THERMOLATENT CATALYST FOR POLYMERIZATION OF ISOCYANATES

Abstract

The present invention relates to novel thermolatent catalysts for the manufacture of isocyanurate and polyisocyanate polymers.

Claims

1. A method for producing a polymer comprising: a) providing a polymerizable composition having a molar ratio of isocyanate groups to all functional groups reactive with isocyanate in the polymerizable composition of at least 3.0:1.0 comprising (i) a liquid phase comprising at least one polyisocyanate, (ii) a solid phase comprising at least one catalyst comprising a metal salt having a carboxylate of an aliphatic carboxylic acid comprising at least 12 carbon atoms or a phenolate as an anion capable of crosslinking the polyisocyanate so that a polymer is formed, wherein said catalyst is solid below a temperature of 50° C. and is liquid or dissolved at a polymerization temperature of 60° C. to 280° C., and b) heating the polymerizable composition to the polymerization temperature and maintaining said temperature at least until the polymerizable composition reaches the gel point.

2. The method of claim 1, wherein the catalyst is present as particles having a number average diameter of 100 nm to 100 μm.

3. The method of claim 1, wherein the anion of the salt is a carboxylate.

4. The method of claim 3, wherein the carboxylate is derived from a carboxylic acid with at least 12 carbon atoms.

5. The method of claim 4, wherein the carboxylate is selected from the group consisting of: laureate, myristate, palmitate, stearate, and dimeric acids.

6. The method of claim 1, wherein the metal is selected from the group consisting of: potassium, lithium, sodium, calcium, and barium.

7. The method of claim 6, wherein the metal is potassium.

8. The method of claim 1, wherein the polyisocyanate is selected from the group consisting of: PDI, HDI, IPDI, H12MDI, TDI, MDI, XDI, TMXDI, and oligomeric polyisocyanates formed from the aforementioned diisocyanates.

9. The method of claim 1, wherein at least 40 wt. % of all polyisocyanates of the polymerizable composition are monomeric and/or oligomeric aliphatic polyisocyanates.

10. The method of claim 1, wherein the polymerizable composition comprises up to 60 wt.-% of at least one aromatic polyisocyanate.

11. The method of claim 1, wherein the metal salt is suspended in a polyethylene glycol derivative having at least three consecutive ethylene oxide units.

12. The method of claim 1, wherein the polymerizable composition reaches a viscosity less than 3 times a starting viscosity at handling temperatures within 90 minutes after mixing, and reaches the gel point within 20 min or less at the polymerization temperature.

13. The method of claim 1, further comprising contacting a fiber with the polymerizable composition provided in method step a) before performing method step b).

14. A method of crosslinking isocyanate groups, comprising catalyzing isocyanate crosslinking with a catalyst comprising at least one metal salt, wherein the metal is selected from the group consisting of potassium, lithium, sodium, calcium, and barium and wherein said metal salt is solid below a temperature of 50° C. and is liquid at a polymerization temperature.

Description

EXAMPLES

[0101] Experiment Information:

[0102] The currently prevailing ambient temperature of 25° C. is described as RT in experimental part.

[0103] The NCO functionality of the various raw materials was determined from the respective data sheet of the raw materials.

[0104] Raw Material:

[0105] Desmodur® N 3600 is a hexamethylene diisocyanate (HDI) trimer (NCO functionality >3) with 23.0 wt.-% NCO content, the viscosity is about 1200 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0106] Desmodur® N 3900 is a HDI trimer (NCO functionality >3) with 23.5 wt.-% NCO content, the viscosity is about 730 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0107] Desmodur® XP 2489 is a HDI isophorone diisocyanate (IPDI) polyisocyanate (NCO functionality >3) with 21.0 wt.-% NCO content, the viscosity is about 22500 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0108] Desmodur® eco N 7300 is a biobased pentamethylene diisocyanate (PDI) trimer (NCO functionality >3) with 21.9 wt.-% NCO content, the viscosity is about 9500 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0109] Desmodur® W is a monomeric dicyclohexylmethane 4,4′-diisocyanate (H.sub.12MDI) (NCO functionality is 2) with 31.8 wt.-% NCO content, the viscosity is about 30 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0110] Desmodur® N 3300 is a hexamethylene diisocyanate (HDI) trimer (NCO functionality >3) with 21.8 wt.-% NCO content, the viscosity is about 3000 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0111] Desmodur® 3133 is a mixture of modified diphenylmethane-4,4′-diisocyanate (MDI) with isomers and homologues of higher functionality with 32.5 wt.-% NCO content, the viscosity is about 25 mPas at 23° C. (DIN EN ISO 3219/A.3), from Covestro AG.

[0112] PEG 400 is polyethylene glycol with a number average molecular weight Mn of 400 and a purity of 99.5 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0113] PEG 200 is polyethylene glycol with a number average molecular weight Mn of 200 and a purity of 99.5 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0114] DEG is diethylene glycol with a purity 98.0 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0115] Potassium stearate was purchased with a purity >98.0 wt.-% from Macklin Inc.

[0116] Potassium acetate was purchased with a purity 92.0 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0117] Potassium oleate was purchased with a purity 99.5 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0118] Potassium 2-ethylhexanoate was purchased with a purity >95 wt.-% from TCI Co., Ltd.

[0119] Potassium laurate was purchased with a purity >95 wt.-% from Micxy reagent Co., Ltd.

[0120] Potassium palmitate was purchased with a purity >95 wt.-% from Spectrum Chemical Mfg. Corp.

[0121] Hydrogenated dimer acid was purchased from Tianjin Heowns Biochemical Technology Co., Ltd.

[0122] Glycerol was purchased with a purity 99.0 wt.-% from Sinopharm Chemical Reagent Co., Ltd.

[0123] DBTL is dibutyltin dilaurate and was purchased with a purity >95 wt.-% from TCI Co., Ltd.

[0124] Determining the Brookfield Viscosity:

[0125] The viscosity of a small amount of reactive resin material including the catalyst was determined according to DIN EN ISO 3219 by Brookfield DV-II+ Pro viscometer. The viscosity of fresh polyisocyanate composition with catalyst was measured immediately after mixing by SpeedMixer at RT (starting viscosity). The time interval between the test time and the end time of mixing was not more than 15 min. The latency of this mixture was monitored by measuring the viscosity of the resin material after storage at 50° C. for 3 hours in a sealed container. The viscosity was tested at the temperature of mixture (50° C.) without cooling down to RT.

[0126] Determining the Tg Value by DSC:

[0127] The glass transition temperature (Tg) of the cured resins was determined by differential scanning calorimetry (DSC) on a TA DSC Q20 according to DIN EN 61006. Pure indium was used as standard for calorimetric calibration. Runs were carried out using empty standard hermetic pans as a reference. About 10 mg resin sample was accurately weighted and capsuled in aluminum hermetic pan for test. The measurement was carried out by heating at a heating rate of −20° C. to 200° C. with 20° C./min heating rate, followed by cooling at a cooling rate of 20° C./min. Nitrogen was used as purge gas. The values in Table 1 were based on the evaluation of 1.sup.st cycle of heating curve. The Tg was taken as the half-height of the corresponding glass transition stage.

[0128] Synthesis of dimer acid potassium salt Hydrogenated dimer acid (55.6 g) was added into water (130.0 g). The beaker was immersed into an oil bath, heated to a temperature between 70 and 80° C., and the mixture was stirred with an IKA stirrer with the speed of 300 rpm. After 15 min, 42.8 wt % KOH aqueous solution (25.5 g; COOH:OH=1:1) was added slowly dropwise to the dimer acid solution. The more KOH solution was added, the more of a white precipitation was obtained. After all potassium hydroxide was added, the mixture was stirred for another 15 min to form a white gel. The white gel was dried in an oven at 80° C. A white solid powder was obtained. The yield was quantitative.

[0129] Determining the Solubility of the Catalyst Salts:

[0130] A simple determination of the solubility of catalyst salts depending on different temperatures is shown in the following example: The catalyst salt (e.g. potassium stearate) and the solvent (e.g. PEG 400) were accurately weighted to prepare dispersions with 9 different concentrations including 0.01, 0.02, 0.05, 1.0, 2.0, 5.0, 10.0, 15.0 and 20.0 wt.-% salt in solvent. Then, the dispersions were stirred at 3 different temperatures: R.T., 50° C., and polymerization temperature (e.g. 180° C.) for 8 hours and checked carefully if there were any solids left in the solution. The highest concentration of the solutions with no residual solids left was defined as the solubility at this corresponding temperature. Following this procedure the solubility of potassium stearate in PEG 400 (polyethylene glycol with molecule weight of 400) at room temperature is 0.02 wt.-%; at 50° C. it is 1.0 wt % and at 180° C. it is 5.0 wt %.

[0131] Dimer acid potassium also shows similar characterization as potassium stearate. The solubility of dimer acid potassium in PEG 400 at room temperature is 1.0 wt.-% and at 180° C. is 10.0 wt.-%.

[0132] Determining the Particle Size of the Carboxylic Acid Salts:

[0133] The particle size of the solid catalyst was determined by using a particle analyzer Zetasizer Nano ZS 3600 from Fa. Malvern at room temperature. The solid catalyst particles were suspended in PEG 400 at room temperature according to the general procedure for catalyst preparation (Method A) and then stepwise diluted until the measurement could be conducted. The average particle size of the solid catalyst was determined for potassium stearate (534 nm; STD 140 nm), potassium laurate (474 nm; STD 274 nm) and potassium palmitate (bimodal; 467 nm, STD 110 nm; 5260 nm, STD 437 nm).

[0134] General Procedure for Catalyst Preparation:

[0135] Method a (Catalyst-Suspension)

[0136] The following example is a typical method for preparing a catalyst system based on suspensions with potassium stearate in PEG 400 or DEG:

[0137] Potassium stearate (5.0 g) was mixed with PEG 400 (95.0 g). The final concentration of potassium stearate was 5 wt.-%. This mixture was mechanically stirred at RT for 10-30 min until most of the potassium salt was well dispersed. This fine suspension of powdered potassium salt in liquid PEG 400 was used as catalyst without further treatment.

[0138] 10 wt.-%, 20 wt.-%, and 30 wt.-% suspensions of potassium stearate in PEG 400, 20 wt.-% suspension of potassium stearate in DEG, 20 wt.-% suspension of potassium palmitate in PEG 400, 11 wt.-% suspension of potassium laurate in PEG 400, and 5 wt.-% and 30 wt.-% suspensions of dimer acid potassium in PEG 400 were prepared exactly as in the aforementioned process except that the final concentration of potassium salts and the type of solvent were adjusted.

[0139] Method B (Catalyst-Solution)

[0140] The following example is a typical method for preparing a catalyst system of clear and homogeneous potassium salt solutions:

[0141] Potassium Acetate (5.0 g) was mixed with PEG 400 (95.0 g). The final concentration of potassium acetate was 5 wt.-%. The mixture was mechanically stirred at RT until all potassium salt was completely dissolved. A clear and homogeneous solution was obtained and used as catalyst without further treatment.

[0142] 5 wt.-% solution of potassium 2-ethylhexanoate in PEG 400, 5 wt.-% solution of potassium oleate in PEG 400 and 15 wt.-% solution of potassium oleate in PEG 400 were prepared exactly as in the aforementioned process except that the type of potassium salt, solvent and concentration of potassium salt were adjusted.

[0143] General Procedure for Polyisocyanurates Sample Preparation:

[0144] The isocyanate components and aforementioned catalyst were carefully weighed in a FlackTek mixing cup and mixed at 2500 rpm for at 60-180 seconds using a SpeedMixer DAC 400 FV. The latency (i.e. viscosity change at 50° C.) of one set of samples was observed and recorded in Table 1. The other set of duplicate samples (10 g of each sample) were heated at a heating platform to 180° C. Periodic observations were made until the polyisocyanurate resin was firm and non-tacky, and the time was recorded.

Example 1

[0145] As described above, a 5 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. 10 g of the mixture were subsequently put into a mold (metal lid, about 6 cm in diameter and about 1 cm high) followed by heating on the heating platform of an IKA RCT stirrer with the setting temperature at 180° C. The cure time was recorded until the resin was firm and non-tacky. The resin was separated from the mold after curing and 10 mg of the resin were used for measuring Tg by DSC. The viscosity of freshly-made resin mixture was measured within 15 min after mixing and checked again after storage at 50° C. oven for 3 hours in a closed container. The results are shown in table 1.

Example 2

[0146] As described above, a 10 wt % suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 3

[0147] As described above, a 15 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 4

[0148] As described above, a 20 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 5

[0149] As described above, a 30 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 6

[0150] As described above, a 20 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3900 (95.0 g) and catalyst suspension (5.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 7

[0151] As described above, a 20 wt.-% suspension of potassium stearate in DEG was obtained and used as catalyst. Desmodur® N 3600 (93.5 g) and catalyst suspension (4.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 8

[0152] As described above, a 10 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® XP 2489 (93.5 g) and catalyst suspension (4.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 9

[0153] As described above, a 15 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® eco N 7300 (95.0 g) and catalyst suspension (5.0 g) were mixed by ixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 10

[0154] As described above, a 20 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (45.0 g), Desmodur® W (45.0 g) and catalyst suspension (4.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 11

[0155] As described above, a 20 wt.-% suspension of potassium palmitate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 12

[0156] As described above, a 11 wt.-% suspension of potassium laurate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 13

[0157] As described above, a 5 wt.-% suspension of dimer acid potassium in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (93.5 g) and catalyst suspension (4.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 14

[0158] As described above, a 30 wt.-% suspension of dimer acid potassium in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (93.5 g) and catalyst suspension (4.0 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Example 15

[0159] As described above, 5 wt.-% suspension of potassium stearate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (119.0 g), Glycerol (20.0 g) and catalyst suspension (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 2.

Example 16

[0160] 40 g Desmodur® N 3300 were premixed with 1.8 g 10 wt.-% potassium stearate in DEG and then mixed with 60 g Desmodur® 3133. At 180 degree the curing time was less than 2 minutes while the gel time at room temperature was 100 minutes. When 10 wt.-% potassium stearate in DEG were replaced by 10 wt.-% potassium acetate in DEG, the reaction mixture reached the gel point almost immediately.

Comparative Example 1

[0161] As described above, a 5 wt.-% clear and homogeneous solution of potassium acetate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst solution (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. After storage at 50° C. in an oven for 3 hours, the reaction mixture solidified to form a white gel, the viscosity value could not be measured anymore. The results are shown in table 1.

Comparative Example 2

[0162] As described above, a 5 wt.-% clear and homogeneous solution of potassium oleate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst solution (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Comparative Example 3

[0163] As described above, a 5 wt % clear and homogeneous solution of potassium 2-ethylhexanoate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst solution (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. After storage at 50° C. in an oven for 3 hours, the reaction mixture solidified to form a white gel, the viscosity value could not be measured anymore. The results are shown in table 1.

Comparative Example 4

[0164] As described above, a 15 wt % clear and homogeneous solution of potassium oleate in PEG 400 was obtained and used as catalyst. Desmodur® N 3600 (91.5 g) and catalyst solution (4.5 g) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 1.

Comparative Example 5

[0165] Desmodur® N 3600 (119.0 g) and Glycerol (20.0 g) without catalyst were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 2.

Comparative Example 6

[0166] Desmodur N 3600 (119.0 g), Glycerol (20.0 g) and DBTL (11.9 mg) were mixed by SpeedMixer. The experiment was conducted in the same way as example 1 and the curing time, Tg and viscosity were recorded. The results are shown in table 2.

TABLE-US-00001 TABLE 1 Viscosity of Viscosity after mixture after Curing Time mixing within storage at 50° C. Example No. Polyisocyanate Catalyst Compositon at 180° C. 15 min at RT for 3 hours Tg Example 1 Desmodur ® N 3600 5 wt % Potassium Stearate in <5 min 812 mPa .Math. s 1428 mPa .Math. s 104° C. PEG 400  .sup. (50″-1′50″) Example 2 Desmodur ® N 3600 10 wt % Potassium Stearate in <5 min 895 mPa .Math. s 1080 mPa .Math. s 104° C. PEG 400 (1′02″-2′05″) Example 3 Desmodur ® N 3600 15 wt % Potassium Stearate in <5 min 860 mPa .Math. s 1548 mPa .Math. s 105° C. PEG 400  .sup. (59″-2′05″) Example 4 Desmodur ® N 3600 20 wt % Potassium Stearate in <5 min 852 mPa .Math. s 1170 mPa .Math. s 105° C. PEG 400  .sup. (59″-2′00″) Example 5 Desmodur ® N 3600 30 wt % Potassium Stearate in <5 min 980 mPa .Math. s 1108 mPa .Math. s 106° C. PEG 400 (1′17″-2′05″) Example 6 Desmodur ® N 3900 20 wt % Potassium Stearate in <5 min 660 mPa .Math. s 898 mPa .Math. s  80° C. PEG 400 (1′30″-3′00″) Example 7 Desmodur ® N 3600 20 wt % Potassium Stearate in <5 min 820 mPa .Math. s 1543 mPa .Math. s 110° C. DEG (1′14″-1′50″) Example 8 Desmodur ® XP 2489 10 wt % Potassium Stearate in <5 min 9000 mPa .Math. s 16500 mPa .Math. s 129° C. PEG 400 (1′22″-2′25″) Example 9 Desmodur ® eco N 15 wt % Potassium Stearate in <5 min 6520 mPa .Math. s 7800 mPa .Math. s 132° C. 7300 PEG 400 (1′15″-1′45″) Example10 Desmodur ® N 3600 20 wt % Potassium Stearate in <5 min 180 mPa .Math. s 230 mPa .Math. s 129° C. Desmodur ® W (1:1) PEG 400 (1′36″-2′30″) Example 11 Desmodur ® N 3600 20 wt % Potassium Palmitate in <5 min 1400 mPa .Math. s 2470 mPa .Math. s 103° C. PEG 400 (1′13″-2′10″) Example 12 Desmodur ® N3600 11 wt % Potassium Laurate in <5 min 1900 mPa .Math. s 3600 mPa .Math. s 105° C. PEG 400 (1′10″-1′50″) Example 13 Desmodur ® N 3600 5 wt % Dimer acid potassium in <5 min 790 mPa .Math. s 1528 mPa .Math. s 112° C. PEG 400 (2′30″-4′19″) Example 14 Desmodur ® N 3600 30 wt % Dimer acid potassium in <5 min 1380 mPa .Math. s 1624 mPa .Math. s 115° C. PEG 400 (2′30″-3′47″) Comparative Desmodur ® N 3600 5 wt % Potassium Acetate in <5 min 904 mPa .Math. s gel 103° C. Example 1 PEG 400 (1′03″-2′10″) Comparative Desmodur ® N 3600 5 wt % Potassium Oleate in <5 min 952 mPa .Math. s 6300 mPa .Math. s 103° C. Example 2 PEG 400 (1′17″-2′10″) Comparative Desmodur ® N 3600 5 wt % Potassium 2- <5 min 1330 mPa .Math. s gel 105° C. Example 3 ethylhexanoate in PEG 400  .sup. (50″-1′45″) Comparative Desmodur ® N 3600 15 wt % Potassium Oleate in <5 min 874 mPa .Math. s 9378 mPa .Math. s 104° C. Example 4 PEG 400 (1′10″-2′15″)

[0167] The experiments show that the polyisocyanurate compositions of examples 1 to 7 had a rapid cure behavior at higher curing temperature with curing time less than 5 min, meanwhile with higher Tg. This curing behavior is comparable with the systems of Comparative Example 1 to 4 which were catalyzed by homogenous solutions of conventional potassium carboxylates salts. Meanwhile the example 1 to 7 showed better storage stability at accelerated aging condition than comparative examples 1 to 4. The viscosity of the examples 1 to 7 after storage at elevated temperature for 3 hours had not doubled, and kept close to 1000 mPa.Math.s which is the optimum viscosity range for the practical operation and impregnation of the fibers in composite applications. Examples 1-7 show that the catalyst concentration used at room or at the elevated temperature will not obviously affect the viscosity change, which is supporting the assumption that no or only little amounts of catalyst are available at low temperature. On the other hand, at higher (curing) temperature the catalyst becomes available. This characteristic of the systems allows for high catalyst loadings without sacrificing pot-life.

[0168] As shown in Table 2, this latent reactive catalyst system can also be applied for polyurethane formation. The viscosity change of example 15 is comparable to Comparative example 5 without any catalyst inside, but the curing rate is faster than the system without catalyst. Comparative example 6 shows that traditional tin catalyst-DBTL will cause fast curing but with very short pot life.

TABLE-US-00002 TABLE 2 Viscosity of Viscosity after mixture after Polyisocyanate + Curing Time mixing within storage at 50° C. Example No. Polyol Catalyst Compositon at 180° C. 15 min at RT for 3 hours Tg Example 15 Desmodur ® N 5 wt % Potassium Stearate in <5 min 1548 mPa .Math. s 421 mPa .Math. s 75° C. 3600 + Glycerol PEG 400 (2′40″-3′50″) Comparative Desmodur ® N No Catalyst >10 min  1548 mPa .Math. s 438 mPa .Math. s 53° C. Example 5 3600 + Glycerol (15′00″-20′00″) Comparative Desmodur ® N DBTL <5 min 1428 mPa .Math. s gel 98° C. Example 6 3600 + Glycerol (1′20″-2′00″)

[0169] Due to the aforementioned prolonged storage stability and the rapid curing, the reaction mixtures disclosed in this invention are very suitable for practical and efficient manufacturing of fiber reinforced polyisocyanurate and polyurethane composites with the possibility of omitting the use of expensive metering apparatus.