Long term improvement of thermal insulation values in rigid polyisocyanurate/polyurethane comprising insulation foams

Abstract

Polyisocyanurate (PIR) and/or polyurethane (PUR) comprising insulation foams having significantly improved long term insulation values are disclosed as well as a processing method to fabricate said improved insulation foams and use of the improved insulation foams for thermal insulation.

Claims

1. A method for making a stabilized aged polyisocyanurate (PIR) comprising insulation foam, said method comprising: combining and/or mixing at least the following ingredients at an isocyanate index higher than 250 to form an insulation foam: a polyisocyanate composition comprising one or more polyisocyanate compounds; at least one catalyst compound suitable for making the stabilized aged polyisocyanurate (PIR) insulation foam; an isocyanate-reactive composition comprising one or more isocyanate reactive compounds including water; at least one physical blowing agent having a lambda gas value ≤12 mW/m.Math.K at 10° C.; at least one CO.sub.2 scavenging compound selected from NaOH and/or KOH; covering at least 50% of the insulation foam with a gas diffusion tight sealing to avoid exchange of air between the insulation foam and the environment; and ageing the insulation foam to achieve the stabilized aged polyisocyanurate (PIR) insulation foam; wherein the insulation foam is covered with a gas diffusion tight sealing and the amount of CO.sub.2 scavenging compound is such that the molar % CO.sub.2 in the stabilized aged polyisocyanurate (PIR) insulation foam is between 0 and 33% calculated on the total moles of CO.sub.2 and the at least one physical blowing agent in the stabilized aged polyisocyanurate (PIR) insulation foam, and the amount of residual at least one CO.sub.2 scavenging compound in the stabilized aged polyisocyanurate (PIR) insulation foam is greater than 0 and up to 10 wt % calculated on the total weight of the stabilized aged polyisocyanurate (PIR) insulation foam, and wherein the ratio of the molar amount of the at least one CO.sub.2 scavenging compound [X] to be added over the theoretical calculated molar amount of CO.sub.2 [X.sub.1] generated by the reaction of the molar amount of water the one more polyisocyanate compounds present in the formulation used to make the foam [X]/[X.sub.1] is higher than 6.

2. The method according to claim 1, wherein one or more polyisocyanate compounds are selected from the group consisting of a toluene diisocyanate, a methylene diphenyl diisocyanate, a polyisocyanate composition comprising a methylene diphenyl diisocyanate, or mixtures thereof.

3. The method according to claim 1, wherein the one or more isocyanate reactive compounds comprise polyols and polyol mixtures having average hydroxyl numbers of from 50 to 1000, and hydroxyl functionalities of from 2 to 8.

4. The method according to claim 1, wherein the at least one physical blowing agent is present in an amount of 1 to 60 parts by weight per hundred parts by weight of the one or more isocyanate reactive compounds.

5. The process according to claim 1, further comprising beside the at least one physical blowing agent having a lambda gas value ≤12 mW/m.Math.K at 10° C. additional blowing agents having a lambda gas value >12 mW/m.Math.K at 10° C. and wherein the ratio of the at least one physical blowing agent having a lambda gas value ≤12 mW/m.Math.K at 10° C. to the additional blowing agents is in the weight ratio 95/5 up to 5/95 calculated on the total weight of all blowing agents.

6. The process according to claim 1, wherein the molar % CO.sub.2 in the stabilized aged foam is between 0 and 27%.

7. The process according to claim 1, wherein the amount of residual at least one CO.sub.2 scavenging compound in the stabilized aged foam is between greater than 0 and 5 wt % calculated on the total weight of the stabilized aged foam.

8. The process according to claim 1, wherein the amount of residual at least one CO.sub.2 scavenging compound in the stabilized aged foam is between greater than 0 and 3 wt % calculated on the total weight of the stabilized aged foam.

9. The process according to claim 1, wherein the gas diffusion tight sealing is selected from a gas barrier polymeric resin layer or a metal foil.

10. The process according to claim 1, wherein the at least one physical blowing agent is selected from the group consisting of cis 1,1,1,4,4,4-hexafluorobut-2-ene, and/or trans 1-chloro-3,3,3-trifluoropropene, or combinations thereof.

11. The process according to claim 1, wherein the at least one physical blowing agent is selected from the group consisting of chlorofluorocarbons (CFCs) and/or hydrofluorocarbons (HFCs) and/or hydrochlorofluorocarbons (HCFCs) having a lambda gas value ≤12 mW/m.Math.K at 10° C.

Description

FIGURES

(1) FIG. 1 illustrates the influence of the CO.sub.2 scavenger on the lambda value (measured at 10° C.) in function of time (ageing at room temperature) for 1 foam made according to the invention (example 1) and for a comparative foam (comparative example 1).

(2) FIG. 2 illustrates the influence of the blowing agent on the lambda value (measured at 10° C.) in function of time (ageing at room temperature) for 3 foams made according to the invention (example 1, example 2 and example 3) and for 2 comparative foams (comparative examples 2+3).

(3) FIG. 3 illustrates the influence of diffusion tight conditions of the foam on the lambda value (measured at 10° C.) in function of time (ageing at room temperature) for a foam made according to the invention (example 1) and for a comparative foam (comparative example 4).

(4) FIG. 4 illustrates the lambda value measured at 10° C. for examples A2-A4 according to the invention and comparative examples A0-A1 in function of time (ageing at room temperature) using HCFO as physical blowing agent and different amounts of CO.sub.2 scavenger (illustrating the required amount of the CO.sub.2 scavenger).

(5) FIG. 5 illustrates the lambda value measured at 10° C. for examples B2-B3 according to the invention and comparative examples B0-B1 in function of time (ageing at room temperature) using cyclo-pentane as physical blowing agent and different amounts of CO.sub.2 scavenger (illustrating the required amount of the CO.sub.2 scavenger).

(6) FIG. 6 illustrates the lambda value measured at 10° C. for examples D2-D3 according to the invention and comparative examples D0-D1 in function of time (ageing at room temperature) using HCFO as physical blowing agent and different amounts of CO.sub.2 scavenger (illustrating the required amount of the CO.sub.2 scavenger).

MEASUREMENT METHODS

(7) 1. Titration Method to Determine the Residual Amount of Scavenger (NaOH) in the Stabilized Aged Foam

(8) A titration method is used to determine the residual amount of NaOH in the stabilized aged foam based on following reaction (which takes place in the stabilized aged foam):
2NaOH+CO.sub.2.fwdarw.Na.sub.2CO.sub.3+H.sub.2O  [1]

(9) Titration Method: A sufficient amount of foam is grinded and mixed with water in a closed system (sealed mixer) The water is filtered A measured amount of such filtered water is titrated with (0.5N) HCl solution Through the titration it is possible to determine the residual NaOH

(10) Titration Reaction:
NaOH+HCl.fwdarw.NaCl+H.sub.2O

(11) 2. Method to Determine the Amount of NaOH Required to have Optimal CO.sub.2 Removal and Minimal Residual NaOH in the Aged Foam A foam sample with the selected formulation is made according to real processing conditions or lab scale conditions without scavenger (NaOH). This sample (being sufficiently sealed with diffusion tight facing according to the invention) is aged until a stable lambda value is achieved (accelerated ageing can be applied). Once the lambda value after ageing is stabilized, the CO.sub.2 amount is measured (with Cell Gas Analysis (CGA)). This is the total CO.sub.2 generated in an aged foam sample without scavenger. The ‘stoichiometric’ amount of NaOH necessary to remove the measured amount of CO.sub.2 in the sample is calculated (referring to the above sole reaction [1]). As 2 mol NaOH react with 1 mol CO.sub.2, the mol ratio NaOH/CO.sub.2=2:1 A small excess to the calculated amount of NaOH is applied, a new prototype sample which include the NaOH scavenger is made according to real processing conditions or lab scale conditions. This new sample (being sufficiently sealed with diffusion tight facing according to the invention) is aged until a stable lambda value is achieved (accelerated ageing can be applied). Once lambda aged is stabilized, the residual NaOH is measured via titration, the residual CO.sub.2 is measured via CGA. The exact amount of NaOH to have the desired CO.sub.2 removal and/or the desired amount of residual NaOH can be fine-tuned via iteration.

Examples

(12) Chemicals Used: Polyisocyanate Suprasec® 5025 (S5025), a standard functionality polymeric MDI composition having an NCO %=31.0 and an average functionality=2.7 and viscosity at 25° C.=210 mPa.$) Polyisocyanate Suprasec® 2085 (S2085), a high functionality polymeric MDI composition having NCO %=30.5 and an average functionality=2.9 and viscosity at 25° C.=625 mPa.Math.s Foam stabilizer: silicon surfactant Catalyst 1: N,N-dimethylcyclohexylamine Catalyst 2: Pentamethyldiethylenetriamine Catalyst 3: 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine Catalyst 4: potassium octoate based catalyst Catalyst 5: potassium acetate based catalyst Sodium hydroxide beads (ex Sigma Aldrich), NaOH (20-40 Mesh) Sodium hydroxide Micropearls ex Prochimica Polyol 1: sucrose/DELA initiated polyether polyol (OHv=585 mg KOH/g, viscosity at 25° C.=4400 mPa.$) Polyol 2: DADPM/DEG initiated polyether polyol (OHv=310 mg KOH/g, viscosity at 25° C.=2000 mPa.$) Polyol 3: glycerol/sorbitol initiated polyether polyol (OHv=500 mg KOH/g, viscosity at 25° C.=610 mPa.$) Polyol 4: PTA based aromatic polyester polyol (OHv=240 mg KOH/g, viscosity at 25° C.=3000 mPa.$) Flame retardant 1: Tris (chloroisopropyl) phosphate (TCPP) Water Blowing agent n-Pentane, Blowing agent cyclo-Pentane, HCFO Blowing agent Solstice® 1233zd ex Honeywell, trans-1-chloro-3,3,3-trifluoropropene, (CHCl═CHCF.sub.3) HFO Blowing agent Opteon® 1100 ex Chemours (cis-1,1,1,4,4,4-hexafluorobut-2-ene, CF.sub.3CH═CHCF.sub.3) HFC Blowing agent Enovate® 245fa ex Honeywell

(13) 1. Fabrication of a PUR Comprising Insulation Foam Using CO.sub.2 Scavenger and HCFO Blowing Agent (Example 1) and Comparative Example 1 Using No CO.sub.2 Scavenger (Illustrating the Effect of the CO.sub.2 Scavenger)

(14) Two polyurethane comprising insulation foams were fabricated using an isocyanate index of 123.

(15) Table 1 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate 1) Example 1 according to the present invention using NaOH as a CO.sub.2 scavenger and HCFO blowing agent Solstice® 1233zd, and 2) Comparative example 1 using no CO.sub.2 scavenger and using HCFO blowing agent 1233zd as blowing agent.

(16) Both foams were produced in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) applying the same gas diffusion tight sealing according to the invention

(17) TABLE-US-00001 TABLE 1 Invention Reaction Comparative (example 1) system 1 pbw pbw Polyol 1 29.7 29.7 Polyol 2 15 15 Polyol 3 50.8 50.8 Catalyst 1 1.9 1.9 Catalyst 2 0.5 0.5 Catalyst 3 0.1 0.1 Foam stabilizer 0.7 0.7 Water 1.3 1.3 Blowing agent 7 7 HCFO (Solstice ® 1233zd) CO.sub.2 scavenger 0 21.6 (NaOH beads) Molar ratio 0 7.5:1 [X]/[X1] .sup.(**) S5025 162 162 Isocyanate Index 123 123 Foam density 63.5 71.7 (kg/m.sup.3) Facing diffusion diffusion tight facing tight facing Lateral Lateral open .sup.(*) open .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing (a multilayer Aluminum comprising foil being impermeable for air) on top and bottom surfaces of the foam and leaving the lateral sides open (thickness). This leads to a foam wherein 83% of the surfaces of the foam are covered with a diffusion tight sealing. .sup.(**) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1].

(18) The residual amount of NaOH measured in the aged foam, measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(19) TABLE-US-00002 Residual measured measured NaOH Amount of CO.sub.2 physical BA Measured scavenger in stabilized (stabilized (stabilized % CO.sub.2 .sup.(**.sup.) in aged Molar ratio the foam lambda aged aged) aged) (stabilized foam [X]/[X1].sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] aged) [%] [% w/w] Comparative 1 — 0 23.6 2.2 1.32 83% 0 (no scavenger) Example 1 7.5:1 7.4 18.6 0.02 1.16 5% 0.7 (with scavenger) .sup.(*.sup.)Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] .sup.(**.sup.) measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam.

(20) FIG. 1 illustrates the lambda value measured at 10° C. for example 1 and comparative example 1 in function of time (ageing at room temperature). The synergistic effect of the CO.sub.2 scavenger in combination with the use of a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (here HCFO blowing agent) under gas diffusion tight conditions is surprising and significant. Example 1 has a surprisingly low stabilized thermal conductivity <19 mW/m.Math.K while the comparative example 1 has a much higher stabilized thermal conductivity with values >23 mW/m.Math.K.

(21) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the example 1 foam stabilizes. To ensure the lambda value remains stabilized, the foam should be covered at least partly with a diffusion tight sealing (a multilayer Aluminum comprising foil being impermeable for air and CO.sub.2) on top and bottom surfaces of the foam.

(22) The comparative example 1 illustrates that the use of low thermal conductivity blowing agents under gas diffusion tight conditions is not sufficient to achieve insulation foams having a long term low lambda value.

(23) 2. Fabrication of a PUR Comprising Insulation Foam Using CO.sub.2 Scavenger, HCFO, HFO and HFC Blowing Agents (Examples 1, 2 and 3) and Comparative Examples 2+3 Using CO.sub.2 Scavenger and Alternative Blowing Agents (Illustrating the Effect of the Blowing Agent)

(24) Four polyurethane comprising insulation foams were fabricated in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) using an isocyanate index of 123.

(25) Table 2 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate 1) Example 1 according to the present invention using NaOH as a CO.sub.2 scavenger and HCFO blowing agent 1233zd, and 2) Example 2 according to the present invention using NaOH as a CO.sub.2 scavenger and HFO blowing agent Opteon® 1100, and 3) Example 3 according to the present invention using NaOH as a CO.sub.2 scavenger and HFC blowing agent Enovate® 245fa 4) Comparative example 2 using CO.sub.2 scavenger NaOH and using n-pentane as blowing agent having a lambda gas >>12 mW/m.Math.K at 10° C., and 5) Comparative example 3 using CO.sub.2 scavenger NaOH and water as the only blowing agent.

(26) All foams were produced applying the same gas diffusion tight sealing according to the invention (wherein 83% of the surfaces of the foam are covered with a gas diffusion tight sealing).

(27) TABLE-US-00003 TABLE 2 Invention Invention Invention Reaction Comparative Comparative (example 1) (example 2) (example 3) system 2 pbw 3 pbw pbw pbw pbw Polyol 1 29.7 29.7 29.7 29.7 29.7 Polyol 2 15 15 15 15 15 Polyol 3 50.8 50.8 50.8 50.8 50.8 Catalyst 1 1.9 1.9 1.9 1.9 1.9 Catalyst 2 0.5 0.5 0.5 0.5 0.5 Catalyst 3 0.1 0.1 0.1 0.1 0.1 Foam stabilizer 0.7 0.7 0.7 0.7 0.7 Water 1.3 2.3 1.3 1.3 1.3 Blowing agent HCFO 7 (Solstice ® 1233zd) Blowing agent 9 HFO (Opteon ® 1100) Blowing agent 3.9 n-pentane Blowing agent 7.2 HFC 245fa CO.sub.2 scavenger 21.3 22.5 21.6 21.7 21.6 (NaOH beads) Molar ratio 7.4:1 4.4:1 7.5:1 7.5:1 7.5:1 [X]/[X1] .sup.(**) S5025 162 181 162 162 162 Isocyanate Index 123 123 123 123 123 Foam density (kg/m.sup.3) 67.6 68.8 71.7 73.1 72.1 Facing diffusion diffusion diffusion diffusion diffusion tight facing tight facing tight facing tight facing tight facing Lateral Lateral Lateral Lateral Lateral open .sup.(*) open .sup.(*) open .sup.(*) open .sup.(*) open .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing (a multilayer Aluminum comprising foil being impermeable for Air) on top and bottom surfaces of the foam and leaving the lateral sides open. This leads to a foam wherein 83% of the surfaces of the foam are covered with a gas diffusion tight sealing. .sup.(**) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1].

(28) The residual amount of NaOH measured in the aged foam, measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(29) TABLE-US-00004 Residual measured measured NaOH Amount of CO.sub.2 physical BA Measured scavenger in stabilized (stabilized (stabilized % CO.sub.2 .sup.(**.sup.) in aged Molar ratio the foam lambda aged aged) aged) (stabilized foam [X]/[X1].sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] aged) [%] [% w/w] Example 1 7.5:1 7.4 18.6 0.02 1.16 5% 0.70 (Solstice LBA) Example 2 7.5:1 7.4 17.8 0.02 2.61 3% 0.60 (Opteon 1100) Example 3 7.5:1 7.4 19.3 0.03 1.96 5% 0.90 (HFC 245fa) Comparative 2 7.4:1 7.4 23.3 0.02 0.7 5% 0.60 (n-pentane) Comparative 3 4.4:1 7.4 28.sup.(***.sup.) 0.09 0 100%  0.10 (Water Blown) .sup.(*.sup.)Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] .sup.(**.sup.) measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam. .sup.(***.sup.)at 14 weeks not yet stabilized.

(30) FIG. 2 illustrates the lambda value measured at 10° C. for example 1, example 2, example 3 and comparative examples 2 and 3 in function of time (ageing at room temperature). The synergistic effect of the CO.sub.2 scavenger in combination with the use of a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. under air diffusion tight conditions is again surprising and significant. The comparative examples illustrate that the use of a CO.sub.2 scavenger under gas diffusion tight conditions is not sufficient to achieve insulation foams having a long term low lambda value.

(31) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the example foams 1, 2 and 3 stabilizes. To ensure the lambda value remains stabilized, the foam should be covered with a gas diffusion tight sealing (impermeable for air) on top and bottom surfaces of the foam.

(32) 3. Fabrication of a PIR Comprising Insulation Foam Using CO.sub.2 Scavenger and HCFO Blowing Agent (Example 1) and Comparative Example 4 Eliminating Gas Diffusion Tight Conditions (Illustrating the Effect of Sealing the Foam)

(33) Two polyurethane comprising insulation foams were fabricated in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) using an isocyanate index of 123.

(34) Table 3 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate 1) Example 1 according to the present invention using NaOH as a CO.sub.2 scavenger and a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (being here HCFO blowing agent Solstice® 1233zd) under gas diffusion tight conditions, and 2) Comparative example 4 using NaOH as a CO.sub.2 scavenger and a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (being here HCFO blowing agent 1233zd but no gas diffusion tight conditions (with gas permeable paper facing).

(35) TABLE-US-00005 TABLE 3 Invention Reaction Comparative (example 1) system 4 pbw pbw Polyol 1 29.7 29.7 Polyol 2 15 15 Polyol 3 50.8 50.8 Catalyst 1 1.9 1.9 Catalyst 2 0.5 0.5 Catalyst 3 0.1 0.1 Foam stabilizer 0.7 0.7 Water 1.3 1.3 Blowing agent 7 7 HCFO (Solstice ® 1233zd) CO.sub.2 scavenger 21.6 21.6 (NaOH beads) Molar ratio 7.5:1 7.5:1 [X]/[X1] .sup.(**) S5025 162 162 Isocyanate Index 123 123 Foam density 70.3 71.7 (kg/m.sup.3) Facing Gas Gas permeable diffusion paper tight facing facing Lateral open .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing (impermeable for Air) on top and bottom surfaces of the foam and leaving the lateral sides open. This leads to a foam wherein 83% of the surfaces of the foam are covered with a gas diffusion tight sealing (a multilayer Aluminum comprising foil being impermeable for Air). .sup.(**) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with isocyanate being present in the formulation used to make the foam [X.sub.1].

(36) The residual amount of NaOH measured in the aged foam, measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(37) TABLE-US-00006 measured Residual measured physical NaOH Amount of CO.sub.2 BA Measured scavenger in stabilized (stabilized (stabilized % CO.sub.2 .sup.(**.sup.) in aged Molar ratio the foam lambda aged aged) aged) (stabilized foam [X]/[X1] .sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] aged) [%] [% w/w] Comparative 4 7.5:1 7.4 21.2 0.07 1.23 14 0.9 Example 1 7.5:1 7.4 18.6 0.02 1.16 5 0.7 .sup.(*.sup.) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] .sup.(**.sup.) measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam.

(38) FIG. 3 illustrates the lambda value measured at 10° C. for example 1 and comparative example 4 in function of time (ageing at room temperature). The synergistic effect of the CO.sub.2 scavenger in combination with the use of a HCFO blowing agent and presence of a sealing is surprising and significant. Example 1 has a surprisingly low stabilized thermal conductivity <19 mW/m.Math.K while the comparative example 4 has no stabilized thermal conductivity, to the contrary the thermal conductivity is increasing (deteriorating) over time.

(39) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the example 1 stabilizes. To ensure the lambda value remains stabilized, the foam should be covered with a gas diffusion tight sealing (impermeable for Air) on top and bottom surfaces of the foam.

(40) The comparative example 4 illustrates that the application of a sealing to achieve gas diffusion tight conditions according to the invention is essential to achieve insulation foams having a long term low lambda value.

(41) 4. Fabrication of a PIR Comprising Insulation Foam Using HCFO as Physical Blowing Agent and Different Amounts of CO.sub.2 Scavenger (Illustrating the Required Amount of the CO.sub.2 Scavenger)

(42) Five polyisocyanurate comprising insulation foams were fabricated using an isocyanate index of 320.

(43) Table 4 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate: 1) Comparative example A0 using no scavenger and using HCFO blowing agent Solstice LBA, and 2) Comparative example A1 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 3:1 and using HCFO blowing agent Solstice LBA, and 3) Example A2 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 15:1 and using HCFO blowing agent Solstice LBA, and 4) Example A3 according to the invention using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 33:1 and using HCFO blowing agent Solstice LBA, and 5) Example A4 according to the invention using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 21:1 and using HCFO blowing agent Solstice LBA.

(44) All foams were produced in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) applying 100% gas diffusion tight EVOH sealing according to the invention.

(45) TABLE-US-00007 TABLE 4 Reaction Comparative Comparative Example Example Example system A0 pbw A1 pbw A2 pbw A3 pbw A4 pbw Polyol 4 80.16 80.16 80.16 80.16 80.16 Flame retardant 1 16 16 16 16 16 Catalyst 2 0.1 0.1 0.1 0.1 0.1 Catalyst 4 1.36 1.36 1.36 1.36 1.36 Catalyst 5 0.45 0.45 0.45 0.45 0.45 Foam stabilizer 1.6 1.6 1.6 1.6 1.6 Water 0.33 0.33 0.33 0.33 0.33 Blowing agent HCFO 32.7 32.7 32.7 32.7 32.7 (Solstice ® 1233zd) CO.sub.2 scavenger 0 2.2 10.9 24.0 15.2 (NaOH Micropearls) Molar ratio — 3:1 15:1 33:1 21:1 [X]/[X1] .sup.(**) S2085 170 170 170 170 170 Isocyanate Index 320 320 320 320 320 Foam density (kg/m.sup.3) 44.7 45.8 46.2 48.2 46.4 Facing diffusion diffusion diffusion diffusion diffusion tight tight tight tight tight facing .sup.(*) facing .sup.(*) facing .sup.(*) facing .sup.(*) facing .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing made of EVOH thereby fully encapsulating the foam (100% coverage). .sup.(**) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the foam [X.sub.1].

(46) The residual amount of NaOH measured in the aged foam, measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(47) TABLE-US-00008 Residual measured measured NaOH Amount of CO.sub.2 HFO % CO.sub.2.sup.(**.sup.) measured scavenger stabilized (stabilized (stabilized (stabilized in aged Molar ratio in the foam lambda aged aged) aged) aged) foam [X]/[X1].sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] [%] [% w/w] Comparative — 0 19.0 2.72 9.14 47%  0 A0 Comparative  3:1 0.7 18.6 1.78 9.21 36%  0 A1 Example A2 15:1 3.5 17.4 0.30 8.84 9% 0 Example A4 21:1 4.8 16.6 0 8.52 0% 0.2 Example A3 33:1 7.3 16.5 0 8.43 0% 2.7 .sup.(*.sup.)Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] .sup.(**.sup.)Measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam.

(48) FIG. 4 illustrates the lambda value measured at 10° C. for examples A2-A4 and comparative examples A0-A1 in function of time (ageing at room temperature). The synergistic effect of the optimized amount of CO.sub.2 scavenger in combination with the use of a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (here HCFO blowing agent) under gas diffusion tight conditions is surprising and significant. Examples A3 and A4 have surprisingly low stabilized thermal conductivity (<17 mW/m.Math.K while the comparative examples A1 and A0 have much higher stabilized thermal conductivity with values (>18.5 mW/m.Math.K).

(49) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the foam stabilizes. To ensure the lambda value remains stabilized, the foam should be covered with a diffusion tight sealing (here made of EVOH thereby fully encapsulating the foam (100% coverage)).

(50) The comparative example A1 illustrates that a molar ratio [X]/[X1] of 3:1 is not enough to have a sufficient CO.sub.2 reduction because with ageing, if the foam is sealed from gas transmission but not from moisture diffusion, the CO.sub.2 amount increases further. Therefore, a molar ratio [X]/[X1] much greater than 3:1 is required.

(51) The example A2 illustrates that even with a molar ratio [X]/[X1] of 15:1, no residual NaOH is found in the aged foam which means that all NaOH was consumed in the CO.sub.2 scavenging process, contributing to lambda reduction. Therefore a molar ratio [X]/[X1] much greater than 3:1 is required.

(52) 5. Fabrication of a PIR Comprising Insulation Foam Using Different Amounts of CO.sub.2 Scavenger and Cyclo-Pentane as a Physical Blowing Agent (Illustrating the Required Amount of the CO.sub.2 Scavenger)

(53) Five polyisocyanurate comprising insulation foams were fabricated using an isocyanate index of 320.

(54) Table 5 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate 1) Comparative example B0 using no scavenger and using cyclo-pentane as physical blowing agent, and 2) Comparative example B1 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 3:1 and using cyclo-pentane as physical blowing agent, and 3) Example B2 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 15:1 and using cyclo-pentane as physical blowing agent, and 4) Example B3 according to the invention using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 33:1 and using cyclo-pentane as physical blowing agent.

(55) All foams were produced in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) applying 100% gas diffusion tight EVOH sealing according to the invention.

(56) TABLE-US-00009 TABLE 5 Reaction Comparative Comparative Example Example system B0 pbw B1 pbw B2 pbw B3 pbw Polyol 4 80.16 80.16 80.16 80.16 Flame retardant 1 16 16 16 16 Catalyst 2 0.1 0.1 0.1 0.1 Catalyst 4 1.36 1.36 1.36 1.36 Catalyst 5 0.45 0.45 0.45 0.45 Foam stabilizer 1.6 1.6 1.6 1.6 Water 0.33 0.33 0.33 0.33 Blowing agent 17.2 17.2 17.2 17.2 Cyclo-pentane CO.sub.2 scavenger 0 2.2 10.9 24.0 (NaOH Micropearls) Molar ratio — 3:1 15:1 33:1 [X]/[X1] .sup.(**) S2085 170 170 170 170 Isocyanate Index 320 320 320 320 Foam density 45.3 45.3 46.5 48.7 (kg/m.sup.3) Facing diffusion diffusion diffusion diffusion tight tight tight tight facing .sup.(*) facing .sup.(*) facing .sup.(*) facing .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing made of EVOH thereby fully encapsulating the foam (100% coverage). .sup.(**) Molar ratio of added CO.sub.2 scavenger [X[ over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1].

(57) The residual amount of NaOH measured in the aged foam, measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(58) TABLE-US-00010 measured Residual measured cyclo NaOH Amount of stabilized CO.sub.2 pentane measured scavenger in lambda (stabilized (stabilized % CO.sub.2.sup.(**.sup.) in aged Molar ratio the foam aged aged) aged) (stabilized foam [X]/[X1].sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] aged) [%] [% w/w] Comparative B0 — 0 21.2 2.98 5.05 48% 0 Comparative B1  3:1 0.7 21.0 2.41 5.1 43% 0 Example B2 15:1 3.7 20.3 0.25 4.92 8% 0 Example B3 33:1 7.7 19.1 0 4.67 0% 1.75 .sup.(*.sup.)Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1]. .sup.(**.sup.)measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam.

(59) FIG. 5 illustrates the lambda value measured at 10° C. for examples B2-B3 and comparative examples B0-B1 in function of time (ageing at room temperature). The synergistic effect of the optimized amount of CO.sub.2 scavenger in combination with the use of a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (here cyclo-pentane blowing agent) under gas diffusion tight conditions is surprising and significant. Example B3 has surprisingly low stabilized thermal conductivity (around 19 mW/m.Math.K while the comparative examples B1 and B0 have much higher stabilized thermal conductivity with values (around 21 mW/m.Math.K).

(60) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the foam stabilizes. To ensure the lambda value remains stabilized, the foam should be covered with a diffusion tight sealing (here gas diffusion tight sealing made of EVOH thereby fully encapsulating the foam (100% coverage)).

(61) The comparative example B1 illustrates that a molar ratio [X]/[X1] of 3:1 is not enough to have a sufficient CO.sub.2 reduction because with ageing, if the foam is sealed from gas transmission but not from moisture diffusion, the CO.sub.2 amount increases further. Therefore a molar ratio [X]/[X1] much greater than 3:1 is required.

(62) 6. Fabrication of a PUR Comprising Insulation Foam Using HFO as Physical Blowing Agent and Different Amounts of CO.sub.2 Scavenger (Illustrating the Required Amount of the CO.sub.2 Scavenger)

(63) Four polyurethane comprising insulation foams were fabricated using an isocyanate index of 123.

(64) Table 6 summarizes the reaction system and amounts of ingredients used in parts by weight (pbw) to fabricate 1) Comparative example D0 using no scavenger and using HFO blowing agent Solstice LBA, and 2) Comparative example D1 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 3:1 and using HCFO blowing agent Solstice 1233zd, and 3) Example D2 using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 5:1 and using HCFO blowing agent Solstice 1233zd, and 4) Example D3 according to the invention using a molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1] of 7.5:1 and using HCFO blowing agent Solstice 1233zd.

(65) All foams were produced in a closed mould with dimensions 30 cm (Length) by 30 cm (Width) by 3 cm (Thickness) applying 100% gas diffusion tight EVOH sealing according to the invention.

(66) TABLE-US-00011 TABLE 6 Reaction Comparative Comparative Example Example system D0 pbw D1 pbw D2 pbw D3 pbw Polyol 1 29.7 29.7 29.7 29.7 Polyol 2 15 15 15 15 Polyol 3 50.8 50.8 50.8 50.8 Catalyst 1 1.9 1.9 1.9 1.9 Catalyst 2 0.5 0.5 0.5 0.5 Catalyst 3 0.1 0.1 0.1 0.1 Foam stabilizer 0.7 0.7 0.7 0.7 Water 1.3 1.3 1.3 1.3 Blowing agent 7 7 7 7 HCFO (Solstice ® 1233zd) CO.sub.2 scavenger 0 8.7 14.4 21.7 (NaOH Micropearls) Molar ratio — 3:1 5:1 7.5:1 [X]/[X1] .sup.(**) S5025 162 162 162 162 Isocyanate Index 123 123 123 123 Foam density 71.4 71.7 74.0 75.8 (kg/m.sup.3) Facing diffusion diffusion diffusion diffusion tight tight tight tight facing .sup.(*) facing .sup.(*) facing .sup.(*) facing .sup.(*) .sup.(*) The foam was fabricated applying a gas diffusion tight sealing made of EVOH thereby fully encapsulating the foam (100% coverage). .sup.(**) Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1].

(67) The residual amount of NaOH measured in the aged foam, the measured stabilized aged lambda values as well as the measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam are given below:

(68) TABLE-US-00012 Residual measured measured NaOH Amount of CO.sub.2 HFO measured scavenger stabilized (stabilized (stabilized % CO.sub.2.sup.(**.sup.) in aged Molar ratio in the foam lambda aged aged) aged) (stabilized foam [X]/[X1].sup.(*.sup.) [% w/w] [mW/m .Math. K] [% w/w] [% w/w] aged) [%] [% w/w] Comparative — 0 23.4 2.86 2.19 79% 0 D0 Comparative 3:1 3.1 22.1 1.12 2.14 61% 0 D1 Example D2 5:1 5.1 20.6 0.23 2.08 25% 0 Example D3 7.5:1   7.5 18.4 0 2.06  0% 0.84 .sup.(*.sup.)Molar ratio of added CO.sub.2 scavenger [X] over the theoretical calculated molar amount of CO.sub.2 generated by the reaction of the molar amount of water with molar amount of isocyanate being present in the formulation used to make the foam [X.sub.1]. .sup.(**.sup.)measured molar % of CO.sub.2 in the stabilized aged foam calculated on the total moles of CO.sub.2 and physical blowing agents in the stabilized aged foam.

(69) FIG. 6 illustrates the lambda value measured at 10° C. for examples D2-D3 and comparative examples D0-D1 in function of time (ageing at room temperature). The synergistic effect of the optimized amount of CO.sub.2 scavenger in combination with the use of a physical blowing agent with a lambda gas ≤12 mW/m.Math.K at 10° C. (here HCFO blowing agent) under gas diffusion tight conditions is surprising and significant. Example D3 has a surprisingly low stabilized thermal conductivity (<19 mW/m.Math.K and while the comparative examples A1 and A0 have much higher stabilized thermal conductivity with values (>22 mW/m.Math.K).

(70) It can be seen that the effect of the CO.sub.2 scavenger is complete after 8 weeks ageing, after that period the lambda value of the foam stabilizes. To ensure the lambda value remains stabilized, the foam should be covered with a diffusion tight sealing (here sealing made of EVOH thereby fully encapsulating the foam (100% coverage)).

(71) The comparative example D1 illustrates that a molar ratio [X]/[X1] of 3:1 is not enough to have a sufficient CO.sub.2 reduction because with ageing, if the foam is sealed from gas transmission but not from moisture diffusion, the CO.sub.2 amount increases further. Therefore, a molar ratio [X]/[X1] much greater than 3:1 is required.