MXPA98003628A - Silicone surfactants for rigid polyurethane foam, prepared with third generation blown agents - Google Patents

Abstract

A method for producing a rigid polyurethane foam by reacting a polyisocyanate and a polyol in the presence of a urethane catalyst, a blowing agent and a silicone surfactant, characterized by employing as a blowing agent an HFC or HCFC with 1 a 4 carbon atoms, preferably HFC-245fa and as the silicone surfactant, a polyether-polysiloxane copolymer having a total surfactant molecular weight of 12,000 to 100,000 g / mol, one percent by weight of siloxane in the surfactant of 10 at 40% by weight, a molecular weight of the polyether portion from 1,200 to 6,000 g / mol and one percent by weight of ethylene oxide in the polyether portion of 30-100% by weight

Description

SILICONE SURFACTANTS FOR RIGID POLYURETHANE FOAM, PREPARED WITH THIRD GENERATION BLOWING AGENTS CROSS REFERENCE TO RELATED APPLICATION This application corresponds to a continuation-in-part of the patent application of the US. Serial No. 08 / 853,136 filed May 8, 1997. FIELD OF THE INVENTION The present invention relates to cell stabilizers, for producing polyurethane foams and more particularly refers to cell stabilizers of silicone surfactant, to produce foams of rigid polyurethane. BACKGROUND OF THE INVENTION Due to changing governmental requirements, specifically the Montreal Protocol, which regulates the use of ozone-depleting materials, the primary blowing agent currently used by the industry (in the US) for applications where good Insulating properties, is HCFC-141b. However, the Montreal protocol dictates that this material can not be used in the U.S.A. after January 1 of 2003. (HCFC-141b should be phased out of Japan in 2004, the dates of phase-outs for other countries vary from 2010-2040). Potential replacements, "third generation" blowing agents, are partially hydrogenated fluorocarbons (HFCs) and some hydrochloro luorocarbons (HFCs) and include compounds HFC-134a, HFC-236ea, HFC-245fa, HFC-365mfc, and HCFC-22 . However, these can not allow optimal performance in current foam formulations. For foams used in various market segments, for example the market of water heaters and domestic equipment, the blowing agent must produce rigid foams with good insulation values, ie low thermal conductivities (low k factors). Both water heaters and refrigerators must meet the energy requirements established by the US Department of Energy. Additionally, it is anticipated that these requirements will become even more stringent in the future. As a direct replacement for HCFC 141b in a foam formulation of household equipment, third generation blowing agents produce rigid foam where there is a small to moderate increase in k factors. The selection of silicone surfactant in the formulation has a direct impact on the magnitude of this increase in the factor k. That is, the proper selection of surfactant can minimize the potential loss in foam insulation capacity when converted to a third generation blowing agent. A variety of papers have been published that discuss the general topic of third generation HFC / HCFC blowing agents and their lower insulation capacity when compared to CFC 11 or HCFC 141b. For example, one is the Barthlemey document, P.P; Leroy, A.; POLYURETHANE. { POLYURETHANE) of 1995, Minutes of the Polyurethanes Conference 1995, September 1995, p. 26- 33. The document by Bogdan, M., C; Williams, D., j.; Logsdon, P., B .; Parker, R., C; Minutes of the Polyurethanes EXPO of 1996, October, 1996, p. 394-403. This document discusses the importance of selecting surfactants for optimization of factor k in rigid polyurethane foam. List several surfactants that have been tested on foams made with HFC-245fa as the blowing agent. In addition, it concludes that Th. Goldschmidt has B8404 and B8462 and OSi 's L - 6900 are the best performance silicone surfactants identified to date to improve foam foam quality blown with HFG - 245fa, including the ky% factor. content of closed cells. These polyether polysiloxane copolymer surfactants, each having a total surfactant molecular weight calculated based on structural NMR analysis of < 10,000 g / mol. In the paper by Bodnar, T., W .; Koch, J., J.; T ornsberry, J., D., "New Surfactant Technology for HCFC-123 and HCFC-141b Blown Rigid Systems", (New Technology of Surfactants for Rigid Foam Systems Blown with HCFC-123 and HCFC-141b), 1991 Polyurethane World Congress, pages 24-26, discusses surfactants to optimize the properties of rigid foam using traditional rigid foam surfactants. The Patents of the U.S.A. Nos. 5,461,084 and 5,426,127 illustrate the use of HFC blowing agents and silicone surfactant B-8426 in rigid polyurethane foam, for low factor k and good physical properties. The patent of the U.S.A. No. 4,997,706 illustrates the use of C2-C6 polyfluorocarbon compounds that do not contain Cl or Br atoms, as physical blowing agents for rigid closed cell polymer foams. The benefit is that the loss in thermal insulation performance over time compared to foams made in the absence of these compounds is reduced. The patent of the U.S.A. No. 5,432,206 describes the silicone surfactants to produce stable polyurethane foam.

The patent of the U.S.A. No. 5,525,640 illustrates the use of certain surfactants for polyurethane foam made with an inert gas blowing agent. BRIEF COMPENDIUM OF THE INVENTION The present invention provides a silicone surfactant (polyether-polysiloxane copolymer) for stabilizing cell formation in the preparation of a rigid polyisocyanate and / or polyurethane foam, by the reaction of a polyisocyanate and polyol in the the presence of a urethane catalyst and a blowing agent containing at least one hydrogen atom and at least one fluorine atom, ie a hydrofluorocarbon with 1 to 4 carbon atoms (HFC) or hydrochlorofluorocarbon (HCFC), having a molecular weight from 50 to 170 g / mol, and a boiling point from -60 ° C to + 50 ° C. The silicone surfactant comprises a polyether-polysiloxane copolymer represented by the following formula: CH 3 CH 3 CH 3 I I (CH 3) 3-Si-0- (Si-0) x-. { Si-0) y- (Si-0), - -Si (CHj), I I I CH3 RR 'R = (CH2) 30- (CH2-CH2-0) a - (CH2-CH (CH3) -0) bR "R' = (CH2) 30- (CH2-CH2-0) c-- (CH2-CH (CH3) -0) dR "'wherein R" is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 - 30; and x / (y + z) is 7-20; and the molecular weight of the total surfactant, based on the formula, is 12,000 100,000 g / mol. The percent by weight of siloxane in the surfactant is 10 to 40% by weight, the average molecular weight of the mixture (BAMW = Blend Average Molecular Weight) of the polyether portion is 1,200-6,000 g / mol, and% by weight of ethylene oxide in the polyether portion is 30-100% by weight. Advantageously, in the production of rigid polyurethane foams using a third generation blowing agent, silicone surfactants provide foams with a higher content of closed cells and lower k-factors than the silicone surfactants traditionally used in the rigid polyurethane foam industry. . In the specification and claims, the term "polyurethane" is meant to mean polyurethane and / or polyisocyanurate as understood in the art. In this way, a rigid polyurethane foam can be a rigid polyisocyanurate and / or polyurethane foam. DETAILED DESCRIPTION OF THE INVENTION The process according to the invention can be easily carried out by conventional means to produce rigid polyurethane foam, except that the general preparation of rigid polyurethane foam using an HFC or HCFC with 1 to 4 carbon atoms, it is carried out using the polyether polysiloxane according to the invention as the cell stabilizer. The rigid polyurethane foam products are prepared using any suitable organic polyisocyanates well known in the art to produce rigid polyurethane foam, including for example hexamethyl diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4.4 * -difenilmetan diisocyanate ("MDI"). Especially convenient are mixtures of diisocyanates commercially known as "crude MDI", commercially available as PAPI from Dow Chemical, which contains about 60% of 4,4'-diphenylmethane diisocyanate together with other isomeric polyisocyanates and higher analogues. Other suitable isocyanates are 2,4- and 2,6-TDI • s individually or together as their commercially available mixtures. Also suitable are "prepolymers" of these polyisocyanates, which comprise a previously partially reacted mixture of a polyisocyanate and a polyether or a polyester polyol. Preferably, the above polyisocyanates are used in an isocyanate index range of 80 to 400.

Suitable polyols are those polyols typically employed in the art to produce rigid polyurethane foam including polyalkylene ether and polyester polyols. Polyalkylene ether polyols include poly (alkylene oxide) polymers such as poly (ethylene oxide) and poly (propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds including diols and triols; for example, among others, ethylene glycol, propylene glycol, 1,3-butan diol, 1,4-butan diol, 1,6-butan diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethyl propane, sugars, such as sucrose and similar low molecular weight polyols. Also useful are polyether amine polyols which can be prepared by reacting an amine, such as ethylene diamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, triethanolamine or the like, with ethylene oxide or propylene oxide. In the practice of this invention, a simple high molecular weight polyether polyol can be employed. Also, mixtures of high molecular weight polyether polyols such as mixtures of different mutifunctional materials and / or materials with different chemical composition or different molecular weight can be used.

Polyester useful polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example adipic acid or phthalic acid / anhydride with ethylene glycol or butanediol, or reacting a lactone with excess of a diol such as caprolactone with propylene glycol. The catalyst composition can be any catalyst well known in the art of urethanes, such as tertiary amines, organ tin and urethane carboxylate catalysts (gelation and / or blowing). Typical examples of useful catalysts are amine catalysts such as triethylene diamine, dimethyl cyclohexylamine, tetramethylhexanediamine, bis (dimethylaminoethyl) -ether, tri (dimethylaminopropyl) hexahydrotriamine, l-isobutyl-2-methylimidazole, 1,2-dimethylimidazole, dimethylaminoethanol, ethylimethanol. , pentamethyldiethylene triamine, pentamethyl dipropylenetriamine, methyl morpholine, ethyl morpholine, quaternary ammonium salts, salts of an organic acid and tin catalysts, such as dibutyltin dilaurate and the like. A catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, convenient amounts of the catalyst composition may be in the range of about 0.01 to 10 parts by weight 100 parts of polyol (0.01 to 10 pphp) of the polyurethane formulation preferably 0.5 to 4 pphp. The third generation blowing agents used in the present invention to produce rigid foams comprise HFC or HCFC with 1 to 4 carbon atoms with a molecular weight of 50 to 170 g / mol, a boiling point of -60 ° C to + 50 ° C, and preferably an ozone depletion potential (ODP = Ozone Depleting Potential) of < 0.10, ODP as described by: "Synthesis of the Reports of the Ozone Scientific Assessment Panel, Environmental Effects Assessment Panel Technology and Economic Assessment Panel, Prepared by the Assessment Chairs for the Parties to the Montreal Protocol" (Summary of panel reports of Ozone Scientific Evaluation, economic evaluation panel and technology, environmental effects assessment panel, prepared by the evaluation chairpersons of the parties to the Montreal Protocol, November 1991. HFCs and HCFCs that meet this criterion include HFC-134a , HFC-236ea, HFC-365mfc, HCFC-22 and preferably HFC-245fa Water may be included in the formulation from 0 to 4 pphp Other blowing agents which may be optionally employed in combination with the defined HFC or HCFC with 1 to 4 carbon atoms, include CFCs, other HCFCs, other HFCs, pentanes and the like.

In the silicone surfactant cell stabilization in an amount of 0.5 to 3.5 pphp, preferably 1.5 to 2.5 pphp, can be any polyether polysiloxane copolymer of the following structure CH3 CH3 CH3 III (CH3) 3-Si-0- (Si-) 0) x- (Si-0) y- (Si-0) z - Si (CH3) 3 III CH3 RR 'R = (CH2) 3-O- (CH2-CH2-0) a-- (CH2-CH (CH3) -0) bR' 'R' = (CH2) 3-0- (CH2-CH2- 0) c-- (CH2-CH (CH3) -0) aR "where the molecular weight of calculated total surfactant, based on the structure is 12,000 to 100,000 g / mol, preferably 15,000 to 30,000 g / mol; the weight percent of siloxane in the surfactant is 10 to 40% by weight, preferably 25 to 35% by weight; the BAMW of the polyether portion is 1200 to 6000 g / mol, preferably 1200 to 3000 g / mol; and the weight percent of ethylene oxide in the polyether portion is 30 to 100% by weight, preferably 30 to 60% by weight. In addition R "can be H, CH3, or C (0) CH3; and x is 50-200, preferably 50 to 170, and + z is 3 to 30, preferably 5 to 25; and x / (y + z) is 7-20, preferably 7 a . These polyether-polysiloxane copolymers can be used as the sole surfactant or in combination with another silicone surfactant which falls outside the range described herein. The prior art, especially the polyurethane foam technique, is replete with examples of polyether-polysiloxane copolymers. The methods and materials employed in producing and terminating the various copolymers in the extreme are well known in the art. The usual procedures for manufacturing these materials, result in a molecule in which one end of the polyether (polyoxyalkylene) is terminated extremely with an unsaturated group such as allyloxy, in order to be able to react with methyl hydrogen polysiloxanes to create the polyether-polysiloxane copolymers. This is possible through hydrosilylation using noble metal catalysts, wherein the polysiloxanes have a certain amount of methyl hydrogen siloxane units in their molecules, which react with the unsaturated groups of the polyethers to form Si-C bonds. In general, the polyether copolymers can be terminated in the extreme before the hydrosilylation or they can end in end after the hydrosilylation. Whichever the case, the normal preparative method for unsaturated polyether copolymers is to electrocheck, for example allyl alcohol with ethylene oxide, and then react this polymer with propylene oxide such that the polyether molecule of copolymer ends with secondary alcohol groups primarily in its end not unsaturated. In other methods, a random copolymer can be formed by reacting ethylene oxide, propylene oxide and allyl alcohol, to provide a material having large amounts of carbinoles or the secondary carbon atoms of the propylene glycol that is formed. In such a way that the polyether materials can be reacted in polysiloxanes, and eventually participate in, for example polyurethane foam production as surfactants, the carbinoles are very often blocked in extreme, a common end-blocker is acyloxy. Methods for synthesizing non-hydrolysable silicone surfactants having polyether side groups are well known. Representative descriptions are provided in the patents of the U.S.A. Nos. 4,147,847 and 4,855,379 which are hereby incorporated by reference. Other typical agents that can be employed in the rigid polyurethane foam formulations include pyro-retardant and chain extenders such as ethylene glycol and butanediol. A general polyurethane rigid foam formulation having 24-40 kg / m3 (1.5 to 2.5 pounds per cubic foot) density (foam for household equipment) containing a silicone surfactant, such as polyether-polysiloxane copolymer according to with the invention and a third generation blowing agent, for example HFC-245fa, will comprise the following components in parts by weight: Formulation of Rigid Foam pbw Polyol 100 Silicone Surfactant 1-3 Blowing Agent 20-40 Water 0-3 Catalyst 0.5-3 Isocyanate Index 80-400 The following examples employ the rigid polyurethane foam formulation of Table 1. Table 1 Component Pair is by PegQ Polyol * 100 amine catalysts 2.6 Water 2.0 HFC-245fab 34.2 MPI PQlimérjcQ index NCO = 115 a Polyether polyol initiated with sucrose, number OH = 360 b 1, 1, 3, 3-pentafluoropropane Example i The ingredients were combined in Table 1 and incubated at 10 ° C until the mixture balanced at temperature. The resin was weighed into a paper cup and secreted surfactant A in an amount equal to 3.0 parts by weight 100 parts of polyol. MDI polymer at 23 ° C is added in such an amount that the isocyanate index (NCO) was 115. The mixture is stirred with a high speed mixer for 8 seconds and emptied into a mold of 30.5x30.5x5.1 cm ( 12x12x2") is heated to 49 ° C. Sufficient of the foaming mixture is added to the mold to give a plate that was over packed at 5% The foam plate is removed from the mold after 4 minutes and aged at 23 ° C by 18 to 24 hours A portion of 20.3x20.3.x2.54 cm (8x8x1") is cut from the center of the plate and tested in a Fox-200 lasercomp thermal fluidimeter. After thermal flux (k-factor) measurements were taken, samples of 2.54x2.54.2.54 cm (lxlxl ") were cut from the foam and tested by a Quantachrome pycnometer to determine the% content of closed cells. the procedure of Example 1 except that surfactant B is used instead of surfactant A.

EXAMPLE The procedure of example 1 is followed except that surfactant C is used instead of surfactant A. Example 4 The procedure of example 1 is followed except that surfactant D is used instead of surfactant A. Example 5 The procedure of Example 1 except that 1.5 parts by weight surfactant D and 1.5 parts by weight of surfactant C were added to the resin mixture instead of 3.0 parts by weight of surfactant A. Example 6 The procedure of example 1 is followed except that Goldschmidt is employed. B8404 instead of surfactant A. Example 7 The procedure of example 1 is followed except that OSI Specialty Niax L-6900 silicone surfactant is used instead of surfactant A. Table 2 Ex. Surfactant Surfactant% Polyether% EO in mol by weight Siloxane BAMW Polyether 1 A 45,600 30.2 1368.4 50 2 B 28,200 31.2 1938.5 41 3 C 6800 35.2 730.9 60 4 D 3200 32.2 586.7 90 Table 2 (Cont.) Ex. Surfactant Surfactant% Polyether% EO in mol by weight Siloxane BAMW Polyether B + C - - - 6 B8404"<10,000 - 7 L-6900b <10,000 - Table 2 (cont) Ex. X / (y + z) factor kc% of cells closed 1 7.4 0.1469 82.5 2 10.8 0.1447 85.4 3 4.2 0.1555 74.9 4 2.4 0.1850 47.8 5 - 0.1481 81.1 6 - 0.1570 76.6 7 0.1501 78.4 at Th. Goldschmidt - percent in mol calculated b OSi Specialty - mol percent calculated c Kcal.cm / m2.hr ° C (Btu.in/pie2.hr°F) Table 2 presents the results of the Examples 1 to 7. It can be seen in the data that surfactants A and D provide markedly lower and higher k-factors percentages of closed cell contents than surfactants C, D, B8404 and L-6900. Surfactants C and D as well as B8404 and L-6900 are all representative of what is currently used in the rigid foam industry. In addition, surfactant B used in conjunction with surfactant C also produces foam with a lower k-factor and higher% closed-cell content than surfactant C alone or the other typical rigid foam surfactants. These data clearly demonstrate that the silicone surfactants according to the invention produce foams with a% higher closed cell content and a lower k-factor than those typically used in the industry. DECLARATION OF INDUSTRIAL APPLICATION The present invention provides polyether-polysiloxane copolymers to produce rigid polyurethane foams.

Claims (20)

1. - In a method for producing a rigid polyurethane foam by reacting a polyisocyanate and a polyol in the presence of a urethane catalyst, a blowing agent, optionally water, and a silicone surfactant, the improvement comprising employing as Blowing agent an HFC with 1 to 4 carbon atoms having a molecular weight of 50 to 170 g / mol and a boiling point of -60 ° C to + 50 ° C, or HCFC-22 and as the silicone surfactant a polyether-polysiloxane copolymer represented by the following formula: CH 3 -H 3 CH 3 (CHj -Yi-O- (Si-0), - (Si-0) y- (Si-0) z - Si (CH3) CH3 R R 'R = (CH2) 3-O- (CH2-CH2-0) a-- < CH2-CH. { CH3) -0) bR '' R '= (CHJ) 3-O- (CH2-CH2-0) e-- (CH2-CH (CH3) -0) dR' 'wherein R "is H, CH3, or C (0) CH3; x is 50-200, y + z is 3 -30, and x / (y + z) is 7-20, the molecular weight of total surfactant is 12,000 to 100,000 g / mol, the The weight percent siloxane in the surfactant is 10 to 40% by weight, the average molecular weight of the mixture of the polyether portion is 1200 to 6,000 g / mol, and the weight% of ethylene oxide in the polyether portion is 30 - 100

2. The method according to claim 1, wherein the blowing agent is HFC-134a, HFC-236ea, HFC-365mfc, HFC-22 or HFC-245fa.

3. The method according to claim 1, wherein the blowing agent is HFC-245fa.

4. - The method according to claim 1, wherein the blowing agent also contains CFC, another HCFC, another HFC or a pentane.

5. - In a method for producing a rigid polyurethane foam, by reacting a polyisocyanate and a polyol in the presence of a urethane catalyst, a blowing agent, optionally water, and a silicone surfactant, the improvement comprising employing as blowing agent an HFC or HCFC with 1 to 4 carbon atoms having a molecular weight of 50 to 170 g / mol, a boiling point of -60 ° C to + 50 ° C, and an ozone depletion potential of < 0.10 and as the silicone surfactant a polyether-polysiloxane copolymer represented by the following formula: (CH3) 3-Si-0- (Si-0) x- (Si-0) y- (Si-0) z - Si (CH3) CH, R = (CH2) 3-O- (CH2-CH2-0) a-- (CH2-CH (CH3) -0) bR '' R '= (CH,) J-0- (CH2-CH2- 0) c-- (CH2-CH (CH3) -0) dR '' where R "is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 -30; and x / (y + z) is 7-20, the molecular weight of total surfactant is 12,000 to 100,000 g / mol, the weight percent of siloxane in the surfactant is 10 to 40% by weight, the average molecular weight of the mixture of the polyether portion is from 1200 to 6,000 g / mol and the weight% of ethylene oxide in the polyether portion is 30-100.

6. In a method for producing a rigid polyurethane foam by reacting a polyisocyanate and a polyol in the presence of a urethane catalyst, a blowing agent, optionally water, and a silicone surfactant, the improvement comprising employing as the blowing agent an HFC with 1 to 4 carbon atoms having a molecular weight of 50 to 170 g / mol, and a boiling point of -60 ° C to + 50 ° C, or HCFC-22 and as a silicone surfactant of 0.5 to 3.5 pphp, a polyether-polysium copolymer loxane represented by the following formula: CH3 CH3 CH3 (CH3), - Si-0- (Si-0) x- (Si-0) y- (Si-0) z- -Si (CHJ 3 III CH3 RR 'R = (CHjh-O- (CH2-CH2 -0) a-- (CH2-CH (CH3) -0) "- R" R '= (CH2) 3-O- (CH2-CH2-0) c - (CH2-CH (CH3) -0 ) aR '' where R "is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 -30; and x / { y + z) is 7 - 20; Molecular total surfactant is 15,000 to 30,000 g / mol, the weight percent of siloxane in the surfactant is 25 to 35% by weight, the average molecular weight of the polyether portion mixture is 1,200 to 3,000 g / mol and the % by weight of ethylene oxide in the polyether portion is 30-60% by weight

7. - The method of conformity with claim 6, wherein the blowing agent is HFC-134a, HFC-236ea, HFC-365mfc , HFC-22 or HFC-245fa

8. The method according to claim 6, wherein the blowing agent is HFC-245fa

9. The method according to claim 6, where because the blowing agent also contains CFC, another HCFC, another HFC or a pentane.

10. The method according to claim 8, wherein the blowing agent also contains CFC, another HCFC, another HFC or a pentane.

ll. - In a method for producing a rigid polyurethane foam by reacting a polyisocyanate and a polyol in the presence of a urethane catalyst, a blowing agent, optionally water, and a silicone surfactant, the improvement comprising employing as the blown an HFC or HCFC with 1 to 4 carbon atoms, which has a molecular weight of 50 to 170 g / mol, a boiling point of -60 ° C to + 50 ° C, and an ozone depletion potential of <; 0.10 and as the silicone surfactant from 0.5 to 3.5 pphp of a polyether-polysiloxane copolymer represented by the following formula: H3 H3 H3 III (CH3) 3-Si-0- (Si-0) x- (Si-0) ) and- < Si-0) z - Si (CH3) 3 I I I CH3 RR 'R = (CH2) 3-0- (CH2-CH2-0) a-- (CH2-CH (CH3) -0) bR' 'R' = (CH2) 3-0- (CH2-CH2- 0) c-- (CH2-CH (CH3) -0) dR '' where R "is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 -30; and x / (y + z) is 7-20, the molecular weight of total surfactant is 15,000 to 30,000 g / mol, the weight percent of siloxane in the surfactant is 25 to 35% by weight, the average molecular weight of the mixture of the polyether portion is 1,200 to 3,000 g / mol and the weight% of ethylene oxide in the polyether portion is 30-60% by weight

12. The method according to claim 11, wherein the blowing agent is HFC-134a, HFC-236ea, HFC-365mfc, HFC-22 or HFC-245fa and optionally contains a CFC, another HCFC, another HFC or a pentane.

13. - A rigid polyurethane foam composition, comprising the following components in parts by weight (pbw): Formulation of rigid foam pbw Polyol 100 Silicone surfactant 1-3 Blowing agent 20-40 Water 0-3 Catalyst 0.5-3 index of Isocyanate 80-400 wherein the blowing agent is an HFC or HCFC with 1 to 4 carbon atoms having a molecular weight of 50 to 170 g / mol, a boiling point of -60 ° C to + 50 ° C , and an ozone depletion potential of < 0.10 and the silicone surfactant is a polyether-polysiloxane copolymer represented by the following formula: CH3 CH3 CH3 (CH3) 3-Si-0- (Si-0), - (Si-0) y- (Si-0) t - Si (CH,). CH, RR = (CH2) 3-0- (CH2-CH2-O) a-- (CH2-CH (CH3) -0) bR '' R '= (CH2) 3-0- (CH2-CH2-0 ) c-- (CH2-CH (CH3) -0) dR '' where R "is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 -30; and x / ( y + z) is 7-20, the molecular weight of total surfactant is 12,000 to 100,000 g / mol, the weight percent of siloxane in the surfactant is 10 to 40% by weight, the average molecular weight of the mixture of the polyether portion is from 1200 to 6,000 g / mol and the% by weight of ethylene oxide in the polyether portion is 30-100.

14. The composition according to claim 13, wherein because the blowing agent is HFC- 134a, HFC-236ea, HFC-365mfc, HFC-22 or HFC-245fa

15. The composition according to claim 13, wherein the blowing agent is HFC-245fa

16. - The composition in accordance with claim 13, wherein the blowing agent also contains a CFC, another HCFC, another HFC or a pentane

17. The composition according to claim 13, in because the blowing agent which is HFC-134a, HFC-236ea, HFC-365mfc, HFC-22 or HFC-245fa and the silicone surfactant is a polyether-polysiloxane copolymer represented by the following formula: CH 3 CH 3 CH 3 III < CH3), - Si-0- (Si-0) x- (Si-0) y- (Si-0), - -Si (CH3) 3 I I I CH3 RR 'R = (CH2) 3-O- (CH2-CH2-0) a - (CH2-CH (CH3) -0) bR' 'R' = (CHa), -0- (CH2-CH2- 0) or-- (CH2-CH (CH3) -0) dR '"where R" is H, CH3, or C (0) CH3; x is 50-200; y + z is 3 -30; and x / (y + z) is 7-20, the molecular weight of total surfactant is 15,000 to 30,000 g / mol, the weight percent of siloxane in the surfactant is 25 to 35% by weight, the average molecular weight of the mixture of the polyether portion is 1,200 to 3,000 g / mol and the weight% of ethylene oxide in the polyether portion is 30-60% by weight

18. The composition according to claim 17, wherein the blowing agent is HFC-245fa

19. The composition according to claim 17, wherein the blowing agent also contains a CFC, another HCFC, another HFC or a pentane

20. The composition according to claim 18, wherein The blowing agent also contains a CFC, another HCFC, another HFC or a pentane.