Silicone polyethers that contain hydrocarbon blowing agents and provide stability to polyol systems.

Abstract

The polyol composition comprises a polyol, a blowing agent, and a polyol having the average chemical formula RSiO(RSiO) x (RR a SiO) y and a silicone polyether having the formula SiR3, where R is C 1~4 alkyl, x is 5 to 55, y is 1 to 10, and x+y is 6 to 60; R a is the average chemical formula -(CH2) p -(EO) n (PO) m (EO) e H, where EO is —CHCHO—, PO is —CHCH(CH)O—, e is 1 to 50, m is 2 to 10, n is 1 to 20, e+n is 25 to 70, and p is 1 to 10, the PO content is greater than 0 weight percent and less than 15 weight percent of the weight of EO+PO, the EO content is greater than 58 weight percent and less than 75 weight percent of the weight of silicone polyether, the blowing agent is greater than 70 volume percent hydrocarbon blowing agent, based on the volume of the blowing agent, and a and (ii) x+y is less than or equal to 50.

Description

[Technical Field]

[0001] The present invention provides particularly stable polyol compositions useful in preparing polyurethane foams, which utilize silicone polyethers as stabilizers.

[0002] (Introduction) A two-part system for preparing polyurethane foam includes part "A" and part "B." Part A includes an isocyanate-functional component. Part B is a polyol formulation that includes one or a combination of polyols and often a blowing agent. When parts A and B are mixed, the polyol in part B reacts with the isocyanate functionality in part A to form the polyurethane foam.

[0003] Historically, blowing agents for Part B have been halogenated substances with high ozone depletion potentials and high global warming potentials. However, it is environmentally desirable to use blowing agents with lower ozone depletion potentials and global warming potentials than halogenated blowing agents. One alternative is to use hydrocarbon blowing agents. The challenge is to achieve compatibility between the hydrocarbon blowing agent and polyols, especially polyether polyols, particularly by increasing the ethylene oxide (EO) content in the polyether polyol. As the EO content of polyether polyols increases, compatibility with the hydrocarbon blowing agent tends to decrease, resulting in phase separation of the blowing agent from the polyether polyol in the Part B component, often within minutes. Phase separation leads to uneven distribution of the blowing agent in the polyol, which then leads to uneven foaming when mixed with the Part A component, producing foams with uneven color, texture, low rise, and / or large holes. Instability of the Part B components can be particularly problematic when storage temperatures can vary over a range of 10 to 30 degrees Celsius (°C) depending on the region and environment in which they are located.

[0004] It is desirable to identify a compatibilizer useful for Part B formulations containing hydrocarbon blowing agents and polyether polyols to stabilize them from phase separation over a temperature range of 10-30° C. over several days. Such a compatibilizer would advance the art of polyurethane foam manufacturing by allowing the formulation and storage of Part B formulations for longer periods of time without the need for constant agitation and without the production of poor quality foam due to polyol / blowing agent phase separation.

[0005] It is desirable to identify a compatibilizer useful in Part B formulations containing hydrocarbon blowing agents and polyether polyols to stabilize them from phase separation over a temperature range of 10° C. to 30° C. over a period of several days. Such a compatibilizer would advance the art of polyurethane foam manufacturing by allowing the formulation and storage of Part B compositions for longer periods of time without the need for constant agitation and without the production of poor quality foam due to polyol / blowing agent phase separation. Summary of the Invention

[0006] The present invention provides silicone polyethers that act as useful compatibilizers in Part B formulations containing hydrocarbon blowing agents and polyether polyols to stabilize them from phase separation over a temperature range of 10-30°C over several days.

[0007] In a first aspect, the present invention provides a polyol composition comprising a polyol, a blowing agent, and a silicone polyether, wherein the silicone polyether has an average chemical formula (I): RSiO(RSiO) x (RR a SiO) y SiR3(I), wherein (a) each R, in each occurrence, is independently selected from alkyl groups having 1 to 4 carbon atoms; (b) subscript x has an average value ranging from 5 to 55; (c) subscript y has an average value ranging from 1 to 10; (d) the sum of x+y has an average value ranging from 6 to 60; and (e) R a The average chemical formula (II): -(CH2)p -(EO) n (PO) m (EO) e (ii) PO refers to —CH2CH2O—; (iii) subscript e has an average value ranging from 1 to 50; (iv) subscript m has an average value ranging from 2 to 10; (v) subscript n has an average value ranging from 1 to 20; (vi) the sum of subscripts e and n has an average value ranging from 25 to 70; and (vii) subscript p has an average value ranging from 1 to 10, provided that the PO content is greater than 0 and simultaneously less than 15 weight percent of the combined weight of EO and PO, and the EO content is greater than 58 weight percent and simultaneously less than 75 weight percent of the weight of the silicone polyether, and the blowing agent is greater than 70 volume percent hydrocarbon blowing agent, based on the volume of the blowing agent, and the following condition is met: (f) R a (g) has a number average molecular weight in the range of 1500 to 2500 grams per mole as determined by size exclusion chromatography; and (g) the sum of the average values ​​of the subscripts x and y is 50 or less.

[0008] In a second aspect, the present invention is a process for preparing a polymer foam, comprising combining a polyol composition according to any one of the preceding claims with a composition comprising an isocyanate-functional component. The process may comprise first preparing the polyol composition and then aging it for one or more days at a temperature in the range of 10 to 30°C before combining it with the composition comprising the isocyanate-functional component.

[0009] The present invention is useful for preparing stable Part B compositions for use in making polyurethane foams. DETAILED DESCRIPTION OF THE INVENTION

[0010] Test methods, unless a date is given with the test method number, refer to the test method most recent as of the priority date of this document. References to test methods include both references to the testing society and to the test method number. The following test method abbreviations and designations apply herein: ASTM refers to the American Society for Testing and Materials, EN refers to European Norm, DIN refers to the Deutsches Institut fuer Normung, and ISO refers to the International Organization for Standards.

[0011] "Multiple" means two or more. "And / or" means "and, or as an alternative." All ranges are inclusive of the endpoints unless otherwise indicated.

[0012] Products identified by trade names refer to compositions available under those trade names as of the priority date of this document.

[0013] "Ca~b", "C a~b " are interchangeable and refer to having a to b carbon atoms.

[0014] "Polyurethane" refers to a polymeric material having multiple urethane linkages. The term "polyurethane" includes "polyisocyanurate" unless otherwise specified. Polyisocyanurate is a form of polyurethane, typically formed from polyhydroxy materials and components with multiple isocyanate groups, such as diisocyanates. Polyisocyanurates are often prepared from derivatives of cyanuric acid.

[0015] In one aspect, the invention is a polyol composition comprising a polyol, a blowing agent, and a silicone polyether.

[0016] The polyol of the polyol composition can be a polyester polyol and / or a polyether polyol. Desirably, the polyol is a polyether polyol. Suitable polyester polyols desirably have an average functionality of 1.8 to 8, preferably 1.8 to 5, and more preferably about 2 to 2.5. The hydroxyl value of the polyester polyol is generally 15 or more, preferably 30 or more, more preferably 100 or more, while generally 750 or less, preferably 550 or less, and more preferably 250 or less. The free glycol content of the polyester polyol is generally 0 or more, preferably 2 or more, while generally 40 or less, preferably 30 or less, and more preferably 15 or less. The acid value of the polyester polyol is generally 0.2 or more. Suitable polyether polyols include linear and branched polyether polyols having multiple acyclic ether oxygens and containing at least 1.8, preferably 3 or more, typically 4 or more, and typically 8 or less isocyanate-reactive groups. Polyether polyols typically have molecular weights ranging from 250 to 7500 based on their hydroxyl number. "Isocyanate-reactive groups" include, and may be, hydroxyl (-OH) groups. The polyol can contain greater than 50 weight percent EO, based on the weight of alkoxy in the polyol.

[0017] Typically, the polyol composition contains polyol at a concentration of 50 weight percent or greater, and can be 55 weight percent or greater, based on the weight of the polyol composition, while typically being present at a concentration of 95 weight percent or less, 90 weight percent or even 85 weight percent or less.

[0018] The blowing agent can be a single compound or a combination of two or more compounds, provided that the blowing agent is greater than 70 volume percent (vol%) hydrocarbon blowing agent, based on the volume of the blowing agent. "Hydrocarbon blowing agent" refers to a combination of one or more hydrocarbons having an average molecular weight of up to 72 grams per mole and a boiling point within the range of -5 degrees Celsius (°C) or higher, -1°C or higher, 25°C or higher, 27.8°C or higher, or even 36°C or higher, while typically being 100°C or lower, preferably 70°C or lower, and may be 40°C or lower. The blowing agent can also be a combination of blowing agents, where the blowing agent is 75% or higher, 80% or higher, 85% or higher, 90% or higher, or even 95% or higher by volume hydrocarbon blowing agent, based on the volume of the blowing agent. Desirably, the blowing agent is 100% by volume hydrocarbon blowing agent, based on the volume of the blowing agent. Examples of suitable hydrocarbon blowing agents include butane (a C4 hydrocarbon), including each isomer, pentane (a C5 hydrocarbon), including each isomer, and combinations thereof. Desirably, the polyol composition is free of hydrofluorocarbons and hydrochlorofluorocarbons, which are often present as blowing agents.More desirably, the polyol composition is free of halogenated blowing agents.

[0019] Typically, the polyol composition contains at least 1 wt. %, preferably at least 5 wt. %, while typically at most 30 wt. %, preferably at most 25 wt. %, of a blowing agent, based on the weight of the polyol composition.

[0020] The polyol composition includes a silicone polyether having the average chemical formula (I): R3SiO(R2SiO) x (RR a SiO) y SiR3(I) wherein each R in each occurrence is independently selected from alkyl groups having 1 to 4 carbon atoms, and can have 1 or more, 2 or more, 3 or more, or even 4 carbon atoms, and can have 4 or fewer, 3 or fewer, 2 or fewer, or even 1 carbon atom; R is desirably the same in each occurrence, and can be methyl in each occurrence; The subscript x has an average value in the range of 5 to 55, and can have an average value of 5 or more, 10 or more, 14 or more, 20 or more, 21 or more, or even 23 or more, while typically being 55 or less, and may be 50 or less, 40 or less, 30 or less, 23 or less, 21 or less, or even 20 or less; the subscript y has an average value in the range of 1 to 10, and can have an average value of 1 or more, 2 or more, 3 or more, 4 or more, while typically being 10 or less, and may be 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or even 4 or less; The sum of x+y has an average value in the range of 6 to 60, and may have an average value of 6 or more, 10 or more, 15 or more, 16 or more, or even 20 or more, while typically being 60 or less, and may be 50 or less, 40 or less, 30 or less, 27 or less, 26 or less, 25 or less, 24 or less, or even 23 or less; and R a has the average chemical formula (II): -(CH2) p -(EO) n (PO) m (EO) e H (II) wherein (i) EO refers to -CH2CH2O-; (ii) PO refers to -CH2CH(CH3)O-; (iii) the subscript e has an average value in the range of 1 to 50, typically 1 or greater, and can have an average value of 5 or greater; 10 or greater, or even 20 or greater, while typically 50 or less, and may be 40 or less, 30 or less, or even 20 or less; (iv) the subscript m has an average value in the range of 2 to 10, typically 2 or more, even 2.5 or more, and at the same time has an average value of 10 or less, and may be 8 or less, 6 or less, 4 or less, or even 3 or less; (v) the subscript n has an average value in the range of 1 to 20, typically 1 or greater, and may have an average value of 5 or greater, 10 or greater, or even 11 or greater, while typically 20 or less, and may be 15 or less, or even 11 or less; (vi) the sum of the subscripts e and n has an average value in the range of 25 to 70, typically 25 or more, and can be 30 or more, or even 31 or more, while typically 70 or less, and can be 50 or less, 40 or less, 35 or less, or even 31 or less; and (vii) the subscript p has an average value in the range of 1 to 11, and typically has an average value of 1 or greater, and may have a value of 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, or even 7 or greater, while typically has an average value of 11 or less, and may have a value of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less; however, the PO content is greater than 0 while being less than 15 weight percent (wt%) of the combined weight of EO and PO, and is typically present at a concentration greater than 0, and may be present at a concentration of 2 wt% or more, 4 wt% or more, 6 wt% or more, 8 wt% or more, even 9 wt% or more, or 9.5 wt% or more, while being 15 wt% or less, or even 12 wt% or less, or even 10 wt% or less, or 9.5 wt% or less, based on the combined weight of EO and PO in the silicone polyether; and the EO content is greater than 58 weight percent and simultaneously less than 75 weight percent of the weight of the silicone polyether, and can be 58 weight percent or more, 59 weight percent or more, 60 weight percent or more, 61 weight percent or more, 62 weight percent or more, 63 weight percent or more, or even 64 weight percent or more, based on the weight of the silicone polyether, while typically is 75 weight percent or less, and can be 70 weight percent or less, 66 weight percent or less, 65 weight percent or less, 63 weight percent or less, or even 60 weight percent or less; and The following two conditions are met: R ahas a number average molecular weight in the range of 1500 to 2500 grams per mole (g / mol), preferably 1500 g / mol or more, and may be 1600 g / mol or more, 1700 g / mol or more, 1800 g / mol or more, 1900 g / mol or more, 2000 g / mol or more, 2100 g / mol or more, 2200 g / mol or more, 2300 g / mol or more, or even 2400 g / mol or more, while typically 2500 g / mol or less, and may be 2400 g / mol or less, 2300 g / mol or less, 2200 g / mol or less, 2100 g / mol or less, 2000 g / mol or less, 1900 g / mol or less, 1800 g / mol or less, 1700 g / mol or less, or even 1600 g / mol or less; and The sum of the average values ​​of the subscripts x and y is 50 or less, and may be 40 or less, 30 or less, 27 or less, 24 or less, 23 or less, 20 or less, 18 or less, or even 16 or less, and may be 6 or more, 10 or more, 12 or more, 14 or more, 15 or more, 16 or more, 18 or more, 20 or more, or even 23 or more, wherein at least one of the following is satisfied:

[0021] 1 H-NMR, 29 Si-NMR and 13 The structure and number average molecular weight of the silicone polyethers were determined by nuclear magnetic resonance (C) spectroscopy using C-NMR on an Agilent 400MR NMR spectrometer (9.4 T) with a 5 mm One NMR probe. 1 H-NMR spectra are collected by dissolving 0.150 grams of sample in 1 gram of benzene-d6 solvent. 1 Prepare the sample for H-NMR using the following parameters: 1 H-NMR spectra were collected: 16 transients with a 5 second acquisition time and a 15 second relaxation time. Spectra were processed with ACD / Spectrus Process (2012 release build 66513) from www.acdlabs.com.

[0022] An Agilent DDR2 NMR spectrometer (11.7 T) equipped with a 16 millimeter (mm) silicon-free AutoX probe was used. 29 Si-NMR and 13 C-NMR spectra are collected by dissolving 6 grams of sample in 2.7 grams of benzene d6 solvent with 0.05 molar chromium acetylacetonate relaxation agent. 29 Si-NMR and 13 Prepare the sample for C-NMR using the following parameters: 29 Collect Si-NMR spectra: 1024 transients with a 1 s acquisition time and a 16 s relaxation time. Use the following parameters: 13 Collect C-NMR spectra: 1024 transients with a 1 s acquisition time and a 13 s relaxation time. Process the spectra with ACD / Spectrus Process (2012 release build 66513) from www.acdlabs.com.

[0023] 29 The Si-NMR spectrum is used to calculate the silicone polyether chain parameters. The highest peak at δ = -22.0 ppm defines the reference, and the integral at δ = 7.15 + / - 0.1 ppm is set to 2. The integral at δ = -22.00 + / - 0.1 ppm gives the chain length ("x"), and the integral at δ = -22.45 + / - 0.1 ppm gives the number of polyether chains ("y").

[0024] 13Use C-NMR to calculate the structural parameters of polyether chains. Reference is set to the C6H6 central peak at δ=128.39 ppm, and the integral value at δ=14.21±0.1 ppm is set as "y", which represents the average number of polyether chains attached to the silicone polyether backbone. The total number of polyether chains not attached to the silicone polyether backbone is calculated by adding the average integral values ​​of the signals at δ=98.19±0.1 ppm and δ=147.64±0.1 ppm ("a1"), the average integral values ​​of the signals at δ=100.58±0.1 ppm and δ=146.91±0.1 ppm ("a2"), and the average integral values ​​of the signals at δ=116.34±10.1 ppm and δ=136.11±0.1 ppm ("a3"). The total number of polyether chains is the sum of the bound and unbound polyether chains (t = a1 + a2 + a3 + y). The average number of ethylene oxide (EO) groups in the polyether chains ("e") is calculated, i.e., the integral of the signals between δ = 68.5 ppm and δ = 72.5 ppm is divided by 2t. The average number of propylene oxide (PO) groups in the polyether chains ("m") is calculated, i.e., the integral of the signals between δ = 72.5 ppm and δ = 78.5 ppm is subtracted by "y" and divided by 2t. The average value of the subscript p is identified by the sum of the integral signals at δ = 14.21 + / - 0.1 ppm, δ = 24.05 + / - 0.1 ppm, and δ = 74.17 + / - 0.1 ppm.

[0025] 1H-NMR is used to confirm the values ​​of a1, a2, and a3.

[0026] Based on the above parameters obtained from the NMR spectrum, the number average molecular weight is calculated as follows: Number average molecular weight = 162 + 74x + (59 + 14n + 44e + 58p + z)y, where "z" has a value of 1 for the terminal hydrogen on the pendant polyether group. The number average molecular weight of the pendant polyether chain is (59 + 14n + 44e + 58p + z).

[0027] The polyol composition may have an organopolysiloxane present in addition to the silicone polyether of formula (I).For example, the polyol composition may have an organopolysiloxane that is a variation of the silicone polyether of formula (I) with formula (II) terminated with non-primary OH.Desirably, the polyol composition contains 5 mole percent (mol%) or less, preferably 4 mole% or less, 3 mole% or less, 2 mole% or less, or even 1 mole% or less, and may not contain the variation of the silicone polyether of formula (I) with formula (II) terminated with non-primary OH, and the mole% is based on the total number of moles of the silicone polyether of formula (I) and the organopolysiloxane with the structural variation of formula (I).

[0028] The silicone polyether is typically present in the polyol composition at a concentration of 0.5 wt. % or more, preferably 1.5 wt. % or more, while at the same time 5 wt. % or less, preferably 4 wt. % or less, based on the weight of the polyol composition.

[0029] The polyol composition can include additional components, such as any one or any combination of two or more of the following: flame retardants (such as tris(chloroisopropyl)phosphate and triethylphosphate), water, catalysts, colorants, diluents, thickeners, and fillers.

[0030] In a second aspect, the present invention is a process for preparing a polymer foam, comprising combining a polyol composition of the present invention with a composition comprising an isocyanate-functional component. One advantage of the polyol composition of the present invention is that it is particularly stable to phase separation, particularly separation of the blowing agent from the polyol. Such stability allows for storage of the polyol composition prior to preparation and combination with a composition comprising an isocyanate-functional component to produce a polymer foam. Thus, the process of the present invention can include first preparing a polyol composition, then aging the polyol composition for one or more days at a temperature in the range of 10 to 30°C before combining it with a composition comprising an isocyanate-functional component, and still produce a polymer foam with a uniform cell size without large holes. [Example]

[0031] The silicone polyethers for the following Examples (Ex) and Comparative Examples (Comp Ex) are prepared by first preparing a siloxane reactant and a polyether reactant, and then reacting the polyether reactant with the siloxane reactant to obtain the silicone polyether.

[0032] Preparation of Siloxane Reactants Table 1 lists the ingredients for preparing the siloxane reactant.

[0033] [Table 1] XIAMETER is a trademark of Dow Silicones. DOWSIL is a trademark of The Dow Chemical Company.

[0034] Prepare Siloxane Reactants 1-8 using the following procedure, referring to Table 2 for the weight percentages of ingredients and properties of the resulting product Siloxanes 1-8.

[0035] The appropriate amounts of cyclic siloxane, SiH siloxane, and endblock siloxane are placed in a three-neck flask equipped with a thermocouple, a cold-water cooled condenser, and mechanical stirring (a glass rod with a polytetrafluoroethylene paddle). The flask is purged with nitrogen for 15 seconds to avoid volatilization of the endblock siloxane. 500 parts per million (ppm) of catalyst based on the total component weight is added to form a reaction mixture. The reaction mixture is heated to 60 degrees Celsius (°C) using an aluminum heating block and held at that temperature for 8 hours with stirring. After 8 hours, heating is discontinued, and the contents of the flask are neutralized by adding a neutralizing agent at a concentration of 2% by weight based on the weight of the flask contents. The contents of the flask are stirred for 12 hours and then filtered through a 5-micrometer filter paper to remove solids. The resulting material is a siloxane reactant having the average structure of Formula (Ia): R3SiO(R2SiO) x (RHSiO) y SiR3(Ia)

[0036] The siloxane reactants are characterized as described above, and the results are shown in Table 2, along with the values ​​of the variables from formula (Ia).

[0037] [Table 2]

[0038] Preparation of Polyether Reactants Table 3 lists the ingredients for preparing the polyether reactants.

[0039] [Table 3] AMBOSOL is a trademark of PQ Corporation.

[0040] Twelve polyether reactants are prepared using a 17.1 L stainless steel reactor, temperature controlled by an external thermostatic control unit. A gravimetric oxide dosing system is used, limited by a maximum pressure inside the reactor of 0.4 MPa (4.0 bar). The oxide feed automatically stops after the desired amount has been delivered.

[0041] Table 4 lists the amount of each reactant used to prepare the polyether reactants and the characterization of the polyether reactants. Each polyether reactant has the formula (III): CH2=CHCHO-(EO) n (PO) m (EO) e H (III) and Table 4 identifies the average values ​​of the variables in formula (III) for the 12 polyether reactants.

[0042] [Table 4]

[0043] Preparation of Polyether Reactant 1, Polyether Reactant 6, and Polyether Reactants 8-11 Initiator 1 and catalyst are charged to a reactor at 23°C. The reactor is thoroughly flushed with nitrogen. While mixing at approximately 250 revolutions per minute (rpm), the reactor contents are brought to 110-115°C. Water is removed from the initiator / catalyst mixture by applying a vacuum of 3 kilopascals (30 millibars). After 1 hour and 30 minutes under vacuum, a sample is removed from the reactor and the water content is determined by titration. The remaining reactor contents are pressurized with nitrogen to approximately 120 kilopascals (1.2 bar). While stirring at 125 rpm, the temperature of the reactor contents is increased to 125°C. Alkylene oxide 1 is added as addition 1 over 2 hours. The reactor contents are digested for 6 hours and then cooled to approximately 70°C. At 60°C, the reactor contents are diluted with solvent (88% by weight isopropyl alcohol and 12% wet weight water) at a concentration of 20 g of solvent per 100 g of product. The resulting mixture was passed through an ion exchange resin at 58°C for 75 minutes: first through a cation exchange resin (Alfa Aesar™ Diaion™ PK228-Na), then through a mixed bed of equal volumes of anion and cation exchange resins (Alfa Aesar™ Diaion™ PA316-CI). Alfa Aesar is a trademark of Thermo Fisher Scientific. Diaion is a trademark of Mitsubishi Chemical Corporation. The solvent was removed using a rotary evaporator by applying a vacuum of 2 kPa (20 mbar) at approximately 85°C, followed by post-treatment with magnesium silicate adsorbent. The mixture was filtered at 40-70°C using a Büchner funnel with a Sartorius Stedim Biotec paper filter type 1288. The resulting polyether was characterized as described above.

[0044] Preparation of Polyether Reactant 2 and Polyether Reactant 3 Polyether reactant 11 and catalyst are charged to a reactor at 23°C. The reactor is flushed thoroughly with nitrogen. While mixing at approximately 250 rpm, the reactor contents are brought to 110-115°C. Water is removed from the initiator / catalyst mixture by applying a vacuum of 3 kilopascals (30 millibars). After 2 hours and 45 minutes under vacuum, a sample is removed from the reactor and the water content is determined by titration. The remaining reactor contents are pressurized with nitrogen to approximately 120 kilopascals (1.2 bar). While stirring at 125 rpm, the temperature of the reactor contents is increased to 125°C. Alkylene oxide 2 is added as addition 2 over 3 hours. The reactor contents are digested for 1 minute, and alkylene oxide 1 is added as addition 3 over 1 hour and 40 minutes. The reaction is digested for 6 hours and then cooled to approximately 70°C. At 60°C, the reactor contents are diluted with solvent (88% by weight isopropyl alcohol and 12% wet water) at a concentration of 20 g of solvent per 100 g of product. The resulting mixture is passed through an ion exchange resin at 58°C for 75 minutes: first through a cation exchange resin (Alfa Aesar™ Diaion™ PK228-Na), then through a mixed bed of equal volumes of anion and cation exchange resins (Alfa Aesar™ Diaion™ PA316-CI). Alfa Aesar is a trademark of Thermo Fisher Scientific. Diaion is a trademark of Mitsubishi Chemical Corporation. The solvent is removed using a rotary evaporator by applying a vacuum of 2 kPa (20 mbar) at approximately 85°C, followed by post-treatment with magnesium silicate adsorbent. The product is filtered at 40-70°C using a Büchner funnel with a Sartorius Stedim Biotec paper filter type 1288. The resulting polyether is characterized as above.

[0045] Preparation of Polyether Reactant 4 and Polyether Reactant 5 Polyether reactant 11 and catalyst are charged to a reactor at 23°C. The reactor is flushed thoroughly with nitrogen. While mixing at approximately 250 rpm, the reactor contents are brought to 110-115°C. Water is removed from the initiator / catalyst mixture by applying a vacuum of 3 kilopascals (30 millibars). After 1 hour 30 minutes under vacuum, a sample is removed from the reactor and the water content is determined by titration. The remaining reactor contents are pressurized with nitrogen to approximately 120 kilopascals (1.2 bar). While stirring at 125 rpm, the temperature of the reactor contents is increased to 125°C. Alkylene oxide 2 is added as addition 2 over 1 hour. The reactor contents are digested for 4 hours 30 minutes, and alkylene oxide 1 is added as addition 3 over 1 hour 40 minutes. The reaction is digested for 6 hours and then cooled to approximately 70°C. At 60°C, the reactor contents are diluted with solvent (88% by weight isopropyl alcohol and 12% wet water) at a concentration of 20 g of solvent per 100 g of product. The resulting mixture is passed through an ion exchange resin at 58°C for 75 minutes: first through a cation exchange resin (Alfa Aesar™ Diaion™ PK228-Na), then through a mixed bed of equal volumes of anion and cation exchange resins (Alfa Aesar™ Diaion™ PA316-CI). Alfa Aesar is a trademark of Thermo Fisher Scientific. Diaion is a trademark of Mitsubishi Chemical Corporation. The solvent is removed using a rotary evaporator by applying a vacuum of 2 kPa (20 mbar) at approximately 85°C, followed by post-treatment with magnesium silicate adsorbent. The product is filtered at 40-70°C using a Büchner funnel with a Sartorius Stedim Biotec paper filter type 1288. The resulting polyether is characterized as above.

[0046] Preparation of polyether reactant 7 Polyether reactant 11 and catalyst are charged to a reactor at 23°C. The reactor is thoroughly flushed with nitrogen. While mixing at approximately 250 rpm, the reactor contents are brought to 110-115°C. Water is removed from the initiator / catalyst mixture by applying a vacuum of 30 mbar (3 kilopascals). After 1 hour and 30 minutes under vacuum, a sample is removed from the reactor and the water content is determined by titration. The remaining reactor contents are pressurized with nitrogen to approximately 1.2 bar (120 kilopascals). While stirring at 125 rpm, the temperature of the reactor contents is increased to 125°C. Alkylene oxide 1 and alkylene oxide 2 are added over 2 hours, followed by an 8-hour digestion period, at which point the reactor contents are cooled to 70°C. At 60°C, the reactor contents are diluted with solvent (88% by weight isopropyl alcohol and 12% wet weight water) at a concentration of 20 g of solvent per 100 g of product. The resulting mixture was passed through an ion exchange resin at 58°C for 75 minutes: first through a cation exchange resin (Alfa Aesar™ Diaion™ PK228-Na), then through a mixed bed of equal volumes of anion and cation exchange resins (Alfa Aesar™ Diaion™ PA316-CI). Alfa Aesar is a trademark of Thermo Fisher Scientific. Diaion is a trademark of Mitsubishi Chemical Corporation. The solvent was removed using a rotary evaporator by applying a vacuum of 2 kPa (20 mbar) at approximately 85°C, followed by post-treatment with magnesium silicate adsorbent. The mixture was filtered at 40-70°C using a Büchner funnel with a Sartorius Stedim Biotec paper filter type 1288. The resulting polyether was characterized as described above.

[0047] Preparation of silicone polyethers The following procedures are used to prepare 11 comparative silicone polyethers and 6 example silicone polyethers.

[0048] Using the ingredients and amounts in Table 4, prepare a 500 g batch by adding the polyether reactants, siloxane reactants, and isopropyl alcohol solvent (if specified) to a three-neck round-bottom flask. Equip the flask with an overhead mechanical stirrer (glass rod with a polytetrafluoroethylene paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. Heat the reaction mixture to 70 °C using an aluminum heating block under a slight nitrogen sparge and vigorous stirring (275 rpm). Catalyze the reaction with 5 ppm platinum catalyst (Karstedt catalyst available from Sigma-Aldrich). Once the resulting exotherm has subsided, heat the reaction to 83 °C for 1 hour. If solvent is present, slowly remove it by applying a vacuum to the warm reaction mixture while maintaining the temperature above 60 °C. Once a vacuum is safely achieved below 1.33 kPa (10 Torr), increase the temperature to 100 °C and maintain at 800 Pa (6 Torr) for 1 hour. The resulting material is a silicone polyether. Characterized as described herein above. The results of the characterization are shown in Table 5 for the variables of formula (I).

[0049] [Table 5]

[0050] [Table 6]

[0051] Preparation of Polyol Composition Polyol compositions containing each sample of silicone polyether in Table 5 are prepared using the following procedure with the ingredients and formulations in Table 6. The polyol compositions are characterized for stability as described below.

[0052] The polyol, flame retardant, water, catalyst, and silicone polyether are combined in the amounts shown in Table 6 and mixed at 2000 rpm in a container with a 5-centimeter (2-inch) Cowles mixer blade until homogeneous. The blowing agent is added and further mixed until a white emulsion, the polyol composition, is formed. The mixture is weighed to determine if any blowing agent has been lost during mixing, and additional blowing agent is added to reach the target amount. The emulsion is filled into two 40-milliliter glass vials, which are then sealed. The remaining emulsion is divided into storage containers, which are sealed to prevent loss of blowing agent. One vial and one storage container are placed in storage at 27°C, and the other vial and storage container are placed in storage at 10°C.

[0053] [Table 7] JEFFCAT is a trademark of JPMorgan Chase Bank. DABCO and POLYCAT are trademarks of Evonik Operations LLC.

[0054] Stability evaluation of polyol compositions For each polyol composition, stability is assessed by visually inspecting the vial once daily for signs of phase separation, such as the formation of a clear layer on top of the white emulsion, the separation of the vial contents into two distinct layers, or any portion of the emulsion transitioning from a white emulsion to a clear, translucent liquid. The number of days it takes for evidence of phase separation to appear is recorded. The longer the number of days it takes for phase separation to appear, the more stable the polyol composition. Table 7 reports the number of days required for evidence of phase separation to appear for the sample polyol compositions.

[0055] Foam appearance test After 6 days of storage, 60 g of the polyol composition is blended with 141.2 g of polymethylene polyphenylisocyanate (CAS 9016-87-9, available from The Dow Chemical Company as PAPI 580N) and mixed thoroughly with a 5 centimeter (2 inch) Cowles mixer blade at 3000 rpm for 5 seconds. The resulting mixture is poured into a 25 cm x 25 cm x 10 cm box and allowed to form a foam. This procedure is followed for both the samples stored at 27°C and the samples stored at 10°C.

[0056] The resulting foam is characterized as follows: The degree of foam rise relative to the height of the box is recorded. Full rise means that the foam fills the entire height of the box. After the degree of foam height is recorded, the foam is removed from the box. The foam is cut in half parallel to the rise of the foam, and the surface of the cut side of the foam is visually inspected for signs of deviation from uniform texture and color. Signs of deviation from uniform texture and color include visible large holes and uneven coloring. Table 7 reports the results of foam appearance testing for foams made using the sample polyol compositions.

[0057] The data in Table 7 show that polyol compositions made using the polyol compositions of the present invention were stable to phase separation for 6 days at both 27°C and 10°C, producing foams with uniform color, texture, and full rise after storage at both temperatures. In contrast, polyol compositions containing silicone polyethers outside the scope of the present invention were unable to remain stable from phase separation even for nearly 6 days at both temperatures, or to produce foams with uniform color, texture, and full rise after storage at both temperatures.

[0058] [Table 8]

Claims

1. 1. A polyol composition comprising a polyol, a blowing agent, and a silicone polyether, wherein the silicone polyether has an average chemical formula (I): R ３ SiO(R ２ SiO) ｘ (RR ａ SiO) ｙ SiR ３ (I) wherein (a) each R, in each occurrence, is independently selected from alkyl groups having 1 to 4 carbon atoms; (b) the subscript x has an average value in the range of 5 to 55; (c) the subscript y has an average value in the range of 1 to 10; (d) the sum of x and y has an average value in the range of 6 to 60; and (e) R ａ has the average chemical formula (II): -(32) ２ ) ) ｐ -(59) ｎ (0) ｍ (59) ｅ 2(99) wherein (i) EO is -CH ２ CH ２ It points to O-, (ii) PO is —CH ２ CH (CH ３ ) O-, (iii) the subscript e has an average value in the range of 1 to 50; (iv) the subscript m has an average value in the range of 2 to 10; (v) the subscript n has an average value in the range of 1 to 20; (vi) the sum of the subscripts e and n has an average value within the range of 25 to 70; and (vii) the subscript p has an average value in the range of 1 to 11; with the proviso that the PO content is greater than 0 and simultaneously less than 15 weight percent of the combined weight of EO and PO, and the EO content is greater than 58 weight percent and simultaneously less than 75 weight percent of the silicone polyether weight; and The blowing agent is greater than 70 volume percent hydrocarbon blowing agent, based on the volume of the blowing agent, and the blowing agent satisfies the following conditions: (f) R ａ has a number average molecular weight in the range of 1500 to 2500 grams per mole as determined by size exclusion chromatography; and (g) The sum of the average values ​​of the subscripts x and y is 50 or less.

2. 10. The polyol composition of claim 1, further characterized in that the polyol composition contains less than 5 mole percent of variations of the silicone polyether of formula (I) having formula (II) that are terminated with non-primary OH, based on the total number of moles of silicone polyether having formula (I).

3. 3. The polyol composition of claim 1 or claim 2, wherein the blowing agent is free of hydrofluorocarbons and hydrochlorofluorocarbons.

4. The polyol composition of any one of claims 1 to 3, wherein the polyol composition is free of halogenated blowing agents.

5. The composition according to any one of claims 1 to 4, wherein the polyol is selected from polyether polyols and polyester polyols.

6. 6. The polyol composition of any one of claims 1 to 5, wherein the polyol is an alkoxy polyol and contains greater than 50 weight percent EO, based on the weight of the alkoxy in the polyol.

7. 7. The polyol composition of claim 1, wherein each R is methyl, subscript x has an average value in the range of 14 to 50, subscript y has an average value in the range of 2 to 7, x+y has an average value in the range of 16 to 60, subscript e has an average value of 20, subscript n has an average value of 11, subscript m has an average value of 2.5, subscript p has an average value of 3, the PO content is 9 to 10 weight percent of the total weight of EO and PO, and the EO content is 59 to 66 weight percent of the weight of the silicone polyether.

8. A process for preparing a polymer foam, comprising combining the polyol composition of any one of claims 1 to 7 with a composition comprising an isocyanate-functional component.

9. 10. The process of claim 8, further characterized by first preparing the polyol composition and then aging it for one or more days at a temperature in the range of 10 to 30°C before combining it with a composition comprising an isocyanate-functional component.

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