerization catalyst equivalents and the ratio of the number of —

CO—

NH—

CO—

groups to the number of isocyanate groups is at most 1.

12. The polyisocyanate composition according to claim 11 further comprising a polyol/monool composition wherein said polyol/monool composition comprises polyester and/or polyether polyols having an average molecular weight of 32-6000 and an average nominal functionality of 1-8.

13. The polyisocyanate composition according to claim 11, the composition having an isocyanate value of 10 to 48% by weight.

14. The polyisocyanate composition according to claim 11, wherein the polyisocyanate composition comprises a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition comprising a methylene diphenyl diisocyanate or a mixture of such polyisocyanate compounds.

15. A process for making a composition according to claim 1 which process comprises combining and mixing the compounds which comprise a carboxamide group having the structure —

CO—

NH₂ and/or the compounds which comprise a group having the structure —

CO—

NH—

CO—

group to the trimerization catalyst.

16. A process for making a composition according to claim 11 which process comprises combining and mixing the compounds of the catalyst composition according to claim 1 and one or more polyisocyanate compounds and optionally a polyol/monool composition which preferably comprises polyester and/or polyether polyols having an average molecular weight of preferably 32-6000 and an average nominal functionality of preferably 1-8, such that the ratio of —

CO—

NH—

CO—

groups over the number of isocyanate groups is at most 1, preferably at most 0.01, more preferably at most 0.0015 and a stable polyisocyanate composition is formed.

17. A process according to claim 16 which process comprises first or at least simultaneously adding the one or more compounds selected from compounds which comprise a carboxamide group having the structure —

CO—

NH₂ and/or compounds which comprise a group having the structure —

CO—

NH—

CO— and

then combining the trimerization catalyst to the polyisocyanate composition.

18. A curable polyisocyanate composition comprising the compounds of the stable polyisocyanate composition according to claim 11, and an epoxy resin wherein the number of equivalents of compounds having a —

CO—

NH—

CO—

group in the curable polyisocyanate composition is smaller than or equal to the number of epoxy equivalents.

20. A process for making a curable polyisocyanate composition according to claim 18, by combining and mixing:

the compounds according to the catalyst composition of claims 1-9, and

a polyisocyanate composition which comprises a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition comprising a methylene diphenyl diisocyanate or a mixture of such polyisocyanates, and

an epoxy resin, and

optionally a polyol/monool composition which preferably comprises polyester and/or polyether polyols having an average molecular weight of preferably 32-6000 and an average nominal functionality of preferably 1-8,

which process comprises first or at least simultaneously adding the one or more compounds selected from compounds which comprise a carboxamide group having the structure —

CO—

NH₂ and/or compounds which comprise a group having the structure —

CO—

NH—

CO— and

then combining the trimerization catalyst to the polyisocyanate composition.

21. A polyisocyanurate comprising material made by allowing a curable composition according to claim 18 to react at elevated temperature.

24. The stable polyisocyanate composition according to claim 11, wherein the number of —

CO—

NH—

CO—

groups to the number of isocyanate groups is at most 0.01.

25. The stable polyisocyanate composition according to claim 11, wherein the number of —

CO—

NH—

CO—

groups to the number of isocyanate groups is at most 0.0015.

26. The polyisocyanate composition according to claim 13, wherein the composition has an isocyanate value of 20 to 33% by weight.

19. (canceled)

22-23. -23. (canceled)