HFO CONTAINING PU FORMULATION

Abstract

The present invention is directed to polyol composition comprising a polyol mixture (PM) comprising a polyetherol (P1) based on a polyhydric alcohol and a polyetherol (P2) based on a diamine; and at least one hydrohaloolefin (HFO) as blowing agent, a process for preparing a polyurethane foam using said polyol composition and the polyurethane foam obtained or obtainable by said process.

Claims

1-15. (canceled)

16. A polyol composition comprising: (a) a polyol mixture (PM) comprising a polyetherol (P1) based on a polyhydric alcohol and a polyetherol (P2) based on a diamine; and (b) at least one hydrohaloolefin (HFO) as blowing agent, wherein the diamine is selected from the group consisting of ethylenediamine, toluenediamine (TDA), and mixtures thereof, wherein polyol (P2) is present in the polyol mixture in an amount in the range of from 1 to 40 parts by weight based on the total weight of the polyol mixture.

17. The polyol composition according to claim 16, wherein the polyhydric alcohol is at least one selected from the group consisting of sucrose, pentaerythritol, glucose, glycerol, glycol, trimethylolpropane (TMP) and sorbitol, and combinations thereof.

18. The polyol composition according to claim 16, wherein the hydrohaloolefin is at least one selected from the group consisting of trans-1-chloro-3,3,3-trifluoro-propene (HCFO-1233zd(E)), cis-1-chloro-3,3,3-trifluoro-propene (HCFO-1233zd(Z)), trans-1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(E)), cis-1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(Z)), trans-1,3,3,3-tetrafluorprop-1-en (HFO-1234ze(E)), and cis-1,3,3,3-tetrafluorprop-1-en (HFO-1234ze(Z)).

19. The polyol composition according to claim 16, wherein the polyol composition comprises at least one tertiary amine as catalyst.

20. The polyol composition according to claim 16, wherein the polyetherol (P2) is a toluene diamine-initiated alkylene oxide polyether polyol.

21. The polyol composition according to claim 16, wherein the polyetherol (P2) has a hydroxyl number in the range of from 100 to 1000 mg KOH/g.

22. The polyol composition according to claim 16, wherein polyol (P1) is present in the polyol mixture in an amount in the range of from 10 to 80 parts by weight based on the total weight of the polyol mixture.

23. The polyol composition according to claim 16, wherein the polyol mixture (PM) comprises at least one polyester polyol (P3).

24. The polyol composition according to claim 23, wherein the polyol (P3) is present in the polyol mixture in an amount in the range of from 1 to 50 parts by weight based on the total weight of the polyol mixture.

25. The polyol composition according to claim 16, wherein the hydrohaloolefin is present in an amount of from 3 to 40 parts by weight based on the total weight of the polyol composition.

26. The polyol composition according to claim 16, wherein the composition further comprises at least one selected from the group consisting of a flame retardant, an ultraviolet stabilizer, a surfactant and a filler.

27. A process for preparing a polyurethane foam, comprising: (i) reacting at least one polyisocyanate with a polyol composition comprising: (a) a polyol mixture (PM) comprising a polyetherol (P1) based on a polyhydric alcohol and a polyetherol (P2) based on a diamine; and (b) at least one hydrohaloolefin (HFO) as blowing agent, wherein the diamine is selected from the group consisting of ethylenediamine, toluenediamine (TDA), and mixtures thereof, wherein polyol (P2) is present in the polyol mixture in an amount in the range of from 1 to 40 parts by weight based on the total weight of the polyol mixture.

28. A polyurethane foam obtained by the process according to claim 27.

Description

EXAMPLES

[0174] 1. Methods:

[0175] 1.1 Determination of the hydroxyl numbers: [0176] The hydroxyl numbers were determined according to DIN 53240 (1971-12).

[0177] 1.2 Determination of the demolding behavior (only for refrigeration): [0178] The demolding behavior was determined by measuring the post-expansion of foam bodies produced using a box mold having the dimensions 70040090 mm.sup.3 at a temperature of 452 C. as a function of the demolding time and the overpacking (OP=the ratio of overall foam density to minimum fill density). The post-expansion was determined by measuring the height of the foam cuboids after 24 hours. [0179] The less the measured height of the foam cuboids differ from 90 mm, the better is the demolding behavior.

[0180] 1.3 Determination of the minimum fill density (only for refrigeration): [0181] For the determination of the minimum fill density a mold box with dimensions 200020050 mm.sup.3 at a temperature of 452 C. is filled with enough polyurethane reaction mixture to just fill the mold without direct contact with the end of the mold. The flow distance is measured. The MFD is then calculated according to MFD=(m*L/(V*s)) where m=shot weight; L=Length of the mold, s=Flow distance=effective length of the foam, V=Volume of the mold

[0182] 1.4. Determination of free rise density: [0183] 1.4.1 Refrigeration: About 900 g of reaction mixture is injected in a PE bag (about 30 cm in diameter). To determine the free rise core density of the foam after curing (24 h later), samples are cut out of the middle of the sample. They are weighed and their volume is determined by immersion in a water bath. These quantities are used to compute their density and the mean value is reported. [0184] 1.4.2 Spray foam: 3 different free rise densities are determined by spray foam. [0185] Beaker free rise density: This is the foam density obtained by a hand-mix foam in a beaker of known volume. The system components are mixed directly in a beaker. After foam curing the part of the foam that stands above the rim of the beaker is cut off. The beaker free rise density is the quotient between the weight of the foam contained in the beaker and its volume. [0186] Core free rise density: Several layers of reaction mixture are sprayed on a PE plate. To determine the free rise core density after curing of the foam, samples are cut out of the middle of the foam without skins. They are weighted and their volume is determined measuring the three dimensions of the cut specimens with a caliper. These quantities are used to compute their density and the mean value is reported. [0187] Total free rise density: From the same foam sprayed on the PE plate to obtain the core free rise density other foam specimens are cut out from the middle of the sample with all skins from bottom to top. They are weighted and their volume is determined by immersion in a water bath. These quantities are used to compute their density and the mean value is reported.

[0188] 1.5 Determination of cream time: [0189] Cream time is defined as time interval between shot commencement and commencement of volume expansion of the reaction mixture.

[0190] 1.6 Determination of string time (also known as gel time): [0191] The string time is defined as time interval between shot commencement and the moment at which fibers can be pulled out of the reaction mixture using a foam strip or a rod.

[0192] 1.7 Determination of rise time: [0193] The rise time is defined as time interval between shot commencement and the end of volume expansion.

[0194] 1.8 Determination of tack free time (only for spray foam): [0195] The tack free time is defined as time interval between shot commencement and the moment at which the top surface of the foam is established as no longer tacker determined by means of a foam strip or a rod.

[0196] 1.9 Determination of thermal conductivity: [0197] 1.9.1 Refrigeration: The thermal conductivity is determined using a heat flow measurement plate instrument Taurus TCA300 DTX at an average temperature of 10 C. In order to produce the test specimens, the polyurethane reaction mixture is introduced into heated mold having dimensions 200020050 mm.sup.3 (14.5% overpacking) and removed from the mold after 5 min (-.fwdarw.Table 1) or 7 min (.fwdarw.Table 2). After storage for 24 h under standard conditions of temperature and humidity, a plurality of cuboids of about 20020050 mm.sup.3 in size are cut out of the middle (positions 10, 900 and 1700 mm based on the start of the mold). The upper and lower side were subsequently removed so that test specimens have dimensions of 20020030 mm.sup.3. [0198] 1.9.2 Spray foam: The thermal conductivity is determined using a heat flow measurement plate instrument Lasercomp FOX 314 or Taurus TCA300 DTX at an average temperature of 10 C. in accordance with European Standard EN 12667. In order to produce the test specimens several layers of reaction mixture are sprayed on a PE plate. [0199] Three types of thermal conductivity values are determined for spray foam: [0200] (a) Initial value of thermal conductivity (in accordance with EN 14315-1-C.3): a test specimen with dimensions of 30030030 mm is cut from a core foam sample, which is maximum 8 days old. After conditioning for at least 16 h of the cut specimen for at least 16 h at 233 C. and 5010% relative humidity the thermal conductivity is determined as before described. [0201] (b) Normality test value of thermal conductivity for fixed increment method to calculate aged value of thermal conductivity (in accordance with EN 14315-1-C.5): a test specimen with dimensions of 300300(20-22) mm is cut from a core foam sample, which is maximum 8 days old. Initial value thermal conductivity of this thinner specimen is determined in the same way as before described. Afterwards this specimen is stored at 702 C. during 211 days. After ageing the specimen is reconditioned for at least 16 h at 233 C. and 5010% and thermal conductivity again measured. Normality test value is the difference between initial and aged value. [0202] (c) Accelerated aged value of thermal conductivity (in accordance with EN 14315-1-C.4): in this case the entire uncut spray foam with all skins from top to bottom is stored at 702 C. during 1755 days. After ageing the foam is conditioned for at least 16 h at 233 C. and 5010%. Afterwards a test specimen with dimensions of 30030030 mm is cut from aged core foam sample and thermal conductivity measured as before described.

[0203] 2. Starting materials: [0204] Polyol A1: Polyetherol based on vic-TDA and PO, OH value: 400 mg KOH/g [0205] Polyol A2: Polyetherol based on vic-TDA, EO and PO, OH value: 160 mg KOH/g [0206] Polyol A3: Polyetherol based on vic-TDA, EO and PO, OH value: 390 mg KOH/g [0207] Polyol B1: Polyetherol based on sucrose, glycerol and PO, OH value: 450 mg KOH/g [0208] Polyol B2: Polyetherol based on sorbitol and PO, OH value: 490 mg KOH/g [0209] Polyol B3: Polyetherol based on glycerol, EO and PO, OH value: 158 mg KOH/g [0210] Polyol C1: Polyetherol based on sucrose, pentaerythritol, DEG and PO, OH value: 403 mg KOH/g [0211] Polyol C2: Polyetherol based on PG and PO, OH value: 104 mg KOH/g [0212] Polyol C3: Polyetherol based on glycerol and PO, OH value: 400 mg KOH/g [0213] Polyol D1: Polyesterol based on terephthalic acid, oleic acid, phthalic anhydride, glycerol and DEG, OH value: 245 mg KOH/g [0214] Polyol D2: Polyetherol based on TMP and EO, OH value: 605 mg KOH/g [0215] Polyol E: Polyetherol based on sucrose, DEG, EO and PO, OH value: 400 mg KOH/g [0216] Catalyst mixture F) comprising: [0217] Catalyst F1): Dimethyl cyclohexylamine [0218] Catalyst F2): Bis-(2-dimethylaminoethyl)ether [0219] Catalyst F3): Potassium acetate [0220] The catalyst mixture F) used in the examples comprises the catalysts F1 to F3, containing 50-95% of catalyst F1, 5-30% of catalyst F2 and 0-35% of catalyst F3. [0221] Catalyst mixture G) comprising: [0222] Catalyst G1): 1,1,3,3-Tetramethylguanidine [0223] Catalyst G2): 1,2-Dimethylimidazole [0224] Catalyst G3): Dibutyl tin dilaurate [0225] Catalyst G4): Pentamethyldiethylenetriamine [0226] The catalyst mixture G) used in the examples comprises the catalysts G1 to G4, containing 50-70% of catalyst G1, 20-40% of catalyst G2, 1-10% of catalyst G3, and 1-10% of catalyst G4. [0227] Surfactant H1): Silicone surfactant, Tegostab B8467, Tegostab B8474 and/or Tegostab B8491 by Evonik [0228] Surfactant H2): Silicone surfactant, Niax Silicone L-6906MB by Momentive and/or Dabco DC 193 by AirProducts [0229] Crosslinker I): Glycerol, OH value: 1825 mg KOH/g [0230] Flame retardant J): Tris (2-chloro isopropyl) phosphate [0231] Isocyanate: Polymeric MDI, NCO content: 31.5 pbw (Lupranat M20)

[0232] 3. Preparation procedure

[0233] 3.1 Refrigeration [0234] A polyol component was produced from the raw materials indicated. The polyol component was mixed with the amount of the indicated isocyanate required to achieve an isocyanate index (=the ratio of actual amount of isocyanate used to theoretical amount of isocyanate required) as shown in Table 1 or Table 2 by means of a high-pressure Puromat KM 16/40 (KraussMaffei) at a discharge rate of 250 g/sec. [0235] The reaction mixture was injected into temperature- controlled molds having dimensions of 2000 mm200 mm50 mm or 400 mm700 mm90 mm and allowed to foam there. The overpacking was 17.5%. [0236] In Table 1 and 2, the respective compositions and the results for the polyurethane foams obtained are summarized. The amount of the blowing agent (HCFO-1233zd(E)) is given in parts per weight, based on 100 parts of the polyol component (.fwdarw.Table 1) or in 100 parts of the polyol component (.fwdarw.Table 2).

TABLE-US-00001 TABLE 1 Refrigeration 1 Comparative example Comparative example Inventive example 1 1,1 1,2 Polyol A1 25.0 Polyol A2 10.0 Polyol A3 Polyol B1 57.0 57.0 55.0 Polyol B2 25.0 24.0 Polyol B3 10.0 11.7 Polyol C1 Polyol C2 Polyol C3 Catalyst composition 3.5 3.5 4.7 F Surfactant H1 3.0 3.0 3.0 H.sub.2O 1.5 1.5 1.6 Sum (without physi- 100 100 100 cal blowing agent) HCFO 30 30 30 Sum (with physical 130 130 130 blowing agent) NCO Index 119 119 119 Reacitivity initial 4 wk.sup.1) initial 4 wk.sup.1) initial 4 wk.sup.1) String time [s] 40 41 55 54 41 44 Free rise density 22.7 23.4 24.4 24.6 22.9 23.6 [g/L] Thermal conductivity 17.9 18.0 18.3 18.5 18.3 18.5 [mW/(m.Math.K)] Post-expansion min initial 4 wk.sup.1) min initial 4 wk.sup.1) min initial 4 wk.sup.1) at 17.5% overpacking Thickness [mm] 4 92.7 93.0 4 tbd tbd 4 94.0 95.3 Thickness [mm] 5 91.8 92.1 5 tbd tbd 5 92.8 94.2 Thickness [mm] 7 90.8 90.9 7 tbd tbd 7 91.6 92.7 .sup.1)Storage condition: Room temperature, 4 wk = after 4 weeks

TABLE-US-00002 TABLE 2 Refrigeration 2 Comparative example Comparative example Inventive example 2 2,1 2,2 Polyol A1 Polyol A2 Polyol A3 19.4 Polyol B1 Polyol B2 Polyol B3 Polyol C1 48.5 48.5 48.1 Polyol C2 9.7 9.7 9.7 Polyol C3 19.4 19.4 Catalyst composition 1.0 1.0 1.4 F Surfactant G1 2.0 2.0 2.0 H.sub.2O 1.9 1.9 1.9 Sum (without physi- 82.5 82.5 82.5 cal blowing agent) HCFO 17.5 17.5 17.5 Sum (with physical 100 100 100 blowing agent) NCO Index 110 110 110 Reacitivity initial 13 wk.sup.1) initial 13 wk.sup.1) initial 13 wk.sup.1) String time [s] 85 89 94 108 84 95 Free rise density 23.3 23.4 24.2 24.5 23.9 24.8 [g/L] Thermal conductivity 19.3 19.6 19.9 20.2 19.9 20.0 [mW/(m.Math.K)] Post-expansion min initial 13 wk.sup.1) min initial 13 wk.sup.1) min initial 13 wk.sup.1) at 17.5% overpacking Thickness [mm] 12 92.0 91.9 12 92.0 92.5 12 92.1 92.3 Thickness [mm] 14 90.9 90.9 14 91.2 91.6 14 91.4 91.7 .sup.1)Storage condition: Room temperature, 13 wk = after 13 weeks [0237] The data summarized in table 1 show that the foams prepared using the polyol composition according to the invention show improved post-expansion. The post-expansion for the initial composition using TDA-based polyols is lower than the post-expansion of the initial composition of the comparative example. After aging, the post-expansion for the composition using TDA-based polyols is lower in absolute and relative figures than the post-expansion of the aged composition of the comparative example. [0238] The data summarized in table 2 show that the foams prepared using the polyol composition according to the invention show improved post-expansion. The initial post-expansions of inventive and comparative examples are comparable, but after aging, the post-expansion for the composition using TDA-based is lower than the post-expansion of the aged composition of the comparative example. Furthermore, after aging the string time of the comparative example is significantly higher than the string time of the inventive example. The reactivity of the aged inventive example remained on the same level as the initial one.

[0239] 3.2 Spray foam [0240] A polyol component was produced from the raw materials indicated. The polyol component was mixed with the amount of the indicated isocyanate required to achieve an isocyanate index of 108 by means of a high-pressure Graco reactor H-25 at a discharge rate of 80 g/sec. [0241] The reaction mixture was sprayed without overpacking in several layers up to a height of at least 50 mm on a non-temperature-controlled plate of PE having dimensions of 8080 mm.sup.2. [0242] In Table 3, the respective compositions and the results for the polyurethane foams obtained are summarized. The amount of the blowing agent (HCFO-1233zd(E)) is given in parts per weight, based in 100 parts of the polyol component.

TABLE-US-00003 TABLE 3 Spray foam Inventive Comparative example 3 example 3 Polyol A3 12.0 Polyol B1 10.0 Polyol D1 36.0 36.0 Polyol D2 5.0 Polyol E 27.3 Catalyst composition G 6.45 6.45 Surfactant H2 0.8 0.8 Crosslinker I 0.8 1.5 Flame retardant J 16.0 16.0 H.sub.2O 1.95 1.95 HCFO 11.0 10.0 Sum 100 100 NCO-Index 108 108 Core free rise density [mg 36.5 37.4 KOH/g] Total free rise density [mg 38.2 38.5 KOH/g] Initial value of thermal con- 20.3 20.5 ductivity [mW/(m .Math. K)] Initial Cream time [s] 3.8 4.1 String time [s] 7.1 7.3 Rise time [s] 11.2 12.5 Beaker free rise density 33.8 34.2 [g/L] After storage.sup.2) Cream time [s] 4.8 4.9 String time [s] 9.5 10.6 Rise time [s] 13.2 17.1 Beaker free rise density 34.2 36.2 [g/L] .sup.2) Storage condition: 45 C., 1 month [0243] The examples show that the composition comprising the TDA-polyol does not age as fast composition is significantly higher than the cream, string and rise time of the inventive example.

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