ISOCYANATE TRIMERIZATION CATALYST FOR MAKING POLYISOCYANURATE COMPRISING FOAMS

Abstract

A trimerization catalyst composition suitable for making a polyisocyanurate comprising (insulation) foam, said composition comprising at least a trimerization catalyst compound selected from one or more organic salts from alkoxides wherein said organic salt is selected from alkali metal, earth alkali metal, a transition metal such as Ti and/or quaternary ammonium organic salts.

Claims

1. A process for making a polyisocyanurate-polyurethane comprising rigid foam (PIR-PUR), having a density <60 kg/m.sup.3, said process comprising combining and mixing at an isocyanate index of at least more than 100, preferably 180 or higher, more preferably higher than 250: a) a polyisocyanate composition comprising one or more polyisocyanate compounds; b) an isocyanate-reactive composition comprising one or more isocyanate reactive compounds; c) a trimerization catalyst composition comprising at least one trimerization catalyst compound selected from one or more organic alkoxides corresponding to the formula (I):
(RO.sup.).sub.xM.sup.+x(I) Wherein R is an organic group which is selected from an hydrocarbyl group wherein the hydrocarbyl groups has 1-4 carbon atoms, x is a number being defined by the oxidation state of M M is selected from an alkali metal ion, an earth alkali metal ion, a transition metal ion such as Ti or a quaternary ammonium ion d) optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerisation catalysts, or combinations thereof

2. The process according to claim 1 wherein the trimerization catalyst compound is selected from potassium ethoxide, sodium ethoxide, potassium methoxide, sodium methoxide, potassium tert-butoxide, titanium isopropoxide and mixtures thereof.

3. The process according to claim 1 wherein the trimerization catalyst compound is present in a solvent.

4. The process according to claim 1 wherein the trimerization catalyst composition further comprises a monool/polyol composition.

5. The process according to claim 4 wherein the polyol/monool composition is an isocyanate reactive agent which comprises polyester and/or polyether polyols having an average molecular weight of 32-6000 and an average nominal functionality of 1-8.

6. The process according to claim 1 wherein the trimerization catalyst compound is present in an amount such that the number of catalyst equivalents over the number of isocyanate equivalents ranges from 0.001 to 0.4, preferably in an amount from 0.01 to 0.26, or from 0.01 to 0.24, or from 0.02 to 0.2.

7. The process according to claim 1 wherein the polyisocyanate compounds are selected from a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition comprising a methylene diphenyl diisocyanate or a mixture of such polyisocyanates.

8. The process according to claim 1 wherein the one or more isocyanate reactive compounds are selected from monools and/or polyols such as glycols, polyether polyols and polyester polyols, mercaptans, carboxylic acids such as polybasic acids, amines, polyamines, components comprising at least one alcohol group and at least one amine group such as polyaminepolyols, urea and amides.

9. The process according to claim 1 wherein the isocyanate reactive compounds are selected from monools or polyols which have an average nominal hydroxy functionality of 1-8 and an average molecular weight of 32-8000 and mixtures of said monools and/or polyols.

10. The process according to claim 1 wherein the isocyanate reactive compounds are selected from monools selected from methanol, ethanol, propanol, butanol, phenol, cyclohexanol and hydrocarbon monools having an average molecular weight of 200-5000 like aliphatic and polyether monools and/or polyols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, sorbitol, sucrose, glycerol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, aromatic and/or aliphatic polyols having a molecular weight of up to 8000, preferably 200-6000 polyester polyols having an average molecular weight of 200-8000, preferably 200-6000, polyether polyester polyols having an average molecular weight of 200-8000, preferably 200-6000 and polyether polyols having an average molecular weight of 200-8000, preferably 200-6000.

11. The process according to claim 1 wherein the blowing agent is selected from isobutene, dimethyl ether, water, methylene chloride, acetone, chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), and/or hydrocarbons and is present in an amount of 1 to 80 pbw parts by weight (pbw), preferably from 5 to 60 pbw calculated per hundred weight parts of the one or more isocyanate reactive compounds (including the weight contribution of the catalyst system diluent).

12. (canceled)

13. (canceled)

14. A polyisocyanurate comprising material obtainable by the process according to claim 1.

15. The polyisocyanurate-polyurethane comprising rigid foam according to claim 12 having a free rise density (measured according to ISO 845) in the range of between 25 kg/m.sup.3 up to 60 kg/m.sup.3, preferably in the range 30 kg/m.sup.3 up to 55 kg/m.sup.3, a thermal conductivity in the range 20 up to 30 mW/mK, preferably 20 up to 25 mW/mK and having a closed cell content higher than 75% calculated on the total amount of closed and open cells being present in the material.

16. (canceled)

Description

FIGURES

[0115] FIG. 1 illustrates the PIR/PUR ratio in the core for a polyisocyanurate comprising insulation foam fabricated according to the present invention and for a polyisocyanurate comprising insulation foam not fabricated according to the invention (comparative) using an isocyanate index of 265 and 300.

[0116] FIG. 2 illustrates the PIR/PUR ratio in the skin for a polyisocyanurate comprising insulation foam fabricated according to the present invention and for a polyisocyanurate comprising insulation foam not fabricated according to the invention (comparative) using an isocyanate index of 265 and 300.

[0117] FIG. 3 illustrates the increase in PIR conversion in the core and the skin for a polyisocyanurate comprising insulation foam fabricated using an isocyanate index of respectively 265 (example 1) and 300 (example 2) according the according to the present invention compared to a polyisocyanurate comprising insulation foam not according to the invention fabricated using an isocyanate index of 265 and 300 (wherein the comparative foam is taken as 100%).

EXAMPLES

Chemicals Used:

[0118] Suprasec 2085 polyisocyanate ex Huntsman, in the examples indicated as S2085

[0119] Flame retardant Tris chloroisopropyl phosphate (TCPP)

[0120] Tegostab B8484 ex Evonik, polyether modified polysiloxane-copolymer

[0121] Catalyst Dabco K15 ex Air Products, Potassium octoate in Diethylene glycol

[0122] Catalyst Cat LB ex Huntsman Potassium Acetate/Ethyleneglycol/water

[0123] Sodium Ethoxide ex Sigma Aldrich, 21% pure in ethanol

[0124] Daltolac 8251 ex Huntsman PO polyol, glycerol initiated OHv=250 mg KOH/g

[0125] Water

[0126] N-Pentane ex Emplura

[0127] Catalyst PMDETA ex Huntsman, Pentaethyldiethylenetriamine

[0128] Suprasec, Daltolac and Daltocel are trademarks of the Huntsman Corporation or an Affiliate thereof and have been registered in one or more but not all countries.

Example 1: Fabrication of a Polyisocyanurate Comprising Insulation Foam Using Isocyanate Index 265

[0129] Two polyisocyanurate comprising insulation foams were fabricated using an isocyanate index of 265. The foam according the according to the present invention was prepared using Na-ethoxide as a trimerization catalyst (example 1). For the comparative foam 1, Cat LB and Dabco K15 was used as a trimerisation catalyst.

[0130] Table 1 summarizes the amounts of ingredients used in pbw (part by weight) to fabricate example 1 according to the present invention using Na-ethoxide as a trimerization catalyst and to fabricate comparative foam 2 using Cat LB and Dabco K15 as a trimerisation catalyst, both at an isocyanate index of 265.

TABLE-US-00001 TABLE 1 Comparative 1 Invention (example 1) pbw pbw S2085 190 198 Daltolac R251 100 100 TCCP 15 15.4 Tegostab B 8484 2 2.06 PMDETA 0.25 0.27 Cat LB 0.40 Dabco K15 2.20 Sodium ethoxide (21%) 2.03 Water 0.50 0.51 n-pentane 19 19.6 ISO index 265 265 Free Rise Density (kg/m.sup.3) 58 56 End of rise (s) 127 132 Cream Time (s) 14 13

[0131] FIG. 1 illustrates the PIR/PUR ratio in the core for example 1 and for the comparative example fabricated using an isocyanate index of 265. The increase in PIR conversion for example 1 compared to the comparative example 1 is significant.

[0132] FIG. 2 illustrates the PIR/PUR ratio in the skin of the foam for example 1 and for the comparative example fabricated using an isocyanate index of 265. The increase in PIR conversion for example 1 in the skin compared to the comparative example 1 is significant and surprising.

[0133] FIG. 3 illustrates the increase in PIR conversion in the core and the skin for a polyisocyanurate comprising insulation foam fabricated using an isocyanate index of respectively 265 (example 1a) according the according to the present invention compared to a polyisocyanurate comprising insulation foam not according to the invention fabricated using an isocyanate index of 265 and 300 (wherein the comparative foam is taken as 100%).

Example 2 Fabrication of a Polyisocyanurate Comprising Insulation Foam Using Isocyanate Index 300

[0134] Two polyisocyanurate comprising insulation foams were fabricated using an isocyanate index of 300. The foam according the according to the present invention was prepared using Na-ethoxide as a trimerization catalyst (example 2). For the comparative foam 2, Cat LB and Dabco K15 was used as a trimerisation catalyst.

[0135] Table 2 summarizes the amounts of ingredients used in pbw (part by weight) to fabricate the example 2 according to the present invention using Na-ethoxide as a trimerization catalyst and to fabricate the comparative foam 2 using Cat LB and Dabco K15 as a trimerisation catalyst, both at an isocyanate index of 300.

TABLE-US-00002 TABLE 2 Comparative 2 Invention (example 2) pbw pbw S2085 218 228 Daltolac R251 100 100 TCCP 16.4 16.9 Tegostab B 8484 2.2 2.3 PMDETA 0.3 0.3 Cat LB 0.4 Dabco K15 2.4 Sodium ethoxide (21%) 2.2 Water 0.5 0.6 n-pentane 21 21.6 ISO index 300 300 Free Rise Density (kg/m.sup.3) 56 61 End of rise (s) 133 115 Cream Time (s) 17 12

[0136] FIG. 1 illustrates the PIR/PUR ratio in the core for example 2 and for the comparative example fabricated using an isocyanate index of 300. The increase in PIR conversion for example 2 compared to the comparative example 2 is significant.

[0137] FIG. 2 illustrates the PIR/PUR ratio in the skin of the foam for example 1 and for the comparative example fabricated using an isocyanate index of 300. The increase in PIR conversion for example 2 in the skin compared to the comparative example 2 is still significant and surprising.

[0138] FIG. 3 illustrates the increase in PIR conversion in the core and the skin for a polyisocyanurate comprising insulation foam fabricated using an isocyanate index of respectively 300 (example 1) according the according to the present invention compared to a polyisocyanurate comprising insulation foam not according to the invention fabricated using an isocyanate index of 300 (wherein the comparative foam is taken as 100%).