WO2022160439A1 - 用于聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物 - Google Patents

用于聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物 Download PDF

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WO2022160439A1
WO2022160439A1 PCT/CN2021/082825 CN2021082825W WO2022160439A1 WO 2022160439 A1 WO2022160439 A1 WO 2022160439A1 CN 2021082825 W CN2021082825 W CN 2021082825W WO 2022160439 A1 WO2022160439 A1 WO 2022160439A1
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weight
parts
blowing agent
foaming
alkanolamine
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PCT/CN2021/082825
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English (en)
French (fr)
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毕戈华
毕玉遂
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山东理工大学
补天新材料技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a carbonate alkanolamine salt composite foaming agent for (casting type) polyurethane rigid foam used in refrigerators, freezers, water heaters, cold chain insulation (refrigerated vehicles) and other industries, and more particularly, to a compound foaming agent composed of high water content
  • a chemical-physically combined blowing agent in which an alkanolamine carbonate chemical blowing agent is combined with cyclopentane and optionally a physical blowing agent with a boiling point in the range of 15-41°C, especially the polyurethane rigid foam It is prepared using polymer polyols containing part of aromatic polyester polyols (eg polyethylene phthalate polyols) and/or toluenediamine polyether polyols as whitestocks.
  • Polyurethane rigid foam material is a high-quality thermal insulation material, which is widely used in refrigerators, freezers, water heaters, cold chain insulation and other industries. For the needs of environmental protection, in these industries, water and cyclopentane are commonly used as foaming agents in the production process of polyurethane foam materials. Due to the relatively high thermal conductivity of cyclopentane, the thermal conductivity of foam materials is also relatively high and energy consumption is large.
  • hydrofluorocarbon physical foaming agents such as HCFC-141b (monofluorodichloroethane, molecular weight 116.95, boiling point 32 °C), CFC-113 (trichlorotrifluoroethane, molecular weight 187.39, boiling point 47.7°C), CFC-11 (trichloromonofluoromethane, molecular weight 137.4, boiling point 23.8°C), HCFC-123 (trifluorodichloroethane, molecular weight 152.93 , boiling point 27.85°C), HFC-245fa (molecular weight 134, boiling point 15.3°C), HFC-365mfc (molecular weight 148, boiling point 40.2°C), LBA (trans-1-chloro-3,3,3-trifluoropropene, molecular weight 130.5, boiling point 19°
  • US6326412 B1 discloses ammonium carbamate as a polyurethane blowing agent, wherein the ammonium carbamate has a viscosity of up to 2200 mPa.s (see specification column 6 lines 51-55, lines 51-55 in column 6), it is viscous or semi-solid state.
  • the thermal insulation properties of polyurethane rigid foam materials used in refrigerators, freezers, water heaters, refrigerated vehicles (cold chain insulation) and other industries are becoming more and more important.
  • the thermal conductivity ⁇ (mW/m ⁇ K, 10° C.) of the Laneige mold (Lance) for rigid polyurethane foams used in these industries is in the range of 19.00-20.00. If the thermal conductivity ⁇ is reduced from 19.00 to 18.90, more preferably to 18.80, 18.70, 18.60, 18.50, 18.40, 18.30, 18.20, 18.10, 18.05, 18.00 or 17.95 (where 17.95-18.00 almost belongs to the lowest limit value, continue to reduce this number becomes very difficult), each advance brings huge economic benefits.
  • the world produces at least tens of millions of refrigerators and freezers every year.
  • a refrigerator or freezer can save 0.1-0.3 kWh of electricity per day, and save 36.5-109.5 kWh of electricity a year.
  • the savings in electricity are staggering.
  • the foaming mixture (made of white and black materials in the high-pressure pouring machine) is usually poured by the spray gun method. Mixed in a mixing chamber) is injected into the mold through a single gate of the mold, and the foaming mixture (material for foaming) undergoes a foaming reaction in the mold, solidifies, and then is demolded.
  • the foaming mixture material for foaming
  • the fluidity of the foaming mixture is very important, and it is required that it can be filled into the irregular mold cavity in a short time. Every corner of the mold ensures that the foaming mixture fills the mold evenly and does not leave dead corners.
  • the foaming process of refrigerators, freezers, water heaters and other industries is actually an online foaming process on an industrialized production line.
  • the inventors of the present application have found through years of research that, relative to the influence of the thermal conductivity of the gas in the cells on the thermal insulation performance of the rigid polyurethane foam, the microstructure of the cells in the rigid polyurethane foam has an impact on the thermal insulation performance of the foam. have a greater impact.
  • the cell microstructure and closed cell ratio in the rigid polyurethane foams mainly determine the thermal insulation properties of the foams.
  • the technical problem to be solved by this application is to optimize the composition of the foaming composition, improve the foaming process, and then change the microstructure of the foam, so as to improve the thermal insulation performance and strength properties of the produced polyurethane rigid foam.
  • the inventors of the present application found that, for a composite foaming agent composed of an alkanolamine carbonate chemical foaming agent and a physical foaming agent, some influencing factors, for example, chemical foaming agent and physical foaming agent, individually or both In complex form, the compatibility with the polymer polyol as a white material, the activity of the chemical blowing agent and the boiling point of the physical blowing agent (which produces initial nucleation) (which affect the rate of the blowing reaction) rise time or cream time), the content and type of alkanolamine (as a cross-linking agent), water content, etc., have a direct impact on the foaming reaction process.
  • some influencing factors for example, chemical foaming agent and physical foaming agent, individually or both In complex form, the compatibility with the polymer polyol as a white material, the activity of the chemical blowing agent and the boiling point of the physical blowing agent (which produces initial nucleation) (which affect the rate of the blowing reaction) rise time or cream time), the content and type of alkan
  • the appropriate expansion speed and curing speed of the foamed mixture formed by mixing the white and black materials are mainly determined. cell microstructure.
  • water and alkanolamines formed by the decomposition of chemical foaming agents (alcoholamines with higher activity are used as catalysts and cross-linking agents first, and water with low activity is used as cross-linking agents in the later stage of the foaming reaction or does not participate in the cross-linking reaction. ) content in turn determines the cross-linking strength of the inner wall of the cells and thus affects the compressive strength and deformation resistance of the foam material.
  • the crosslinking of the inner walls of the cells is beneficial in preventing cell rupture and thus increasing the closed cell ratio, which in turn improves the thermal insulation properties of the foam.
  • Polyurethane rigid foam for applications in refrigerators, freezers, water heaters and cold chain insulation (refrigerated vehicles) industries that have high requirements in terms of thermal insulation properties (hereinafter referred to as "polyurethane rigid foam for refrigerators” or "PU foam for refrigerators")
  • PU foam for refrigerators Polyurethane rigid foam for refrigerators
  • PU foam for refrigerators a corresponding appropriate foaming speed is required in the industrial polyurethane foaming process.
  • the foaming speed of related fields is shown in Table A below:
  • polyisocyanates eg, polymethylene polyphenyl polyisocyanates, or polymeric MDI
  • black materials various additives (eg, polyurethane catalysts, foams, etc.) are added.
  • the polymer polyol composition for foaming of the stabilizer and optional flame retardant, optional chain extender and optional crosslinking agent) and blowing agent is referred to as "white stock”.
  • various auxiliary agents such as polyurethane catalysts, foam stabilizers and optional flame retardants, optional chain extenders and optional crosslinking agents
  • dry white stock that is to say, "dry white material” refers to: “white material” without foaming agent, or a dry white material for polyurethane foaming containing polymer polyols and other auxiliary agents other than foaming agent material.
  • the polyurethane catalyst in a "dry white stock” or “white stock” includes a secondary amine-type early stage catalyst (ie, an early stage catalyst) and a tertiary amine-type late stage crosslinking catalyst (ie, a late stage catalyst).
  • the object of the present invention is to design specific blowing agent compositions for (casting) rigid polyurethane foams for refrigerators, freezers, water heaters (electric or solar water heaters) or refrigerated vehicles.
  • a pouring machine or high pressure, medium pressure or low pressure pouring machine
  • the foaming mixture has high fluidity and can evenly fill the entire mold, and the foaming is completed within a specified time (the mold opening time or demolding time is generally about 180 seconds).
  • the ideal cell microstructure of rigid polyurethane foam refers to a fine (or fine) cell structure with uniform cell size. That is to say, on the one hand, the foam has a lower density, on the other hand, the number of foam per unit volume is as large as possible (from the SEM picture, the number of cells per unit area should be as large as possible), the average cell diameter is smaller, and the cell size is relatively uniform, and the closed cell ratio is high.
  • the foam density is generally 28-36Kg/m 3 ; in the water heater industry, the foam density is generally 33-40Kg/m 3 .
  • the average cell diameter is in the range of 180-240 microns (preferably 190-230 microns, more preferably 195-220 microns), especially,
  • the size of the cells is relatively uniform, and the microstructure of such cells is fine or ideal. That is to say, the more the number of cells per unit volume, the average cell diameter is between 180-240 microns, the more uniform cell diameter and the higher the closed cell ratio, the more ideal the cell microstructure is .
  • said parts by weight are (approximately) relative to 80-115 parts by weight (preferably 85-110 parts by weight, more preferably 90-100 parts by weight or 100-115 parts by weight) of the polycomponent containing polymer Dry white material for polyurethane foaming of alcohols and other auxiliaries except foaming agent (abbreviation, dry white material), or (approximately) relative to 80-115 parts by weight (preferably 85-110 parts by weight, more Preference is given to 90-100 parts by weight or 100-115 parts by weight) of all polymer polyols present in the dry white.
  • Polymer polyols used in dry whites include polyether polyols (eg, polypropylene oxide polyols) and/or polyester polyols (eg, aromatic polyester polyols or PET polyols).
  • a high-water content, low-alcoholamine bicarbonate content carbonate alkanolamine salt foaming agent composition for preparing cast-type polyurethane rigid foam
  • FC carbonic alkanolamine salt foaming agent composition
  • FC foaming agent composition
  • the foaming mixture including black and white materials is injected into the mold through a (single) pouring gate, so that the foaming mixture is uniformly filled throughout the mold.
  • the cavity is then opened or demolded for approximately 180 seconds from the start of injection. That is, the pre-, mid- and post-reactions were completed within 3 minutes.
  • a high water content, low alcohol amine bicarbonate content carbonate alkanolamine salt blowing agent composition for preparing polyurethane rigid foam
  • the FC contains a carbonate alkanolamine salt chemical blowing agent (F1) with high water content and low alkanolamine bicarbonate content.
  • FC carbonate alkanolamine salt blowing agent composition
  • the (hydrofluorocarbons) physical blowing agent (F2) with a boiling point in the range of 15-41° C., wherein the physical blowing agent (F2) is selected from HFC-245fa, HFC-365mfc, one or more (two or three) of LBA and hexafluorobutene;
  • the relative consumption (or mass ratio) of various components is: the amount of water (F3) is 0-2 parts by weight, 0-1.5 parts by weight, more preferably 0-1 parts by weight, further preferably 0-0.5 parts by weight parts, more preferably 0-0.1 parts by weight; the amount of physical foaming agent (F2) is 0-7 parts by weight, preferably 0-6.5 parts by weight, preferably 0-6 parts by weight, preferably 0-5.5 parts by weight, preferably 0- 5 parts by weight, more preferably 0-4.5 parts by weight, preferably 0-4 parts by weight, more preferably 0-3.5 parts by weight, more preferably 0-3 parts by weight, more preferably 0-2.5 parts by weight, most preferably 0 parts by weight; The amount of blowing agent (F1) is 1-10 parts by weight, preferably 1.2-9.5 parts by weight, preferably 1.3-9 parts by weight, preferably 1.4-8.5 parts by weight, preferably 1.5-8 parts by weight, preferably 2.8-8 parts by weight, and, The amount of cyclopentane is
  • the sum of the mass of water (F3) + physical foaming agent (F2) + chemical foaming agent (F1) is: 4-10 parts by weight, preferably 4-9.5, 4-9, 4.5-9, 4.5-8.5, for example 4.999 servings, 5 servings, 5.499 servings, 5.5 servings, 6, 7 or 8 servings.
  • the mass of cyclopentane is 10-20 parts by weight, preferably 10.5-19.5, 11-19, 11.5-18.5, 12-18, 12-17.5, such as 13, 14, 15, 16 or 17.
  • the mass of the physical blowing agent (F2) is 0 parts by weight. More preferably, the mass of water (F3) and physical foaming agent (F2) are both 0 parts by weight.
  • the mass ratio (or relative consumption) of cyclopentane is: (4-10 parts by weight): (10-20 parts by weight), preferably (4-9.5): (10-20), (4-9): (10-20), (4-9):(10-18), (4-9):(10-16), preferably (4.5-10):(10-20), (5-9.5):( 10-20), (5-9.5):(10-18), (5-9.5):(10-16), (5-9):(10-20), (5-9):(10- 18), (5-9):(10-16
  • chemical blowing agents (F1) contain the following ingredients (or components):
  • the sum of the weights of components (A), (B), (C) and (D) is 90-100 wt %, preferably 92-100 wt %, preferably 93- 100wt%, preferably 95-100wt%, preferably 98-100wt%, preferably 98.5-100wt%, preferably 99-100wt%, preferably 99.5-100wt%, preferably 99.8-100wt%, more preferably 100wt%.
  • the total C2-C9 alcohol amines in the chemical blowing agent (F1) comprise or mainly comprise 70-100 mol %, preferably 72-100 mol %, preferably 75-100 mol %, preferably 77-100 mol %, preferably 80-100 mol % , preferably 82-100mol%, preferably 85-100mol%, preferably 87-100mol%, preferably 90-100mol%, preferably 92-100mol%, preferably 95-100mol%, preferably 97-100mol%, preferably 98-100mol%) of Specific C4-C9 diolamines which are (I) C4-C7 diolamines with only hydroxyethyl groups (Ia), (II) C5-C9 with hydroxyisopropyl groups Diolamines (IIa) or (III) Combinations or mixtures of component (I) alcoholamines (Ia) and component (II) alcoholamines (IIa), the mol % is based
  • the pH of the chemical blowing agent (F1) is 8.6-10.4, preferably 8.8-10.2, preferably 9-10.1, more preferably 9.2-10, preferably 9.3-9.7, more preferably 9.4-9.6.
  • the blowing agent composition (FC) is used for the production of insulating foams for use at low temperatures (eg for the production of insulating foams for refrigerators or freezers), water (F3)+physical blowing agent (F2)+
  • the sum of the mass of the chemical blowing agent (F1) is (5.5-10) parts by weight, preferably 6-10 parts by weight, and the mass of cyclopentane is 10-20 parts by weight, preferably 12-18 parts by weight; or, water
  • the ratio (or relative amount) of the sum of the mass of F3) + physical foaming agent (F2) + chemical foaming agent (F1) to the mass of cyclopentane is (5.5-10): (10-20), preferably ( 6-10):(12-18) or (5.5-9):(10-20) or (5.5-8.5):(10-20).
  • the chemical blowing agent (F1) is used in an amount of more than 5 parts by weight (eg, 5 or 5.5 or 6 parts by weight) (additionally, for example, F2 or water (F3) is used in an amount of 0-1 parts by weight), so that
  • the foamed material white material + black material
  • the foamed material has suitable inspiration time and drawing time
  • the cell size of the obtained foam material is relatively uniform
  • the foam material has a lower product density (eg 28-36 Kg/m 3 ) while significantly improving the mechanical strength (crosslinking density of cell walls and resistance to shrinkage deformation) and thermal insulation properties of the resulting foam.
  • the blowing agent composition (FC) is used for the preparation of insulating foams for use at higher temperatures (eg 70-110°C) (eg for the preparation of water heaters (electric or solar))
  • the sum of the mass of water (F3) + physical foaming agent (F2) + chemical foaming agent (F1) is (4-10) parts by weight, preferably 4-9 parts by weight, preferably 4-8 parts by weight, preferably 5 -7 parts by weight, preferably 5.5-6 parts by weight
  • the mass of cyclopentane is 10-20 parts by weight, preferably 12-18 parts by weight or 12-16 parts by weight
  • the ratio (or relative amount) of the sum of the mass of )+chemical blowing agent (F1) to the mass of cyclopentane is (4-10 parts by weight): (10-20 parts by weight), more preferably (4-9 parts by weight) parts): (12-18 parts by weight), preferably (4-8 parts by weight): (12-16 parts by weight).
  • the chemical blowing agent (F1) is used in an amount of 3-5.5 parts by weight (eg, less than 5.5 or less than 5 parts by weight, such as 3-5.499 parts, or 4 parts) (additionally, for example, F2 or water (F3) with 0-1 parts by weight), so that the produced foam material has a higher product density (for example, about 40Kg/m 3 ), and the foam material is suitable for a higher temperature (for example, 70-110 ° C) to play a thermal insulation effect, At the same time, the production cost of the foam material is reduced.
  • the above-mentioned high water content alkanolamine carbonate chemical foaming agent (F1) refers to a carbonate alkanolamine salt chemical foaming agent (F1) with high water content and low alcohol amine bicarbonate content.
  • N-propyl in this application includes N-n-propyl and N-isopropyl.
  • the specific C4-C9 diolamines are selected from (I) C4-C7 diolamines having only hydroxyethyl groups (Ia) and (II) C5-C9 diolamines having hydroxyisopropyl groups One or more of the alkanolamines (IIa).
  • the specific C4-C9 diolamines are: (I) C4-C7 diolamines (Ia) having only hydroxyethyl groups, or, (I) alcoholamines (Ia) and (II) having hydroxyl groups Mixtures or combinations (III) of isopropyl C5-C9 diolamines (IIa).
  • the chemical blowing agent (F1) does not Alcoholamine bicarbonate is present.
  • the above-mentioned chemical foaming agent (F1) is prepared by a neutralization method in which CO2 gas is introduced into a mixture of C2-C9 alcohol amine and water; preferably, the neutralization method comprises: in C2-C9 alcohol The CO2 gas with a gauge pressure of 0.09-0.4MPa (0.9-4atm, such as 0.09-0.35MPa or 0.1-0.3MPa) is passed into the mixture of amine and water until it is saturated, optionally, the above-mentioned product is further added to the obtained product C2-C9 alkanolamines (preferably, the specific C4-C9 diolamines described above, such as diethanolamine and/or diisopropanolamine) such that the pH of the product is in the range 8.6-10.4 (preferably 8.8-10.2, 9-10.1, preferably 9.2-10, preferably 9.2-9.7, preferably 9.4-9.6), to obtain chemical blowing agents (F1); preferably, wherein the amount of water in the mixture of C2-C9 alcohol
  • the above-mentioned C2-C9 alkanolamines described herein include the above-mentioned specific C4-C9 diolamines, wherein the specific C4-C9 diolamines and the composition (mol%) thereof are the same as defined above.
  • the pressure of the CO gas introduced into the mixture of C2-C9 alkanolamine and water should be selected (generally according to the basicity of the C2-C9 alkanolamine), which pressure is sufficient to make the C2-C9 alkanolamine as formed as possible
  • the stoichiometric amount of bis(C2-C9 alcoholamine) carbonate is neutralized by CO2 but does not form more than 10wt% (eg 0-10wt%, preferably 0-9wt%, 0-8wt%, 0-7wt%, 0-6wt% %, 0-5wt%, 0-4wt%, 0-3wt%, 0-2wt%, 0-1wt%, 0-0.5wt%, most preferably 0wt%) of C2-C9 alkanolamine bicarbonate, the wt % is based on the weight of the chemical blowing agent (F1) formed (ie, the carbonate amine salt hydrate).
  • the appropriate CO pressure is selected according to the basicity of different C2-C9 alkanolamines so that the C2-C9 alkanolamines can form carbonic acid bis(C2-C9 alkanolamine) salts as much as possible
  • the stoichiometric amount is neutralized by CO and the content of C2-C9 alkanolamine bicarbonate in the obtained chemical blowing agent (F1) is as low as possible, for example below 10wt%, more preferably below 8wt% or even Below 5 wt%, the choice of CO pressure is easily achievable by those skilled in the art.
  • a chemical foaming agent (F1) containing two or more different basic alcohol amines and the content of the formed alcohol amine bicarbonate is relatively low it can be prepared by using different CO 2 gases respectively.
  • the carbonate of each alkanolamine (almost free of alkanolamine bicarbonate) was prepared by passing CO 2 gas into each alkanolamine under the pressure of Then two or more neutralized products containing almost no alkanolamine bicarbonate are mixed in corresponding proportions to obtain a mixture containing a plurality of alkanolamine carbonates and a smaller amount of alkanolamine bicarbonate
  • a chemical blowing agent (F1) A chemical blowing agent (F1).
  • the inventors found through experiments that a small amount of unstable alcoholamine bicarbonate present in the foaming agent composition (FC) has a great influence on the foaming reaction, resulting in the rise time in the foaming reaction. Shorten (eg to 1-2 seconds). For example, due to the presence of bicarbonate, a violent reaction occurs immediately after mixing the white and black materials, and the foam expands rapidly and out of control. The reason for this may be that the alkanolamine bicarbonate is unstable (easily decomposed) and the reactivity is high. Therefore, it is important to control the content of alcoholamine bicarbonate in the chemical blowing agent (F1) below 10 wt% (especially below 8 wt% or 5 wt%).
  • FC foaming agent composition
  • the performance of the foaming agent composition can be further improved.
  • the specific C4-C9 diolamines are: (I) alcoholamines (Ia), or (III) composed of component (I) alcoholamines (Ia) and component (II) alcoholamines (IIa) ); more preferably, the specific C4-C9 diolamine is (III) a combination consisting of components (I) alcoholamines (Ia) and (II) alcoholamines (IIa) or a mixture; therefore, wherein the molar ratio of component (I) alcoholamines (Ia) to component (II) alcoholamines (IIa) is 1:(0-2.5), preferably 1:(0.1-2.5), Preferably 1:(0.1-2), more preferably 1:(0.2-1.5), more preferably 1:(0.22-1.2), more preferably 1:(0.24-0.9), more preferably 1:(0.25-0.5), more preferably Preferably 1:(0.27-0.4), more preferably 1:(0.29-0.45), most preferably 3:1.
  • the mol% of component (I) is 28-100 mol%, More preferably 33-91wt%, more preferably 40-83wt%, more preferably 45-82wt%, more preferably 52-81wt%, more preferably 66-80wt%, more preferably 71-78wt%, more preferably 68-77wt%, most preferably Preferably 75 mol%, based on the total molar amount of component (I) and component (II).
  • C2-C9 alkanolamines include specific C4-C9 diolamines (eg C4-C9 diolamines (Ia+IIa) with hydroxyethyl and/or hydroxyisopropyl groups, such as Diethanolamine or diisopropanolamine), secondary amine type C3-C6 monoalcoholamine (eg secondary amine type C3-C6 monoalcoholamine with hydroxyethyl or hydroxyisopropyl (Ib+IIb), such as N-methyl base monoisopropanolamine or N-methylethanolamine) and optional primary amine type C2-C9 monoalcoholamines and optional tertiary amine type C4-C7 monoalcoholamines and optional tertiary amine type C6- C9 triolamines.
  • specific C4-C9 diolamines eg C4-C9 diolamines (Ia+IIa) with hydroxyethyl and/or
  • C4-C9 diolamines (Ia+IIa) with hydroxyethyl and/or hydroxyisopropyl include, for example, diethanolamine, diisopropanolamine, ethanolisopropanolamine, N-methyl diethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N- Methylethanolisopropanolamine, N-ethylethanolisopropanolamine, and N-propylethanolisopropanolamine.
  • secondary amine-type C3-C6 monoalcoholamines (Ib+IIb) with hydroxyethyl or hydroxyisopropyl include, for example, N-methylmonoethanolamine, N-ethylmonoethanolamine, N-propyl monoethanolamine, N-methyl monoisopropanolamine, N-ethyl monoisopropanolamine and N-propyl monoisopropanolamine.
  • the total C2-C9 alkanolamine in the chemical blowing agent (F1) may also comprise less than 30 mol%, for example 0-30 mol%, preferably 0-28 mol%, preferably 0-25 mol%, preferably 0-23 mol%, preferably 0-20mol%, preferably 0-18mol%, preferably 0-15mol%, preferably 0-13mol%, preferably 0-10mol%, preferably 0-8mol%, preferably 0-5mol%, preferably 0-3mol%, preferably 0 - 2 mol% of other C2-C9 alcoholamines than the specific C4-C9 diolamines mentioned above.
  • these other C2-C9 alcohol amines are selected from secondary amine type C3-C6 monoalcoholamines (Ib+IIb) with hydroxyethyl or hydroxyisopropyl (ie, (Ib) with hydroxyethyl only)
  • secondary amine type C3-C5 mono-alcohol amine and (IIb) secondary amine type C4-C6 mono-alcohol amine with only hydroxyisopropyl group wherein, only secondary amine type C3 with hydroxyethyl group -C5 monoalcoholamine (Ib) is one or more selected from N-methylmonoethanolamine, N-ethylmonoethanolamine and N-propylmonoethanolamine; and, secondary only having hydroxyisopropyl Amine type C4-C6 monoalcoholamine (IIb) is one or more selected from N-methyl monoisopropanolamine, N-ethyl monoisopropanolamine and N-
  • the mol% is based on the total molar amount of C2-C9 alcoholamines present in the chemical blowing agent (F1) (or based on the C2-C9 alcoholamines present in components (A), (C) and (D) The total molar amount of C9 alkanolamines).
  • the specific C4-C9 diolamine is selected from the group of C4-C7 diethanolamines (which includes diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and N-propyldiethanolamine), C6 -C9 diisopropanolamines (which include diisopropanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine and N-propyldiisopropanolamine) and C5- A kind of in C8 ethanol isopropanolamines (it includes ethanol isopropanolamine, N-methylethanol isopropanolamine, N-ethylethanol isopropanolamine and N-propyl alcohol isopropanolamine) or two or more (preferably, two or more); more preferably, the specific C4-C9 diolamines are composed of (C4-C7 diethanolamines) and (C6
  • the secondary amine type C3-C6 monoalcoholamine (Ib+IIb) is selected from N-methyl monoethanolamine, N-methyl monoisopropanolamine, N-ethyl monoethanolamine, N-ethyl monoethanolamine One or two or more of monoisopropanolamine, N-propyl monoethanolamine and N-propyl monoisopropanolamine.
  • C2-C9 alcohol amines in the chemical blowing agent (F1) are likely to include, in addition to the specific C4-C9 diolamines mentioned above, as well as secondary amine-type C3-C6 monoalcohols with hydroxyethyl or hydroxyisopropyl C2-C9 other than amines (ie, (Ib) secondary amine type C3-C5 monoolamines with only hydroxyethyl groups and (IIb) secondary amine type C4-C6 monoolamines with only hydroxyisopropyl groups) Alcohol amines (abbreviated as "impurity alcohol amines IA”), such as primary amine type C2-C9 monoalcoholamines, tertiary amine type C4-C9 monoalcoholamines (such as N-dimethylethanolamine and N-dimethylethanolamine) isopropanolamine), tertiary amine type C6-C9 triolamines (eg triethanol
  • the content of such other alcoholamines (impurity alcoholamines IA) in the chemical foaming agent (F1) should be as small as possible, generally 0-30mol, preferably 0-28mol%, preferably 0-25mol%, preferably 0- 23mol%, preferably 0-20mol%, preferably 0-18mol%, preferably 0-15mol%, preferably 0-13mol%, preferably 0-10mol%, preferably 0-8mol%, preferably 0-5mol%, preferably 0-3mol% , preferably 0-2 mol%, based on the total molar amount of C2-C9 alcoholamines present in the chemical blowing agent (F1) (or based on the C2 present in components (A), (C) and (D) -total molar amount of C9 alkanolamines).
  • C2-C9 alkanolamines in chemical blowing agent (F1) to include, in addition to the specific C4-C9 diolamines mentioned above, other alkanolamines: (Ib) Secondary amines with only hydroxyethyl groups Type C3-C5 monoalcoholamines, (IIb) secondary amine type C4-C6 monoalcoholamines with only hydroxyisopropyl groups, and the above-mentioned so-called "impurity alcoholamines IA"; the total mol% of all these other alcoholamines is 0-30mol%, preferably 0-28mol%, preferably 0-25mol%, preferably 0-23mol%, preferably 0-20mol%, preferably 0-18mol%, preferably 0-15mol%, preferably 0-13mol%, preferably 0- 10mol%, preferably 0-8mol%, preferably 0-5mol%, preferably 0-3mol%, preferably 0-2mol%, based
  • the parts by weight stated above are (approximately) relative to or based on 80-115 parts by weight (preferably 85-110 parts by weight, more preferably 85-100 or 90-100 parts by weight or 90-115 parts by weight or 100-115 parts by weight , such as 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 102, 105, 107, 108, 110, 112, 113 or 114 parts by weight)
  • the dry white material for polyurethane foaming containing polymer polyols and other auxiliary agents other than foaming agent are (approximately) relative to or based on 80-115 parts by weight (preferably 85-110 parts by weight, more preferably 85-100 or 90-100 parts by weight or 90-115 parts by weight or 100-115 parts by weight , such as 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96,
  • the other adjuvants include polyurethane catalysts, foam stabilizers and optional flame retardants, optional chain extenders and optional crosslinking agents.
  • the blowing agent composition (FC) is used for mixing with dry white material and polyisocyanate as black material to carry out a foaming reaction, thereby producing a rigid polyurethane foam.
  • the amount of chemical foaming agent (F1) is greater than 12 parts by weight and the amount of CP is correspondingly reduced, the viscosity of the obtained white material increases significantly.
  • the physical blowing agents (F2) described here namely HFC-245fa, HFC-365mfc, LBA and hexafluorobutene, are all HFC-based physical blowing agents.
  • blowing agent composition (FC) does not contain the physical blowing agent (F2)
  • the chemical blowing agent (F1) and cyclopentane are contained in separate containers.
  • the blowing agent composition (FC) further contains a physical blowing agent (F2)
  • the chemical blowing agent (F1) is contained in a separate container, and the physical blowing agent (F2) and cyclopentane are separately in different containers or in the same container.
  • blowing agent composition (FC) of the present invention is used for the preparation of cast-type rigid polyurethane foam, more preferably for the preparation of cast-type rigid polyurethane foam in the production process of refrigerators, freezers, water heaters or refrigerated vehicles.
  • the amount of chemical foaming agent (F1) is generally not less than 3 parts by weight, which can make the obtained rigid polyurethane foam have good thermal insulation properties and strength properties.
  • the chemical blowing agent (F1) is used in an amount of less than 3 parts by weight (for example, 1-2.8 parts by weight), it is mainly used for nucleation in the early stage of the foaming reaction because it occurs immediately when the white material is mixed with the black material CO2 gas.
  • the physical foaming agent uses the heat of reaction to make the foaming mixture heat up and then vaporize to generate bubbles, which is a hysteretic foaming and expansion.
  • the aforementioned nucleation in the early stage is beneficial to increase the number of cells and improve the uniformity of cell size, thereby also helping to improve the microstructure of the rigid polyurethane foam, thereby improving the thermal insulation performance of the foam to a certain extent.
  • the amount of physical blowing agent (F2) should be reduced, more preferably reduced to 0 parts by weight.
  • the amount of chemical blowing agent (F1) is correspondingly increased in order to obtain rigid foams having the specified foam density or an equivalent foam density.
  • the blowing agent composition (FC) comprises only component (1) chemical blowing agent (F1) and component (2) cyclopentane, ie component (2) physical blowing agent (F2) and component (2) (3)
  • the dosage of water (F3) is all 0 parts by weight.
  • the mass ratio (or relative amount) of chemical blowing agent (F1) to cyclopentane is (4-10 parts by weight): (10-20 parts by weight), preferably (4-9.5): (10-20 ), (4-9):(10-20), (4-9):(10-18), (4-9):(10-16), preferably (4.5-10):(10-20) ,(5-9.5):(10-20),(5-9.5):(10-18),(5-9.5):(10-16),(5-9):(10-20),( 5-9):(10-18), (5-9):(10-16), more preferably (5.5-9):(10-20), (5.5-8.5):(10-20), preferably (5.5-8): (10-20), preferably (5.5-8): (10.5-19.5), (5.5-8): (11-19), (5.5-8): (11.5-18.8), ( 5.5-8):(12-18.5), (5.5-8):(13-18), preferably (5.6-8):(10.5-19.5), preferably (5.7-8):(11-19), preferably (5.
  • the cost of rigid foam production is significantly reduced, and at the same time, unexpectedly, the rigid polyurethane foam formed has a very low thermal conductivity, that is, the Laneige mold (Lance) ⁇ (mW/m ⁇ K, 10°C). This coefficient is hereinafter referred to simply as thermal conductivity ( ⁇ ).
  • the blowing agent composition (FC) is used in an amount sufficient to make the prepared
  • the density of the (cast) rigid polyurethane foam is in the range of 25-38Kg/cm 3 , preferably 26-37Kg/cm 3 , preferably 27-36.5Kg/cm 3 , preferably 28-36Kg/cm 3 , preferably 28.5-35.5 Kg/cm 3 , preferably 29-35 Kg/cm 3 , such as 30, 31, 32, 33 or 34 Kg/cm 3 .
  • the sum of the water amounts of both the component (1) high water content alkanolamine carbonate chemical blowing agent (F1) and the component (4) optional water (F3) is 1- 3.7wt% (preferably 1.1-3.5wt%, preferably 1.2-3.3wt%, preferably 1.25-3wt% or 1.3-2.5wt% or 1.4-2wt%, eg 1.5, 1.6, 1.7, 1.8wt%), (approximately) With respect to or based on 100 parts by weight of dry white.
  • the amount of water in this range can make the foaming composition have ideal flowability, and at the same time ensure that the prepared rigid foam has excellent strength properties and thermal insulation properties.
  • the chemical blowing agent (F1) consists of components A), B), optionally C) and optionally D); preferably, the chemical blowing agent (F1) consists of components A), B) and optionally C) consists or consists of components A), B) and optionally D); more preferably, the chemical blowing agent (F1) consists of components A) and B).
  • a foaming agent composition (FC)
  • the specific C4-C9 diolamine is composed of diethanolamine and diisopropanolamine according to 1:(0.15-3), preferably 1:(0.2-1.5), more preferably 1:(0.22-1.2), more preferably 1:(0.24-0.9), more preferably 1:(0.25-0.5), more preferably 1:(0.27-0.4), more preferably Preference is given to a mixture consisting of a molar ratio of 1:(0.29-0.45).
  • the pH of the chemical blowing agent (F1) is 9.2-10, preferably 9.3-9.7, more preferably 9.4-9.6.
  • the content of component (D) C2-C9 alkanolamine bicarbonate is 0-5wt%, 0-4wt%, 0-3wt%, 0-2wt%, 0-1wt%, 0-0.5wt%, Most preferably 0 wt%.
  • the thermal conductivity ⁇ (mW/m ⁇ K, 10°C) of the Laneige mold (Lance) of the rigid polyurethane foam (density in the range of 25-38Kg/cm 3 ) obtained using this blowing agent composition (FC) is lower than 18.30 or below 18.20 or below 18.10 or even below 18.05.
  • Diisopropanolamine which is present in a small amount in the chemical blowing agent (F1) composed of diethanolamine and diisopropanolamine, plays a compatibilizing or solubilizing effect, which can improve the blowing agent composition (FC) and dry white.
  • the compatibility between the polymer polyols in the material can form a transparent and uniform white material, improve the microstructure and closed cell rate of the polyurethane rigid foam, and thus can reduce the thermal conductivity of the foam ⁇ (mW/m ⁇ K, 10° C.) is reduced, for example, to below 18.05.
  • the present invention provides a white material for polyurethane foaming, which comprises: (1) a dry white material for polyurethane foaming comprising polymer polyols and other auxiliary agents other than a foaming agent, wherein the other auxiliary agents Including polyurethane catalyst, foam stabilizer and optional flame retardant, optional chain extender and optional crosslinking agent; and (2) the above-mentioned alkanolamine carbonate blowing agent composition (FC).
  • a dry white material for polyurethane foaming comprising polymer polyols and other auxiliary agents other than a foaming agent, wherein the other auxiliary agents Including polyurethane catalyst, foam stabilizer and optional flame retardant, optional chain extender and optional crosslinking agent; and (2) the above-mentioned alkanolamine carbonate blowing agent composition (FC).
  • the polymer polyols in the dry white material comprise 8-52wt% (preferably 9-50wt%, preferably 10-48wt%, preferably 12-47wt%, preferably 15-45wt%, preferably 16-40wt%, More preferably 18-35 wt%) of aromatic/semi-aromatic polyester polyols such as polyethylene phthalate polyol, polyethylene isophthalate polyol or polyethylene terephthalate Ethanol ester polyol) and/or toluenediamine polyoxypropylene polyol and 92-48wt% (preferably 91-50wt%, preferably 90-52wt%, preferably 88-53wt%, preferably 85-55wt%, preferably 84-60wt% , more preferably 82-65 wt%) (non-toluenediamine-type or non-toluenediamine-initiated) polyoxypropylene polyols, ie, polyoxypropylene poly
  • the present invention also provides a composition (or mixture) for polyurethane foaming, which comprises:
  • polyisocyanate preferably, polymethylene polyphenyl polyisocyanate or polymeric MDI
  • the ratio (ie, material ratio) of the black material (1) to the sum of the mass of the dry white material (2) and the blowing agent composition (3) is 1.1-1.36:1, preferably 1.13-1.35:1, preferably 1.15-1.30:1, preferably 1.17-1.27:1, preferably 1.18-1.25:1, most preferably 1.2:1.
  • Aromatic/semi-aromatic polyester polyols in this application refer to aromatic polyester polyols and/or semi-aromatic polyester polyols, usually with low viscosity (25°C) (eg 3000-8000 cps, such as 3200- 5000 or 3500-4000).
  • polymer polyols in dry whites since it contains a small amount of aromatic polyester polyols (ie PET polyols), preferably, polyethylene phthalate and polyethylene isophthalate Ester polyol, more preferably polyethylene phthalate.
  • aromatic polyester polyols ie PET polyols
  • polyethylene phthalate and polyethylene isophthalate Ester polyol more preferably polyethylene phthalate.
  • Toluylenediamine polyoxypropylene polyol refers to a toluenediamine-initiated or initiated polyoxypropylene polyol.
  • the amount of toluenediamine polyoxypropylene polyol is reduced or not used.
  • diethanolamines such as diethanolamine or N-methyldiethanolamine have lower viscosities, but they are associated with dry whites comprising polyoxypropylene polyols and small amounts of polyester polyols and/or toluenediamine polyether polyols
  • the compatibility between the materials is slightly poor (the white material obtained by mixing the dry white material and the foaming agent containing diethanolamines under stirring is then rapidly defoamed by centrifugation, and it is found that the material has a layering phenomenon, that is, There is a thinner layer of material at the bottom), and the thermal insulation performance of the obtained rigid polyurethane foam is not ideal.
  • diisopropanolamines such as diisopropanolamine, ethanolisopropanolamine, and N-methyldiisopropanolamine
  • ethanolisopropanolamine have higher viscosities (in the When mixing dry white material and foaming agent containing diisopropanolamine to obtain white material under manual stirring, it is obvious that the stirring of white material is more difficult and the white material has higher viscosity), resulting in the difference between white material and black material.
  • the degree of mixing is not uniform, and the thermal insulation properties of the obtained rigid polyurethane foam are not optimal.
  • the use of these (diisopropanolamines and/or ethanolisopropanolamines) in combination with diethanolamines can significantly improve the obtained blowing agent between the dry whites Compatibility, can form a uniform, transparent white material, which in turn improves the microstructure of the prepared foam and increases the closed cell rate, so that the thermal conductivity of the foam almost reaches the lowest limit value (for example, the ⁇ value is as low as 18.10 or even low on 18.02).
  • the combined use of the above two types of alkanolamines may lead to doping effects that reduce the viscosity of each other.
  • the present invention also provides the use of the above-mentioned alkanolamine carbonate foaming agent composition (FC) for formulating a composition for polyurethane foaming.
  • FC alkanolamine carbonate foaming agent composition
  • the present invention also provides a method for preparing a rigid polyurethane foam, the method comprising: mixing the polymer polyol composition white material comprising the blowing agent composition (FC) described above with a polyisocyanate (preferably, polymethylene) as the black material base polyphenyl polyisocyanate or polymeric MDI) for mixing and foaming; preferably, casting foaming is carried out using a casting machine.
  • FC blowing agent composition
  • the present invention also provides the rigid polyurethane foam obtained by the above-mentioned method for preparing rigid polyurethane foam, wherein the density of the rigid polyurethane foam is in the range of 25-38Kg/cm 3 , preferably 26-37Kg/cm 3 , preferably 27 Kg/cm 3 . -36.5Kg/ cm3 , preferably 28-36Kg/ cm3 , preferably 28.5-35.5Kg/ cm3 , preferably 29-35Kg/ cm3 , eg 30, 31, 32, 33 or 34Kg/ cm3 .
  • the Lance thermal conductivity ⁇ (mW/m ⁇ K, 10° C.) of the rigid polyurethane foam is lower than 18.50, preferably lower than 18.40, more preferably lower than 18.30, more preferably lower than 18.20, more preferably lower than 18.05.
  • blowing agent composition for the application of the blowing agent composition (FC) in the preparation of rigid polyurethane foams in the refrigerator, freezer, water heater and refrigerated vehicle industries, when the relative amount of cyclopentane in the blowing agent (FC) was further increased to 22 wt. Parts above will result in the formation of a two-phase system (phase separation phenomenon) in the formulated white stock. Among them, the presence of oil droplets was found when the white material was stirred, and in addition, stratification occurred when standing, which means that too much cyclopentane got rid of the constraints of water and polymer polyols (or, cyclopentane The solubility of alkane in the white material is limited), it no longer participates in the formation of multi-component complexes.
  • a homogeneous foaming system cannot be formed in the foaming reaction, and the diameter of the cells in the obtained foam is particularly non-uniform (in which the oil droplets become the vaporization centers, and macropores or super-large pores are generated at the positions of the oil droplets), and the diameter of the cells Typically above 300 microns or even above 350 microns, the insulating properties of the foam are significantly reduced.
  • the described phase separation phenomenon shows that only when the content of physical blowing agent (F2) and/or cyclopentane in the foaming composition (FC) is within a certain range, the physical blowing agent (F2) and Cyclopentane has good compatibility with dry whites and can form transparent and uniform whites.
  • the inventor has found through experiments that due to the presence of a part of benzene ring-containing polyester polyol and toluenediamine polyether polyol in the dry white material, the use of such dry white material can improve the performance of cyclopentane in the white material system. At the same time, it can also improve the compatibility of HFC-245fa, HFC-365mfc, LBA and hexafluorobutene in the white material system. However, since hexafluorobutene has a higher molecular weight, higher density and higher polarity, and the higher density will affect the density distribution of hexafluorobutene in the white material, therefore, it is in the white material system.
  • hexafluorobutene The compatibility of hexafluorobutene is worse than that of HFC-245fa, HFC-365mfc, and LBA in white material. Therefore, in the present invention, the use of hexafluorobutene is not preferred.
  • Proper rise time and fluidity of the foaming mixture is very important for in-mold foaming in the field of refrigerators, freezers, water heaters or refrigerated vehicles, because the foaming mixture is injected into the mold through a single injection port. Lumen with complex structure. If the rise time is too short or the fluidity is too poor, the foaming mixture foams and hardens in the area close to the injection port in the mold, and the foaming mixture cannot reach further areas, therefore, it cannot be filled uniformly Filling the entire cavity of the mold, which leads to poor mold opening performance of the rigid foam and uneven overall density distribution of the foam in the mold.
  • the opening time of the mold is often about 180 seconds, so the wire drawing time is also important.
  • the pH of the chemical blowing agent (F1) is lower than 8.6, the activity of the chemical blowing agent (F1) is low and the alkalinity decreases, and the ability of the blowing agent (F1) to bind the acidic CO gas decreases, and during the foaming process
  • the white material and the black material are stirred and mixed, in the initial stage of the reaction, the white material is slightly heated up due to the reaction heat, so that CO 2 quickly escapes from the foaming mixture, and the CO 2 gas cannot fully exert the foaming effect, resulting in the foam of the obtained foam.
  • the size of the holes is reduced.
  • the chemical blowing agent (F1) when the pH of the chemical blowing agent (F1) is higher than 10.4 or even higher than 10.5, the chemical blowing agent (F1) has high activity and high alkalinity, which means that there is more in the blowing agent (F1) Alkaline alkanolamines, these basic alkanolamines that exist in excess quickly play a catalytic role in the early stage, causing the speed of the foaming reaction to run out of control (for example, the initiation time is 1-3 seconds, and the foaming reaction material rapidly expands and rises), in addition, The foaming reaction (chain growth reaction) catalyzed in the early stage is too fast, which also seriously interferes with the effect of the tertiary amine catalyst in the later stage of catalytic cross-linking, reducing the strength and deformation resistance of the resulting foam.
  • the excess component (C) in the chemical blowing agent (F1) is free C2-C9 alcohol amines (mainly including specific C4-C9 diolamines (Ia+IIa) and optional secondary amine type C3-C6 monoalcoholamines ( Ib+IIb)) is used on the one hand to adjust the pH of the chemical blowing agent (F1) and reduce the content of alkanolamine bicarbonate, and on the other hand it is used as a pre-catalyst to adjust the foaming speed in the foaming reaction (e.g.
  • the component (C) C2-C9 alkanolamines (mainly including (Ia+IIa) and optionally (Ib+IIb)) together with water are used in the middle and late stages of the foaming reaction Cross-linking agent to improve the strength of the inner wall of the cell, thereby improving the strength and deformation resistance of the foam.
  • the foaming mixture obtained by mixing the material and black material can be smoothly carried out at the optimal foaming speed (set-up time and wire drawing time), wherein the foaming mixture has high fluidity and can evenly fill the entire mold
  • the inner cavity of the obtained rigid polyurethane foam has a Lance thermal conductivity ⁇ (mW/m ⁇ K, 10°C) lower than 18.05 or 18.03, which almost reaches the limit value of the thermal insulation performance, which reflects the thermal insulation performance of the foam. huge progress.
  • the boiling point of the physical foaming agent (F2) is lower than 15°C or higher than 41°C, it will affect the smooth progress of the foaming process.
  • the chemical foaming agent (F1) reacts with the polyisocyanate to generate CO gas to exert the nucleation and foaming effect in the early stage, and then with the increase of the temperature of the reaction mixture, the physical foaming is successively performed.
  • the foaming agent and cyclopentane play a role in foaming, which is conducive to the smooth progress of the foaming process.
  • the blowing agent with a low boiling point volatilizes and escapes immediately when the blowing agent composition (FC) is mixed with the dry white material, and in addition, the early foaming effect It can also cause the composition of the foaming reaction mixture to become non-uniform.
  • the boiling point of the physical foaming agent (F2) is higher than 41°C, the foaming effect of the physical foaming agent (F2) is slightly delayed, which affects the smooth progress of the foaming reaction.
  • the high-boiling physical blowing agent (F2) in the cells loses support for the cells due to condensation and becomes liquid, causing the foam to shrink and deform during subsequent use.
  • all C2-C9 alkanolamines in the chemical blowing agent (F1) contain less than 70 mol% of a specific C4-C9 diolamine, it means that so-called all C2-C9 alkanolamines contain more other C2-C9 alcohols Amines, for example, (Ib) secondary amine type C3-C5 monoalcoholamines having only hydroxyethyl groups and (IIb) secondary amine type C4-C6 monoalcoholamines having only hydroxyisopropyl groups, and the above-mentioned so-called "impurities" alkanolamines IA".
  • the foaming mixture will start to rise.
  • the time is greatly shortened (for example, 1-2 seconds), and the reaction is rapid and the foam expands rapidly, which leads to the uncontrolled foaming process, and it is impossible to carry out the foaming reaction at a stable speed. have adverse effects. Therefore, in the blowing agent composition (FC), the lower the content of primary amine type C2-C9 monoalcoholamine, the better.
  • the speed of the foaming reaction is also affected.
  • the inventors found that when the C2-C9 alkanolamine in the chemical blowing agent (F1) contains a relatively large amount (eg, greater than 40 mol%) of triethanolamine, it will cause the foam to have a "core burning" phenomenon, that is, the core of the foam presents Dark yellow or burnt yellow.
  • the rigid polyurethane foam obtained by the above method is provided, especially, when the density of the rigid polyurethane foam is in the range of 25-38Kg/cm 3 , its Lance thermal conductivity ⁇ (mW/m ⁇ K, 10°C) is below 18.80, preferably below 18.70, below 18.60, below 18.50 or below 18.40, more preferably below 18.30, 18.20, 18.10, 18.04.
  • the inventors of the present application have found through a large number of experiments that by optimizing the composition of the blowing agent, the microstructure and closed cell ratio of the rigid foam can be optimized, so that the thermal conductivity of the rigid polyurethane foam can be ideally reduced, and even lower to the current limit.
  • the density (core density, ASTM D 1622-03) of the rigid polyurethane foam obtained by the present invention is in the range of 25-38Kg/ cm3 , preferably 26-37Kg/ cm3 , preferably 27-36.5Kg/ cm3 , preferably 28- 36Kg/cm 3 , preferably 28.5-35.5Kg/cm 3 , preferably 29-35Kg/cm 3 , when the average cell diameter is in the range of 170-230 microns (preferably 180-220 microns, more preferably 170-210), generally,
  • the thermal conductivity (Mw/m ⁇ k, 10° C.) of the rigid polyurethane foam is lower than 18.40, more preferably lower than 18.30, more preferably lower than 18.20, more preferably lower than 18.05 or 18.03.
  • the content of alcoholamine bicarbonate in the chemical blowing agent (F1) should be reduced as much as possible, such as In the neutralization reaction of passing CO 2 gas into the alkanolamine, an appropriate pressure of CO 2 gas is selected for different basic alkanolamines.
  • the performance of the blowing agent composition such as the compatibility between the composition and the dry white material
  • the foam after mixing the black material and the white material is improved.
  • the foam mixture has the ideal fluidity to fill the entire mold uniformly and make the foaming mixture have suitable rise time and drawing time, suitable for single-port casting polyurethane rigid foam in the field of refrigerators, freezers, water heaters and refrigerated vehicles Production.
  • the prepared foams have good mold opening properties.
  • the alkanolamine carbonate foaming agent composition (FC) of the (casting type) polyurethane rigid foam of the present invention has good compatibility with the dry white material for foaming, and can form a uniform, transparent and Flowable foaming system and can be used to obtain polyurethane rigid foam with good cell microstructure and closed cell ratio, especially, when the polymer polyols in the dry white material contain 10-52wt% (preferably 15- 45wt%, more preferably 18-35wt%) of aromatic/semi-aromatic polyester polyol and/or toluenediamine polyoxypropylene polyol and 90-48wt% (ie balance) (preferably 85-55wt%, more preferably 82 -65 wt%) of polyoxypropylene polyols (eg, sucrose-initiated polyoxypropylene polyols, or pentaerythritol-initiated polyoxypropylene polyols).
  • FC alkanolamine carbonate foaming
  • the chemical blowing agent (F1) is prepared by a neutralization method of feeding CO gas in a mixture of C2-C9 alkanolamines and water, wherein the C2-C9 alkanolamines contain a major amount (70-100 mol %) of the specific C4-C9 diolamines.
  • a suitable pressure of CO gas is selected according to the basicity of the particular C4-C9 diolamine, which is sufficient to neutralize the alkanolamine and CO in the stoichiometric amount of carbonate formation, on the other hand the pressure of CO is not Should be so high that too much alkanolamine bicarbonate is formed.
  • a suitable CO pressure should be such that the chemical blowing agent (F1) prepared by the neutralization method by passing CO gas into a (saturated or near-saturated) mixture of alkanolamine and water contains a small amount (0.1-20 wt% , preferably 0.1-14 wt%) of unneutralized C2-C9 alkanolamines (especially specific C4-C9 diolamines), therefore, the rigid foams formed by using this chemical blowing agent (F1) have very good Thermal insulation properties.
  • the foaming agent of the present invention has obvious cost advantages, compared with the third and fourth generation fluorine-containing foaming agents.
  • the polymer polyols used for the preparation of (casting) polyurethane rigid foams in the refrigerator, freezer, water heater and refrigerated vehicle (cold chain insulation) industries usually contain 8-52 wt% of aromatic polyester polyols and/or toluene Diamine polyether polyol and the balance of non-toluene diamine type polyoxypropylene polyol, cyclopentane and chemical blowing agent can form a transparent and homogeneous system with good fluidity in such a system, making the foaming uniform , the formation of fine cells and cell size uniform.
  • FIG. 1A and 1B are SEM photographs of the foam of Example 1.
  • FIG. 2 is a SEM photograph of the foam of Comparative Example 1.
  • FIG. 3 is an SEM photograph of the foam of Example 3.
  • FIG. 4 is a SEM photograph of the foam of Comparative Example 2.
  • FIG. 5 is a SEM photograph of the foam of Example 4.
  • FIG. 6 is a SEM photograph of the foam of Comparative Example 3.
  • FIG. 6 is a SEM photograph of the foam of Comparative Example 3.
  • FIG. 7 is an SEM photograph of the foam of Example 5.
  • FIG. 8A, 8B and 8C are SEM photographs of the foam of Example 6.
  • FIG. 9 is a SEM photograph of the foam of Comparative Example 4.
  • FIG. 10 is a SEM photograph of the foam of Comparative Example 6.
  • FIG. 11 and 12 are SEM photographs of the two foams of Example 8.
  • the initiation time is generally 6-7 seconds, and the drawing time is generally 30-45 seconds (preferably 35-40 seconds).
  • the present invention designs a specific foaming agent composition for the rigid polyurethane foam used in refrigerators, freezers, water heaters, and cold chain insulation (refrigerated vehicles) industries.
  • polyether polyols polyoxypropylene polyols
  • (aromatic) polyester polyols used in the preparation of polyurethane foams or in foaming compositions are selected from the following varieties: polyether polyols (Polyoxypropylene polyol), for example, polyether polyol 4110 (sucrose initiator polyoxypropylene polyol) of BEFAR GROUP CO., LTD., Nanjing Hongbaoli Co., Ltd.
  • Polyether 450 (sorbitol starter polyoxypropylene polyol), MN500 (glycerol starter polyoxypropylene polyol) and SA 460 (sorbitol starter polyoxyethylene polyol) of Shandong Lanxing Dongda Chemical Co., Ltd. propylene polyol), SA 460 (sorbitol initiator polyoxypropylene polyol), SU380 (sucrose initiator polyoxypropylene polyol) and SA380 (sorbitol initiator polyoxypropylene polyol) from Zibo Nuoli Chemical Co., Ltd.
  • YD8260 polyoxypropylene polyol with sucrose and diethylene glycol as initiator
  • YD403 polyoxypropylene polyol with ethylenediamine initiator
  • YD460 toluene diamine
  • SD7100 toluenediamine-type polyoxypropylene polyol from Shanghai Dongda Chemical Co., Ltd.
  • (aromatic) polyester polyols for example, Nanjing Jinling Stepan Chemical Co., Ltd.
  • catalysts are selected from: 33LV (A-33): 33% triethylenediamine solution in dipropylene glycol, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, 70% bis(dimethylamino) Ethyl) ether in dipropylene glycol, 70% potassium caprylate in diethylene glycol, dibutyltin dilaurate, PT303, PT304, potassium acetate, PC-8 (N,N-dimethylcyclohexylamine), PC -5(N,N,N,N,N-pentamethyldiethylenetriamine), PC-41 (tris(dimethylaminopropyl)hexahydrotriazine), triethanolamine, JXP-508, JXP -509, TMR-2 (2-hydroxy-N,N,N-trimethyl-1-propanamine formate), TMR-3, TMR-4.
  • silicone oil type foam stabilizers or silane surfactants B8525 and B8408 of Evonik Degussa (China) Investment Co., Ltd., AK-158, AK-8805, AK-8812, AK-8809, AK-8818 and AK-8860, DC8545, DC1990, DC5188, DC6070, DC3042 and DC3201 from Gas and Chemicals, and Silicone Oil 8841 from Shanghai Maihao Chemical Technology Co., Ltd.
  • Non-Silane Surfactants LK-221 and LK-443 from Gas & Chemicals.
  • Commonly used flame retardants TCPP, TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, tetrabromophthalic anhydride diol.
  • the following introduces the method of CO 2 aeration to prepare the carbonate alkanolamine salt chemical foaming agent (F1) (CFA), that is, the carbonate alkanolamine salt hydrate in the following examples.
  • F1 carbonate alkanolamine salt chemical foaming agent
  • Carbonate alkanolamine salt hydrate 1 is obtained, which is called “chemical foaming agent” (CFA) or as carbonate alkanolamine salt chemical foaming agent (F1).
  • CFA chemical foaming agent
  • the alcoholamine-water mixture was determined to have absorbed about 514 g (about 11.68 mol) of CO2 (molecular weight 44).
  • 11.7 mol (210.6 g) of water participated in the neutralization reaction.
  • the amount of free water in Hydrate 1 was 703.76 g (16.86%).
  • MMEA methyl monoethanolamine
  • 1kg of water were mixed and added to 5 liters of transparent quartz glass high-pressure reactors, and stirring was started, and the reactor was sealed, and then under constant stirring, the temperature was controlled Between 40-65 °C, the carbon dioxide is introduced into the reactor, the control pressure is not higher than 0.1MPa (that is, the range of 0.09-0.1MPa), the temperature is controlled for 10 hours, and the pressure is released after cooling to below 40 °C. product can be. Carbonic alkanolamine salt hydrate 2 (CFA) is obtained.
  • CFA Carbonic alkanolamine salt hydrate 2
  • the alcoholamine-water mixture was determined to have absorbed about 913 g (about 20.75 mol) of CO2 .
  • the mixture (hydrate 2) forms part (about 1.5 mol, 3.75 mol % by mol %, based on the mol of the total alkanolamine, or about 204 g) of alkanolamine bicarbonate (molecular weight 136), the content of the latter wt % is about 4.2 wt%.
  • 20.75 moles (373.5 grams) of water participated in the neutralization reaction.
  • the amount of free water in Hydrate 2 was 626.5 g (12.75 wt%).
  • CFA carbonate amine salt hydrate 3
  • Hydrate 6 of Preparation Example 6 (reference) and Hydrate 4 of Preparation Example 4 were prepared according to the mol ratio of monoisopropanolamine:diisopropanolamine of 6.5:3.5 (mol% of monoolamine was 65mol% ) was mixed to obtain Hydrate 7A with a viscosity of about 1044 centipoise (25°C).
  • Hydrate 6 of Preparation Example 6 (reference) and Hydrate 4 of Preparation Example 4 were prepared according to the 1:1 mole ratio of monoisopropanolamine:diisopropanolamine (the mol% of monoolamine was 50 mol% ) was mixed to obtain Hydrate 7B with a viscosity of about 1182 centipoise (25°C).
  • Hydrate 3 of Preparation Example 3 and Hydrate 4 of Preparation Example 4 were mixed according to a 3:1 molar ratio of N-methyldiethanolamine:diisopropanolamine to obtain Hydrate 8 with a viscosity of about 915 centipoise (25°C).
  • Hydrate 6 of Preparation Example 6 (reference) and Hydrate 4 of Preparation Example 4 were prepared according to the mol ratio of monoisopropanolamine:diisopropanolamine of 0.36:1 (mol% of monoalcoholamine was about 26 mol %) to obtain Hydrate 9 with a viscosity of about 1255 centipoise (25°C).
  • Hydrate 6 of Preparation Example 6 (reference) and Hydrate 1 of Preparation Example 1 were prepared according to the molar ratio of monoisopropanolamine:(ethanolamineamine+diisopropanolamine) of 0.36:1 (monoalcoholamine mol% is about 26 mol%) and mixed to obtain Hydrate 10 with a viscosity of about 532 centipoise (25°C).
  • Blowing agent 6 parts by weight of carbonate amine salt hydrate 1 (CFA) prepared from Example 1 above and 18 parts by weight of cyclopentane as blowing agents.
  • Dry white material it consists of the following components: 40 parts by weight of polyether polyol SD-7100 (toluenediamine type polyoxypropylene polyol, produced by Shanghai Dongda Chemical Co., Ltd.), 20 parts by weight of polyether Polyol SA-460 (sorbitol initiator polyoxypropylene polyol, produced by Zibo Nolly Chemical Co., Ltd.
  • polyether polyol SD-7100 toluenediamine type polyoxypropylene polyol, produced by Shanghai Dongda Chemical Co., Ltd.
  • polyether Polyol SA-460 sorbitol initiator polyoxypropylene polyol, produced by Zibo Nolly Chemical Co., Ltd.
  • Black material 156 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as black material.
  • pouring foaming was carried out by a high pressure casting foaming machine (RSC16/16, KraussMaffei, Germany) using the same formulation (or composition) as described above.
  • the foaming agent, dry white material and black material are input into the pouring foaming machine through their respective material pipelines for stirring and mixing, and then the mixed foaming material is poured into the Lanige mold by the spray gun for foaming.
  • the specific operation is as follows: first, set the amount of foaming material for the first pouring of the pouring machine to be about 200g, then pour the set amount of foaming material into a plastic bag from a spray gun for free foaming, and measure the foaming material
  • the start-up time is 6 seconds and the wire drawing time of the spray gun is 35 seconds.
  • the amount of the pouring material is set, and the corresponding set amount of foaming material is poured into the Laneige mold for foaming.
  • the mold is opened (ie, the inner and outer clamping molds are opened). Samples of the foam were taken for analysis of the microstructure and thermal insulation properties of the foam. Two foam samples were taken from two batches of foam products for SEM analysis. SEM photographs of the two samples are shown in Figures 1A and 1B.
  • the number of cells per unit area is higher, the average cell diameters of the cells of the two foam samples are smaller (about 217 ⁇ m and about 210 ⁇ m) and the size of the cells is relatively uniform.
  • the inspiration time of the foaming process was measured to be 6 seconds, and the drawing time was 35 seconds.
  • the heuristic time and the drawing time are in good agreement with the time frame on the industrial production line of the refrigerator, therefore, the foam is suitable for use in the refrigerator.
  • Example 1 was repeated except that the amount of blowing agent (water + CP) was as shown in Table 1.
  • An SEM photograph of the foam is shown in FIG. 2 .
  • the average cell diameter of the foam was about 346 microns.
  • the haze phenomenon is attributed to the poor compatibility between the blowing agent (water+CP) without alkanolamine carbonate or alkanolamine and the dry white stock.
  • Blowing agent 7 parts by weight of the carbonate amine salt hydrate 2 (CFA) prepared in Example 2 above and 18 parts by weight of cyclopentane (CP) as blowing agents.
  • Dry white material it consists of the following components: 40 parts by weight of toluenediamine polyether polyol SD-7100, 20 parts by weight of polyether polyol SA-460, 10 parts by weight of aromatic polyester polyol PS -4051, 20 parts by weight of polyether polyol YD-8260, 10 parts by weight of polyether polyol YD-403, 3 parts by weight of silicone oil foam stabilizer 8841 (produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.1 Parts by weight of N,N,N,N,N-pentamethyldiethylenetriamine (codenamed PC-5, produced by Evonik Degussa Co., Ltd.), 0.5 parts by weight of amine catalyst BX-405 (produced by American Evonik Degussa Co., Ltd.) and 1 part by weight of tris(dimethylaminopropyl) hexahydrotriazine (code name PC-41, produced by American Evonik Degussa Co., Ltd.).
  • Black material 156 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as black material.
  • pouring foaming was carried out by a high pressure casting foaming machine (RSC16/16, KraussMaffei, Germany) using the same formulation (or composition) as described above.
  • the starting time of the foamed material was measured to be 3 seconds and the wire drawing time of the spray gun was 27 seconds.
  • the amount of the pouring material was set according to the volume of the Laneige mold, and the corresponding set amount of foaming material was poured into the Laneige mold for foaming.
  • the mold is opened (ie, the inner and outer clamping molds are opened). It was found that the foam was concentrated in the vicinity of the gate, and there was no foam in the far region of the mold cavity, that is to say, the foam did not fill the entire mold cavity.
  • the density distribution of the foam in the mold is not uniform.
  • Foaming agent 3 parts by weight of carbonate amine salt hydrate 3 (CFA) prepared by Example 3 above, 1.8 parts by weight of water, 3 parts by weight of HFC-245fa and 17 parts by weight of cyclopentane as foaming agent alkyl.
  • CFA carbonate amine salt hydrate 3
  • Dry white material it consists of the following components: 40 parts by weight of polyether polyol SD-7100, 20 parts by weight of polyether polyol SA-460, 10 parts by weight of polyester polyol PS-4051, 20 parts by weight of polyether polyol Parts of polyether polyol YD-8260, 10 parts by weight of polyether polyol YD-403, 3 parts by weight of foam stabilizer 8841 (produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.1 parts by weight of N, N, N,N,N-Pentamethyldiethylenetriamine (code PC-5, produced by Evonik Degussa Co., Ltd.), 0.5 parts by weight of amine catalyst BX-405 (produced by Evonik Degussa, USA) Said Co., Ltd.) and 1 part by weight of tris(dimethylaminopropyl)hexahydrotriazine (code name PC-41, produced by Evonik Degussa Co., Ltd.).
  • Black material 157 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as black material.
  • Example 2 The same foaming reaction procedure as in Example 1 was repeated.
  • the rise time of the foamed material was measured to be 6 seconds and the muzzle draw time was 35 seconds.
  • the SEM photograph of the rigid foam is shown in FIG. 3 .
  • the average cell diameter of the cells is small (about 228um, slightly larger than the average cell diameter of Example 1) and the size of the cells is relatively uniform.
  • Example 3 was repeated except that the amount of blowing agent (245fa+CP) was as shown in Table 1.
  • a SEM photograph of the foam is shown in FIG. 4 .
  • the cells of the foam are large and non-uniform in size.
  • the haze phenomenon was attributed to the poor compatibility between the alkanolamine carbonate-free blowing agent (245fa+CP) and the dry white.
  • Blowing agent 3 parts by weight of carbonate amine salt hydrate 4 prepared from Example 4 above, 1.8 parts by weight of water, 3 parts by weight of LBA and 17 parts by weight of CP (cyclopentane) as blowing agents.
  • Dry white material it consists of the following components: 40 parts by weight of polyether polyol SD-7100, 20 parts by weight of polyether polyol SA-460, 10 parts by weight of polyester polyol PS-4051, 20 parts by weight of polyether polyol Parts of polyether polyol YD-8260, 10 parts by weight of polyether polyol YD-403, 3 parts by weight of foam stabilizer 8841 (produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.1 parts by weight of N, N, N,N,N-Pentamethyldiethylenetriamine (code PC-5, produced by Evonik Degussa Co., Ltd.), 0.5 parts by weight of amine catalyst BX-405 (produced by Evonik Degussa, USA) Said Co., Ltd.) and 1 part by weight of tris(dimethylaminopropyl)hexahydrotriazine (code name PC-41, produced by Evonik Degussa Co., Ltd.).
  • Black material 157 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as black material.
  • Example 2 The same foaming reaction procedure as in Example 1 was repeated.
  • the rise time of the foamed material was measured to be 6 seconds and the muzzle draw time was 35 seconds.
  • the SEM photograph of the rigid foam is shown in FIG. 5 .
  • the average cell diameter of the cells is small (about 239 um is slightly larger than the average cell diameter of Example 1) and the size of the cells is relatively uniform.
  • Example 4 was repeated except that the blowing agent was (LBA+CP), wherein the amount of blowing agent (LBA+CP) was as shown in Table 1.
  • a SEM photograph of the foam is shown in FIG. 6 .
  • the cells of the foam are large and non-uniform in size.
  • Example 3 was repeated, except that 3 parts by weight of alkanolamine carbonate hydrate 1 in Example 1 was used instead of 3 parts by weight of alkanolamine carbonate hydrate 3 .
  • An SEM photograph of the obtained rigid foam is shown in FIG. 7 .
  • the average cell diameter of the cells is small (about 220 um, slightly larger than that of Example 1) and the size of the cells is relatively uniform.
  • CFA in the table refers to high-water carbonic acid organic alcohol amine salt foaming agent; the ⁇ value (or K factor) is measured according to GB/T 10295-2008, and the foam size is 20*20*2.5cm.
  • the "expansion rate (180s)" in the table refers to the expansion rate measured after opening the Laneige mold from the start of injection into the Laneige mold to 180 seconds (3 minutes).
  • the size of the Lance mold is 1600*300*80mm.
  • the overall foam is divided into left and right parts (ie, left and right sides) with the long side as the direction. From the bottom to the top of each part, a density point (density measurement point) is taken every 20cm, and the left and right sides are taken together. There are 16 density points, and the difference between the highest density value and the lowest density value is taken as the density range. The average of the densities of these 16 density points is the average density.
  • the carbonic acid organic alcohol amine salt hydrate with high water content and low alcohol amine bicarbonate content is used in combination with cyclopentane as a chemical foaming agent, or the hydrate is combined with hydrofluorocarbons.
  • the foaming agent and cyclopentane are used in combination, the prepared polyurethane foam material has excellent overall performance, low thermal conductivity and good thermal insulation performance.
  • the rigid polyurethane foams obtained using the foaming compositions containing (diethanolamines+diisopropanolamines) in Examples 1 and 5 had very excellent thermal insulation properties.
  • Example 1 was repeated, except that the carbonate amine salt hydrate 1A, 1B and 1C prepared in Example 1 were replaced with the same amount of carbonate alkanolamine salt hydrate 1 prepared in Example 1, respectively. Polyurethane rigid foams 6A-6C were obtained. Compare with the foam of Example 1.
  • Example 1 was repeated except that the amount of cyclopentane (18 parts) was changed to 24 parts by weight of cyclopentane.
  • Foaming reaction process It was measured that the starting time of the foaming material was 7 seconds and the wire drawing time of the spray gun was 43 seconds.
  • FIG. 9 A SEM photograph of the foam is shown in FIG. 9 . It can be clearly seen from the SEM pictures that the average pore diameter of the cells is large (about 330 microns) and the size of the cells is not uniform. In addition, many oversized cells can be seen in the SEM pictures. These super large cells may be formed by oil droplets (cyclopentane) as foaming centers during the foaming process.
  • oil droplets cyclopentane
  • Example 1 was repeated, and experiments 1a, 2a, 3a and 4a were carried out, except that the hydrates 5, hydrated and Compound 6, Hydrate 7A and Hydrate 7B were used instead of Hydrate 1 in Example 1, and were foamed by casting to obtain rigid polyurethane foams 5, 6, 7A and 7B. It is mainly to investigate the initiation time and wire drawing time of the foaming process.
  • Example 6 Preparation Example 6 with reduced alkanolamine bicarbonate content was used compared to the rise time (3 seconds) and the drawing time (27 seconds) in Example 2 (comparative).
  • the start-up time and wire drawing time of experiment 1a were prolonged respectively, but still could not meet the requirement of refrigerator pouring foaming.
  • Example 1 was repeated, except that Hydrate 8, Hydrate 9 and Hydrate 10 in Preparation Example 8, Preparation Example 9 and Preparation Example 10 were respectively used in the same amount instead of Hydrate 1 in Example 1. Pouring foaming, polyurethane rigid foams 8, 9 and 10 were obtained. It is mainly to investigate the initiation time and wire drawing time of the foaming process.
  • Example 1 was repeated, except that only the non-toluenediamine-type polyether polyol was included in the white stock, but the polyester polyol and the toluene-diamine-type polyether polyol were not included. That is, the composition of the dry white material is as follows;
  • Dry white material it is composed of the following components: 40 parts by weight of polyether polyol SA-460 (sorbitol initiator), 30 parts by weight of polyether polyol YD-8260 (with sucrose and diethylene glycol as Initiator), 30 parts by weight of polyether polyol YD-403 (ethylenediamine initiator), 3 parts by weight of foam stabilizer 8841 (produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.1 parts by weight of N ,N,N,N,N-Pentamethyldiethylenetriamine (codenamed PC-5, produced by Evonik Degussa Co., Ltd.), 0.5 parts by weight of amine catalyst BX-405 (produced by American Evonik Degussa Co., Ltd.) Produced by Evonik Degussa Co., Ltd.) and 1 part by weight of tris(dimethylaminopropyl) hexahydrotriazine (code name PC-41, produced by Evonik Deguss
  • FIG. 10 An SEM photograph of the formed foam is shown in FIG. 10 . There are coarse cells, resulting in a higher thermal conductivity of the foam. The ⁇ (Mw/m ⁇ k, 10° C.) of the foam was 18.95.
  • the non-toluenediamine-type polyoxypropylene polyol has good fluidity
  • the cyclopentane-containing blowing agent composition of the present invention is not compatible with the non-polyester polyol or toluenediamine-type polyoxypropylene polyol. The compatibility between the dry white materials (non-toluenediamine polyoxypropylene polyols) is not very good.
  • Example 3 was repeated, and experiments 1a and 2d were carried out, except that in experiment 1d, 1 part by weight of alcohol amine carbonate hydrate 1 in Example 1 was used as CFA (chemical blowing agent) and 5 parts by weight of 245fa, and in addition, In experiment 2d, 2 parts by weight of alcohol amine carbonate hydrate 1 from Example 1 were used as CFA (chemical blowing agent) and 4 parts by weight of 245fa.
  • CFA chemical blowing agent
  • 2d 2 parts by weight of alcohol amine carbonate hydrate 1 from Example 1 were used as CFA (chemical blowing agent) and 4 parts by weight of 245fa.
  • the ⁇ (Mw/m ⁇ k, 10° C.) of the foam of Experiment 1d was 18.59.
  • the ⁇ (Mw/m ⁇ k, 10° C.) of the foam of Experiment 2d was 18.52.
  • the SEM photographs of the rigid foams obtained in Experiment 1d and Experiment 2d are shown in Figure 11 and Figure 12, respectively.
  • Example 1 was repeated except that the CP was 12 parts by weight and the CFA was 4 parts by weight.
  • the product density of the resulting foam ie, the density of the foam product measured after opening the casting mold
  • the thermal conductivity K factor mW/m ⁇ K, 22.5° C.

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Abstract

用于浇注型聚氨酯硬质泡沫制备中的化学-物理结合型的碳酸醇胺盐发泡剂组合物，它包括：1)高水含量和低碳酸氢盐含量的碳酸醇胺盐化学发泡剂(F1)；和2)环戊烷；3)任选的，沸点在15-41℃范围内的物理发泡剂(F2)，其中物理发泡剂(F2)是选自于HFC-245fa、HFC-365mfc、LBA和六氟丁烯中的一种或多种(两种或三种)；其中化学发泡剂(F1)包括：A)67-90wt％的碳酸二(C2-C9醇胺)盐；B)10-33wt％的水；C)0-20wt％的C2-C9醇胺。

Description

用于聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物 技术领域
本发明涉及用于冰箱、冰柜、热水器、冷链保温(冷藏车)等行业的(浇注型)聚氨酯硬质泡沫的碳酸醇胺盐复合发泡剂，更具体地说，涉及由高水含量的碳酸醇胺盐化学发泡剂与环戊烷和任选的沸点在15-41℃范围内的物理发泡剂相结合的一种化学-物理结合型发泡剂，尤其所述聚氨酯硬质泡沫是采用包含部分的芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇)和/或甲苯二胺聚醚多元醇的聚合物多元醇作为白料所制备的。
背景技术
聚氨酯硬质泡沫材料是优质的绝热保温材料，广泛应用于冰箱、冰柜、热水器、冷链保温等行业。为了环保的需要，在这些行业，聚氨酯泡沫材料生产过程中常用水和环戊烷作为发泡剂，由于环戊烷的导热系数比较高导致泡沫材料的导热系数也比较高，能耗大，为了降低泡沫材料的导热系数，提高保温材料的保温性能，降低能耗，要加入其他氢氟烃类物理发泡剂，例如HCFC-141b(一氟二氯乙烷，分子量116.95，沸点32℃)，CFC-113(三氯三氟乙烷，分子量187.39，沸点47.7℃)，CFC-11(三氯一氟甲烷，分子量137.4，沸点23.8℃)，HCFC-123(三氟二氯乙烷，分子量152.93，沸点27.85℃)，HFC-245fa(分子量134，沸点15.3℃)，HFC-365mfc(分子量148，沸点40.2℃)，LBA(反式-1-氯-3,3,3-三氟丙烯，分子量130.5，沸点19℃)，六氟丁烯(分子量164，沸点33℃)等。某些氯氟烃的价格昂贵。这些氢氟烃类物理发泡剂的生产过程中也会产生含氯氟的副产物，对环境有影响。
US6326412 B1公开了作为聚氨酯发泡剂的氨基甲酸铵，其中氨基甲酸铵的粘度高达2200mPa.s(参见说明书第6栏第51-55行,lines 51-55 in column 6)，它为粘稠或半固体状态。
目前，用于冰箱、冰柜、热水器、冷藏车(冷链保温)等行业中的聚氨酯硬质泡沫材料的绝热性能越来越重要。一般，用于这些行业中的聚氨酯硬质泡沫的兰芝模(Lance)导热系数λ(mW/m·K，10℃)是在19.00-20.00范围。如果导热系数λ从19.00降低至18.90,更优选地降低至18.80，18.70，18.60，18.50，18.40，18.30，18.20，18.10，18.05，18.00或17.95(其中17.95-18.00几乎属于最低的极限值，继续降低此数值将变得非常困难)，则每一个进步都带来巨大的经济利益。例如，世界全每年生产至少几千万台冰箱和冷柜，通过这些冰箱和冷柜使用改进的硬质泡沫，一台冰箱或冷柜每天节省0.1-0.3度电，一年节省36.5-109.5度电。仅仅就全世界每年生产的冰箱和冷柜数量而言，节省的电力是惊人的。
在冰箱、冰柜、热水器、冷藏车(冷链保温)等行业中的聚氨酯硬质泡沫的工业化生产中，通常使用喷枪的浇注方法将发泡用混合物(由白料和黑料在高压浇注机的混合室中混合而成)经由模具的单个浇注口被注入该模具内，发泡用混合物(发泡用物料)在模具内进行发泡反应、固化，然后进行脱模。例如，在冰箱生产流水线中，平均2-3分钟有一台冰箱下线，因此，发泡用混合物的流动性是非常重要的，要求它能够在较短的时间内填充到不规则的模具内腔的每一个角落，确保发泡混合物在模具内填充均匀并且不留死角。冰箱、冷柜、热水器等行业的发泡工艺实际上是在工业化生产流水线上的在线发泡工艺。
本领域的技术人员认为聚氨酯硬质泡沫材料中泡孔内的气体的导热系数决定了泡沫材料的绝热性能，即，泡孔内气体的导热系数越低，泡沫材料的绝热性能越好。因而，致力于开发新型的气态下具有更低导热系数的含氟发泡剂。
发明内容
本申请的发明人通过多年的研究发现，相对于泡孔内气体的导热系数对于聚氨酯硬质泡沫材料的绝热性能的影响而言，聚氨酯硬质泡沫材料中泡孔微观结构对于泡沫材料的绝热性能有更大的影响。在具有优异的绝热性能的这些聚氨酯硬质泡沫中，聚氨酯硬质泡沫材料中泡孔微观结构和闭孔率主要地决定了泡沫材料的绝热性能。
本申请所要解决的技术问题是通过对发泡组合物的组成进行优化，改进发泡工艺，进而改变泡沫的微观结构，以便提高所生产聚氨酯硬质泡沫的绝热性能和强度性质。
为了获得具有良好的泡孔微观结构的聚氨酯硬质泡沫，本申请的发明人致力于研究由碳酸醇胺盐化学发泡剂和物理发泡剂组成的化学-物理复合发泡剂。
本申请的发明人发现，对于由碳酸醇胺盐化学发泡剂和物理发泡剂组成的复合发泡剂而言，一些影响因素，例如，化学发泡剂和物理发泡剂，各自或两者以复合物形式，与作为白料的聚合物多元醇之间的相容性，化学发泡剂的活性和物理发泡剂(它产生初始成核作用)的沸点(它们影响发泡反应的起发时间或乳白时间)，醇胺(作为交联剂)的含量和类型，水的含量，等等，对于发泡反应过程具有直接的影响。
在发泡过程中，由白料和黑料混合所形成的发泡混合物的合适膨胀速度和固化速度(即合适的发泡速度，它包括起发时间、拉丝时间和结皮时间)主要地决定了泡孔微观结构。另外，水和由化学发泡剂分解所形成的醇胺(活性较高的醇胺先作为催化剂和交联剂，活性低的水在发泡反应的后期作为交联剂或不参与交联反应)的含量又决定了泡孔内壁的交联强度并且进而影响泡沫材料的压缩强度和抗变形性能。此外，泡孔内壁的交联有利于防止泡孔破裂和因此提高闭孔率，而闭孔率的提高又会提高泡沫的绝热性能。
对于在绝热性能方面具有高要求的冰箱、冰柜、热水器和冷链保温(冷藏车)行业中的应用的聚氨酯硬质泡沫(下面简称“冰箱用聚氨酯硬质泡沫”或“冰箱用PU泡沫”)来说，在冰箱、冷柜、热水器或冷藏车的生产中工业化聚氨酯发泡过程中需要相应的合适的发泡速度。一般来说，在工业化生产的在线发泡工艺中，相关领域的发泡速度如下表A中所示：
表A：生产不同类型泡沫的发泡速度
Figure PCTCN2021082825-appb-000001
通常，用于制备聚氨酯硬质泡沫的多异氰酸酯(例如，多亚甲基多苯基多异氰酸酯，即聚合MDI)被称作“黑料”，而添加了各种助剂(如聚氨酯催化剂、泡沫稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂)和发泡剂的发泡用聚合物多元醇组合物被称作“白料”。其中，添加了各种助剂(如聚氨酯催化剂、泡沫稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂)、但仅仅没有添加发泡剂的发泡用聚合物多元醇组合物被称作“干白料”。也就是说，“干白料”是指：不含发泡剂的“白料”，或包含聚合物多元醇类和除发泡剂之外的其它助剂的一种聚氨酯发泡用干白料。
通常，在“干白料”或“白料”中的聚氨酯催化剂包括仲胺型的前期催化剂(即，前期催化剂)和叔胺型的后期交联催化剂(即，后期催化剂)。
本发明的目的是针对冰箱、冰柜、热水器(电热水器或太阳能热水器)或冷藏车用的(浇注型)聚氨酯硬质泡沫，设计特定的发泡剂组合物。通常，在冰箱、冰柜或冷藏车的生产流水线上的发泡反应中，使用浇注机(或高压、中压或低压浇注机)将包含黑料和白料的发泡用混合物经由单个注料口注入模具中，发泡用混合物具有较高的流动性并且能够均匀地填充满整个模具，在规定的时间内(开模时间或脱模时间一般为180秒左右)完成发泡。
对于聚氨酯硬质泡沫的理想的泡孔微观结构而言，它是指细腻(或细密)且泡孔尺寸均匀的泡孔结构。也就是说，一方面泡沫具有较低的密度，另一方面，单位体积的泡沫的数量是尽可能多(从SEM照片看，单位面积的泡孔的数量应该尽可能多)，平均泡孔直径是更小，和泡孔尺寸是比较均匀，以及闭孔率是高的。目前，在冰箱、冰柜行业，泡沫密度一般是28-36Kg/m 3；在热水器行业，泡沫密度一般是33-40Kg/m 3。一般，在本申请中，当泡沫的密度是在25-42Kg/m 3范围，平均泡孔直径是在180-240微米(优选190-230微米，更优选195-220微 米)范围内，尤其，泡孔的尺寸比较均匀，这样的泡孔微观结构是细腻的或理想的。也就是说，在单位体积内泡孔的数量越多，泡孔的平均直径在180-240微米之间，泡孔直径更均匀和闭孔率越高，这样的泡孔微观结构是越理想的。
在本申请中，“任选的”表示有或没有。
在本申请中，优选，所述的重量份是(大约)相对于80-115重量份(优选85-110重量份，更优选90-100重量份或100-115重量份)的包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料(简称，干白料)，或是(大约)相对于80-115重量份(优选85-110重量份，更优选90-100重量份或100-115重量份)的在干白料中存在的全部聚合物多元醇。用于干白料中的聚合物多元醇包括聚醚多元醇(例如聚氧化丙烯多元醇)和/或聚酯多元醇(例如芳族聚酯多元醇或PET多元醇)。
根据本发明的第一个实施方案，提供一种用于制备浇注型聚氨酯硬质泡沫的高水含量、低醇胺碳酸氢盐含量的碳酸醇胺盐发泡剂组合物(FC)，更具体地说，一种用于制备用于冰箱、冰柜或冷藏车中的(浇注型)聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物(FC，foaming agent composition)。在冰箱、冰柜或冷藏车生产过程的浇注发泡反应中，包括黑料和白料的发泡用混合物通过(单个)浇注口被注入模具中，让发泡用混合物均匀地填充满整个模具内腔，然后，自注料开始起经过大约180秒的时间开模或脱模。也就是说，在3分钟之内完成前前、中期和后期的反应。
具体地说，根据本发明的第一个实施方案，提供一种用于制备聚氨酯硬质泡沫的高水含量、低醇胺碳酸氢盐含量的碳酸醇胺盐发泡剂组合物(FC)，该FC包含高水含量和低的醇胺碳酸氢盐含量的碳酸醇胺盐化学发泡剂(F1)。
也就是说，本发明提供用于一种用于制备聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物(FC)，它包括以下组分：
(1)高水含量的碳酸醇胺盐化学发泡剂(F1)；和
(2)环戊烷；
(3)任选的，沸点在15-41℃范围内的(氢氟烃类)物理发泡剂(F2)，其中物理发泡剂(F2)是选自于HFC-245fa、HFC-365mfc、LBA和六氟丁烯中的一种或多种(两种或三种)；
(4)任选的，水(F3)；
其中，各种组分的相对用量(或质量之比)是：水(F3)的量是0-2重量份，0-1.5重量份，更优选0-1重量份，进一步优选0-0.5重量份，更优选0-0.1重量份；物理发泡剂(F2)的量是0-7重量份，优选0-6.5重量份，优选0-6重量份，优选0-5.5重量份，优选0-5重量份， 更优选0-4.5重量份，优选0-4重量份，更优选0-3.5重量份，更优选0-3重量份，更优选0-2.5重量份，最优选0重量份；化学发泡剂(F1)的量是1-10重量份，优选1.2-9.5重量份，优选1.3-9重量份，优选1.4-8.5重量份，优选1.5-8重量份，优选2.8-8重量份，优选3-8重量份，优选3.5-7.5重量份，优选4-7重量份，优选4.5-6.5重量份，优选5-6.5重量份，更优选5-6重量份，例如5.5重量份；和，环戊烷的量是10-20重量份，优选10.5-19.5重量份，优选10.5-19重量份，优选11-18.5重量份，优选11.5-18重量份，例如，12、13、14、15、16、17或17.5重量份。
一般，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和，优选水(F3)+化学发泡剂(F1)的质量之和(即，F2为0)，更优选化学发泡剂(F1)的质量(即，F3和F2为0)，是：4-10重量份，优选4-9.5，4-9，4.5-9，4.5-8.5，例如4.999份、5份、5.499份、5.5份、6、7或8份。环戊烷的质量是10-20重量份，优选10.5-19.5，11-19，11.5-18.5，12-18，12-17.5，例如13、14、15、16或17。优选，物理发泡剂(F2)的质量是0重量份。更优选，水(F3)和物理发泡剂(F2)的质量均为0重量份。
一般，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和与环戊烷的质量之比(或相对用量)，优选水(F3)+化学发泡剂(F1)的质量之和(即，F2为0)与环戊烷的质量之比(或相对用量)，更优选化学发泡剂(F1)的质量(即，F3和F2都为0)与环戊烷的质量之比(或相对用量)，是：(4-10重量份):(10-20重量份)，优选(4-9.5):(10-20)，(4-9):(10-20)，(4-9):(10-18)，(4-9):(10-16)，优选(4.5-10):(10-20)，(5-9.5):(10-20)，(5-9.5):(10-18)，(5-9.5):(10-16)，(5-9):(10-20)，(5-9):(10-18)，(5-9):(10-16)，更优选(5.5-9):(10-20)，(5.5-8.5):(10-20)，优选(5.5-8):(10-20)，优选(5.5-8):(10.5-19.5)，(5.5-8):(11-19)，(5.5-8):(11.5-18.8)，(5.5-8):(12-18.5)，(5.5-8):(13-18)，优选(5.6-8):(10.5-19.5)，优选(5.7-8):(11-19)，优选(5.8-7.8):(11.5-18.8)，优选(5.9-7.6):(12-18.5)，优选(6-7):(13-18)。这里，(4-10):(10-20)也可以表示为(1-2.5):(2.5-5重量份)，以此类推。
一般，化学发泡剂(F1)包含以下成分(或组分)：
(A)67-90wt％的碳酸二(C2-C9醇胺)盐；该含量优选是68-89.5wt％，更优选69-89wt％，70-88.5wt％，71-88wt％，72-87.5wt％，73-87wt％，例如74、75、76、78、79、80、81、82、83、84、85或86wt％；
(B)10-33wt％的水；该水含量优选是10.5-32wt％，优选11-31wt％，11.5-30wt％，12-29wt％，12.5-28wt％，13-27wt％，例如14、15、16、18、19、20、21、22、23、24、25或26wt％；
(C)0-20wt％的(游离)C2-C9醇胺；该含量优选是0.01-19wt％，优选0.02-18wt％，更优选0.03-17wt％，更优选0.04-16wt％，优选0.06-15wt％，例如0.08、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、10.5、11、12、13或14wt％；
和
(D)0-10wt％的C2-C9醇胺碳酸氢盐；该含量优选是0-9wt％，优选0-8wt％，0-7wt％，0-6wt％，0-5wt％，0-4wt％，0-3wt％，0-2wt％，0-1wt％，0-0.5wt％，最优选0wt％；
上述百分比是基于化学发泡剂(F1)的总重量。
一般，组分(A)、(B)、(C)和(D)的重量之和是基于化学发泡剂(F1)的总重量的90-100wt％，优选92-100wt％，优选93-100wt％，优选95-100wt％，优选98-100wt％，优选98.5-100wt％，优选99-100wt％，优选99.5-100wt％，优选99.8-100wt％，更优选100wt％。
一般，在化学发泡剂(F1)中的全部C2-C9醇胺包含或主要包含70-100mol％，优选72-100mol％，优选75-100mol％，优选77-100mol％，优选80-100mol％，优选82-100mol％，优选85-100mol％，优选87-100mol％，优选90-100mol％，优选92-100mol％，优选95-100mol％，优选97-100mol％，优选98-100mol％)的特定C4-C9二醇胺，所述特定C4-C9二醇胺是(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)、(II)具有羟基异丙基的C5-C9二醇胺类(IIa)或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物，该mol％是基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量(或基于在组分(A)、(C)和(D)中存在的C2-C9醇胺类的总摩尔量)，并且，(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)是选自于二乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和N-丙基二乙醇胺中的一种或多种，和，(II)具有羟基异丙基的C5-C9二醇胺类(IIa)是选自于二异丙醇胺、乙醇异丙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-丙基二异丙醇胺、N-甲基乙醇异丙醇胺、N-乙基乙醇异丙醇胺和N-丙基乙醇异丙醇胺中的一种或多种。
一般，化学发泡剂(F1)的pH是8.6-10.4，优选8.8-10.2，优选9-10.1，更优选9.2-10，优选9.3-9.7，更优选9.4-9.6。
优选，当发泡剂组合物(FC)用于制备在低温下使用的绝热泡沫材料(例如用于制备冰箱或冷柜的绝热泡沫材料)时，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和是(5.5-10)重量份，优选6-10重量份，环戊烷的质量是10-20重量份，优选12-18重量份；或者，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和与环戊烷的质量之比(或相对用量)是(5.5-10): (10-20)，优选(6-10):(12-18)或(5.5-9):(10-20)或(5.5-8.5):(10-20)。例如，化学发泡剂(F1)以大于5重量份(例如5或5.5或6重量份)的用量使用(另外，例如，F2或水(F3)以0-1重量份的量使用)，以便使得发泡物料(白料+黑料)具有较高的流动性，发泡物料具有合适的启发时间和拉丝时间，所得泡沫材料的泡孔尺寸是比较均匀的，泡沫材料具有较低的产品密度(例如28-36Kg/m 3)，同时显著提高所得泡沫材料的机械强度(泡孔壁的交联密度和抗收缩变形)和绝热性能。
优选，当发泡剂组合物(FC)用于制备在较高温度(如70-110℃)下使用的保温泡沫材料(例如用于制备热水器(电热水器或太阳能热水器)的保温泡沫材料)时，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和是(4-10)重量份，优选4-9重量份，优选4-8重量份，优选5-7重量份，优选5.5-6重量份，环戊烷的质量是10-20重量份，优选12-18重量份或12-16重量份；或者，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和与环戊烷的质量之比(或相对用量)是(4-10重量份):(10-20重量份)，更优选(4-9重量份):(12-18重量份)，优选(4-8重量份):(12-16重量份)。例如，化学发泡剂(F1)以3-5.5重量份(例如小于5.5或小于5重量份，如3-5.499份，或4份)的用量使用(另外，例如，F2或水(F3)以0-1重量份的量使用)，使得所生产的泡沫材料具有较高的产品密度(例如大约40Kg/m 3)，泡沫材料适合在较高温度(例如70-110℃)下发挥保温效果，同时降低泡沫材料的生产成本。
上述高水含量的碳酸醇胺盐化学发泡剂(F1)是指高水含量和低醇胺碳酸氢盐含量的碳酸醇胺盐化学发泡剂(F1)。本申请中“N-丙基”包括N-正丙基和N-异丙基。
也就是说，所述特定C4-C9二醇胺是选自于(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)和(II)具有羟基异丙基的C5-C9二醇胺类(IIa)中的一种或多种。优选，所述特定C4-C9二醇胺是：(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)，或，(I)醇胺类(Ia)与(II)具有羟基异丙基的C5-C9二醇胺类(IIa)的混合物或结合物(III)。
一般，当化学发泡剂(F1)中存在大于0wt％(例如大于0.01wt％)的游离醇胺(例如C2-C9醇胺或其它醇胺)时，在化学发泡剂(F1)中不存在醇胺碳酸氢盐。
优选，上述的化学发泡剂(F1)是通过在C2-C9醇胺和水的混合物中通入CO 2气体的中和方法来制备的；优选，该中和方法包括：在C2-C9醇胺和水的混合物中通入表压力为0.09-0.4MPa(0.9-4atm，例如0.09-0.35MPa或0.1-0.3MPa)的CO 2气体至饱和为止，任选地，在所得产物中进一步添加上述C2-C9醇胺(优选，以上所述的特定C4-C9二醇胺，例如二乙醇胺和/或二异丙醇胺)，以使得产物的pH值在8.6-10.4范围(优选8.8-10.2，9-10.1，优选9.2-10，优选9.2-9.7，优选9.4-9.6)，获得化学发泡剂(F1)；优选，其中在C2-C9醇胺和水的混合物中的水量应使得 所制备的化学发泡剂(F1)中的(游离)水含量为10-33wt％，优选是10.5-32wt％，优选11-31wt％，11.5-30wt％，12-29wt％，12.5-28wt％，13-27wt％，例如14、15、16、18、19、20、21、22、23、24、25或26wt％。这里所述的上述C2-C9醇胺包含上述的特定C4-C9二醇胺，其中特定C4-C9二醇胺和其组成(mol％)与以上所定义相同。优选，向C2-C9醇胺和水的混合物中通入的CO 2气体的压力应该进行选择(一般根据C2-C9醇胺的碱性)，该压力足以使得C2-C9醇胺尽可能按照形成碳酸二(C2-C9醇胺)盐的化学计量被CO 2中和但形成不超过10wt％(例如0-10wt％，优选0-9wt％，0-8wt％，0-7wt％，0-6wt％，0-5wt％，0-4wt％，0-3wt％，0-2wt％，0-1wt％，0-0.5wt％，最优选0wt％)的C2-C9醇胺碳酸氢盐，该wt％基于所形成的化学发泡剂(F1)(即，碳酸醇胺盐水合物)的重量。
在通入CO 2气体的中和方法中，针对不同C2-C9醇胺的碱性来选择合适的CO 2压力以便使得C2-C9醇胺尽可能按照形成碳酸二(C2-C9醇胺)盐的化学计量被CO 2中和并且所获得的化学发泡剂(F1)中的C2-C9醇胺碳酸氢盐的含量是尽可能低，例如低于10wt％、更优选低于8wt％或甚至低于5wt％，CO 2压力的选择是本领域技术人员容易实现的。另外，为了制备包含两种或两种以上的不同碱性的醇胺并且所形成醇胺碳酸氢盐的含量较低的一种化学发泡剂(F1)，能够通过分别在不同的CO 2气体的压力下向每一种醇胺中通入CO 2气体来制备每一种醇胺的碳酸盐(几乎不含醇胺碳酸氢盐)。然后将几乎不含醇胺碳酸氢盐的两种或多种的中和产物按照相应的比例进行混合，以获得含有多种醇胺碳酸盐和含有较少量的醇胺碳酸氢盐的一种化学发泡剂(F1)。另外，对于通过通入CO 2气体从碱性较强的醇胺(例如，(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺，或(IIb)具有羟基异丙基的仲胺型C4-C6单醇胺)制备含有较大量的醇胺碳酸氢盐的一种醇胺碳酸盐产物的情况，能够进一步在产物中添加弱碱性的二醇胺来使得醇胺碳酸氢盐转化为醇胺碳酸盐，从而减少产物中的碳酸氢盐的含量至大约0wt％，也就是说，形成了含有较强碱性的醇胺与较弱碱性的醇胺的一种醇胺混合物，但是，这种醇胺混合物仍然不是优选的，因为它含有较强碱性的醇胺(如N-甲基乙醇胺)，而这些较强碱性的醇胺对于发泡反应的起发时间有影响。
首先，发明人通过实验发现，在发泡剂组合物(FC)中存在的少量的、不稳定的醇胺碳酸氢盐对于发泡反应有很大的影响，导致发泡反应中的起发时间缩短(例如至1-2秒)。例如，由于碳酸氢盐的存在，在白料与黑料混合后立即发生剧烈的反应，泡沫迅速膨胀而失控。其原因可能是醇胺碳酸氢盐是不稳定的(容易分解)并且反应活性是较高的。因此，控制化学发泡剂(F1)中醇胺碳酸氢盐的含量低于10wt％(尤其低于8wt％或5wt％)是比较重要的。
其次，在控制碳酸氢盐的含量的情况下，进一步对于C2-C9醇胺中的各种醇胺进行选择， 还能够进一步改进发泡剂组合物的性能。
优选，所述特定C4-C9二醇胺是：(I)醇胺类(Ia)，或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物；更优选，所述特定C4-C9二醇胺是(III)由组分(I)醇胺类(Ia)和(II)醇胺类(IIa)组成的结合物或混合物；因此，其中组分(I)醇胺类(Ia)与组分(II)醇胺类(IIa)的摩尔比是1:(0-2.5)，优选1:(0.1-2.5)，优选1:(0.1-2)，更优选1:(0.2-1.5)，更优选1:(0.22-1.2)，更优选1:(0.24-0.9)，更优选1:(0.25-0.5)，更优选1:(0.27-0.4)，更优选1:(0.29-0.45)，最优选3:1。优选，在(III)由组分(I)醇胺类(Ia)和(II)醇胺类(IIa)组成的结合物或混合物中，组分(I)的mol％是28-100mol％，更优选33-91wt％，更优选40-83wt％，更优选45-82wt％，更优选52-81wt％，更优选66-80wt％，更优选71-78wt％，更优选68-77wt％，最优选75mol％，基于组分(I)和组分(II)的总摩尔量。
一般，在本申请中，C2-C9醇胺包括(include)特定C4-C9二醇胺(例如具有羟乙基和/或羟基异丙基的C4-C9二醇胺(Ia+IIa)，如二乙醇胺或二异丙醇胺)、仲胺型C3-C6单醇胺(例如具有羟乙基或羟基异丙基的仲胺型C3-C6单醇胺(Ib+IIb)，如N-甲基单异丙醇胺或N-甲基乙醇胺)和任选的伯胺型C2-C9单醇胺类和任选的叔胺型C4-C7单醇胺类和任选的叔胺型C6-C9三醇胺类。
一般，具有羟乙基和/或羟基异丙基的C4-C9二醇胺(Ia+IIa)包括(include)，例如，二乙醇胺、二异丙醇胺、乙醇异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-丙基二异丙醇胺、N-甲基乙醇异丙醇胺、N-乙基乙醇异丙醇胺和N-丙基乙醇异丙醇胺。
一般，具有羟乙基或羟基异丙基的仲胺型C3-C6单醇胺(Ib+IIb)包括(include)，例如，N-甲基单乙醇胺、N-乙基单乙醇胺、N-丙基单乙醇胺、N-甲基单异丙醇胺、N-乙基单异丙醇胺和N-丙基单异丙醇胺。
一般，在化学发泡剂(F1)中的全部C2-C9醇胺还可能包含低于30mol％，例如0-30mol％，优选0-28mol％，优选0-25mol％，优选0-23mol％，优选0-20mol％，优选0-18mol％，优选0-15mol％，优选0-13mol％，优选0-10mol％，优选0-8mol％，优选0-5mol％，优选0-3mol％，优选0-2mol％的除了上述特定C4-C9二醇胺之外的其它C2-C9醇胺类。例如，这些其它C2-C9醇胺类是选自于具有羟乙基或羟基异丙基的仲胺型C3-C6单醇胺(Ib+IIb)(即，(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺和(IIb)仅仅具有羟基异丙基的仲胺型C4-C6单醇胺)中的一种或多种；其中，仅仅具有羟乙基的仲胺型C3-C5单醇胺(Ib)是选自于N-甲基单乙醇胺、N-乙基单乙醇胺和N-丙基单乙醇胺中的一种或多种；和，仅仅具有羟基异丙基的仲胺型C4-C6 单醇胺(IIb)是选自于N-甲基单异丙醇胺、N-乙基单异丙醇胺和N-丙基单异丙醇胺中的一种或多种。这里，该mol％是基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量(或基于在组分(A)、(C)和(D)中存在的C2-C9醇胺类的总摩尔量)。
一般，所述特定C4-C9二醇胺是选自于C4-C7二乙醇胺类(它包括二乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和N-丙基二乙醇胺)、C6-C9二异丙醇胺类(它包括二异丙醇胺，N-甲基二异丙醇胺、N-乙基二异丙醇胺和N-丙基二异丙醇胺)和C5-C8乙醇异丙醇胺类(它包括乙醇异丙醇胺、N-甲基乙醇异丙醇胺、N-乙基乙醇异丙醇胺和N-丙基乙醇异丙醇胺)中的一种或两种或更多种(优选，两种或更多种)；更优选，所述特定C4-C9二醇胺是由(C4-C7二乙醇胺类)与(C6-C9二异丙醇胺类和/或C5-C8乙醇异丙醇胺类)组成的混合物，例如按照按照0.3-5:1(优选0.7-4.5:1)的摩尔比；更优选，所述特定C4-C9二醇胺是由(C4-C7二乙醇胺类)与(C6-C9二异丙醇胺类和/或C5-C8乙醇异丙醇胺类)按照1.5-4.5:1摩尔比(优选1.8-4.2:1，更优选2-4:1，更优选2.3-3.7:1，更优选2.5-3.5:1，更优选2.7-3.3:1，更优选2.8-3.2:1，尤其3:1摩尔比)所组成的混合物；更优选，所述特定C4-C9二醇胺是由(二乙醇胺)和(二异丙醇胺和/或乙醇异丙醇胺)按照1.5-4.5:1摩尔比所组成的混合物，更优选，摩尔比是1.8-4.2:1，更优选2-4:1，更优选2.3-3.7:1，更优选2.5-3.5:1，更优选2.7-3.3:1，更优选2.8-3.2:1，尤其3:1。
一般，所述仲胺型C3-C6单醇胺(Ib+IIb)是选自于N-甲基单乙醇胺、N-甲基单异丙醇胺、N-乙基单乙醇胺、N-乙基单异丙醇胺、N-丙基单乙醇胺和N-丙基单异丙醇胺中的一种或两种或多种。
一般，在化学发泡剂(F1)中的全部C2-C9醇胺有可能包括，除了上述特定C4-C9二醇胺以及具有羟乙基或羟基异丙基的仲胺型C3-C6单醇胺(即，(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺和(IIb)仅仅具有羟基异丙基的仲胺型C4-C6单醇胺)之外的其它C2-C9醇胺类(简称“杂质醇胺类IA”)，例如，伯胺型C2-C9单醇胺类，叔胺型C4-C9单醇胺类(例如N-二甲基乙醇胺和N-二甲基异丙醇胺)，叔胺型C6-C9三醇胺类(例如三乙醇胺、三异丙醇胺)，等等。化学发泡剂(F1)中此类其它醇胺类(杂质醇胺类IA)的含量应该是尽可能少，一般是0-30mol，优选0-28mol％，优选0-25mol％，优选0-23mol％，优选0-20mol％，优选0-18mol％，优选0-15mol％，优选0-13mol％，优选0-10mol％，优选0-8mol％，优选0-5mol％，优选0-3mol％，优选0-2mol％，基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量(或基于在组分(A)、(C)和(D)中存在的C2-C9醇胺类的总摩尔量)。
另外，在化学发泡剂(F1)中的全部C2-C9醇胺有可能包括，除了上述特定C4-C9二醇胺 之外的其它醇胺类：(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺，(IIb)仅仅具有羟基异丙基的仲胺型C4-C6单醇胺，和上述所谓“杂质醇胺类IA”；全部这些其它醇胺类的总计mol％是0-30mol％，优选0-28mol％，优选0-25mol％，优选0-23mol％，优选0-20mol％，优选0-18mol％，优选0-15mol％，优选0-13mol％，优选0-10mol％，优选0-8mol％，优选0-5mol％，优选0-3mol％，优选0-2mol％，基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量(或基于在组分(A)、(C)和(D)中存在的C2-C9醇胺类的总摩尔量)。
以上所述的重量份是(大约)相对于或基于80-115重量份(优选85-110重量份，更优选85-100或90-100重量份或90-115重量份或100-115重量份，例如86、87、88、89、90、91、92、93、94、95、96、97、98、99、100、102、105、107、108、110、112、113或114重量份)的包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料。其中所述其它助剂包括聚氨酯催化剂，发泡稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂。所述发泡剂组合物(FC)用于与干白料和作为黑料的多异氰酸酯混合来进行发泡反应，从而制备聚氨酯硬质泡沫。当化学发泡剂(F1)的量大于12重量份以及CP的用量相应减少时，所得白料的粘度明显增大。
这里所述的物理发泡剂(F2)，即HFC-245fa、HFC-365mfc、LBA和六氟丁烯，都属于氢氟烃类物理发泡剂。
当发泡剂组合物(FC)不包含物理发泡剂(F2)时，化学发泡剂(F1)和环戊烷分别装在单独的容器中。另外，当发泡剂组合物(FC)进一步包含物理发泡剂(F2)时，化学发泡剂(F1)装在单独的容器中，而物理发泡剂(F2)和环戊烷分别被装在不同的容器中或被装在同一容器中。
本发明的发泡剂组合物(FC)用于浇注型聚氨酯硬质泡沫的制备，更优选用于在冰箱、冰柜、热水器或冷藏车生产过程中的浇注型聚氨酯硬质泡沫的制备。
在本申请中，化学发泡剂(F1)的用量一般不少3重量份，这能够使得所获得的聚氨酯硬质泡沫具有良好的绝热性能和强度性能。
如果化学发泡剂(F1)以小于3重量份的用量(例如1-2.8重量份)使用，则它主要用于发泡反应的前期成核作用，因为在白料与黑料混合时立即产生CO 2气体。而物理发泡剂是利用反应热使得发泡混合物升温之后发生汽化来产生气泡，这是一种滞后的起泡、膨胀。所述的前期成核作用有利于增加泡孔的数量和提高泡孔尺寸的均匀性，因而也有助于改进聚氨酯硬质泡沫的微观结构，从而在一定的程度上提高泡沫的绝热性能。当然，更优选的是以高于3重量份(即3-8重量份)的用量使用，以便获得更好的综合性能的聚氨酯硬质泡沫。
当在发泡剂组合物(FC)中存在水(F3)时，这意味着，通过另外使用少量(至多2重量份) 的水和相应地同时减少物理发泡剂的用量以降低硬质泡沫生产成本，但是，这会降低所生产泡沫的强度和抗变形性能，同时还会降低泡沫的闭孔率而使得绝热性能下降。因此，优选的是，水(F3)的量应该减少，更优选减少至0重量份。
另外，当在发泡剂组合物(FC)中存在物理发泡剂(F2)时，这意味着，物理发泡剂(F2)的用量越高，硬质泡沫生产成本显著地提高，而且导致硬质泡沫的强度性质下降，但是所生产泡沫的绝热性能并没有显著地提高。因此，优选的是，物理发泡剂(F2)的用量应该减少，更优选减少至0重量份。当物理发泡剂(F2)的用量减少时，化学发泡剂(F1)的用量相应地提高，以便获得具有规定的泡沫密度或同等的泡沫密度的硬质泡沫。
优选，发泡剂组合物(FC)仅仅包括组分(1)化学发泡剂(F1)和组分(2)环戊烷，即，组分(2)物理发泡剂(F2)和组分(3)水(F3)的用量均为0重量份。因而，化学发泡剂(F1)与环戊烷的质量之比(或相对用量)是(4-10重量份):(10-20重量份)，优选(4-9.5):(10-20)，(4-9):(10-20)，(4-9):(10-18)，(4-9):(10-16)，优选(4.5-10):(10-20)，(5-9.5):(10-20)，(5-9.5):(10-18)，(5-9.5):(10-16)，(5-9):(10-20)，(5-9):(10-18)，(5-9):(10-16)，更优选(5.5-9):(10-20)，(5.5-8.5):(10-20)，优选(5.5-8):(10-20)，优选(5.5-8):(10.5-19.5)，(5.5-8):(11-19)，(5.5-8):(11.5-18.8)，(5.5-8):(12-18.5)，(5.5-8):(13-18)，优选(5.6-8):(10.5-19.5)，优选(5.7-8):(11-19)，优选(5.8-7.8):(11.5-18.8)，优选(5.9-7.6):(12-18.5)，优选(6-7):(13-18)，更优选(6-7):(14-18)，更优选(6-7):(15-18)，更优选(6-7):(16-18)。
在这些情况下，一方面显著降低硬质泡沫生产成本，同时，出乎预料地，还使得所形成的硬质聚氨酯泡沫具有极低的导热系数，即，兰芝模(Lance)λ(mW/m·K，10℃)。该系数在下面简称导热系数(λ)。
一般，相对于或基于80-115重量份(优选85-110重量份，优选90-100重量份，如100重量份)的干白料，发泡剂组合物(FC)的用量足以使得所制备的(浇注型)聚氨酯硬质泡沫的密度是在25-38Kg/cm 3范围，优选26-37Kg/cm 3，优选27-36.5Kg/cm 3，优选28-36Kg/cm 3，优选28.5-35.5Kg/cm 3，优选29-35Kg/cm 3，例如30、31、32、33或34Kg/cm 3。
在本申请中优选的是，组分(1)高水含量的碳酸醇胺盐化学发泡剂(F1)和组分(4)任选的水(F3)两者的水量之和是1-3.7wt％(优选1.1-3.5wt％，优选1.2-3.3wt％，优选1.25-3wt％或1.3-2.5wt％或1.4-2wt％，例如1.5、1.6、1.7、1.8wt％)，(大约)相对于或基于100重量份的干白料。在这一范围内的水量能够使得发泡用组合物具有理想的流动性，同时确保所制备的硬质泡沫具有优异的强度性能和绝热性能。
化学发泡剂(F1)由组分A)、B)、任选的C)和任选的D)组成；优选，化学发泡剂(F1)由组分 A)、B)和任选的C)组成或由组分A)、B)和任选的D)组成；更优选，化学发泡剂(F1)由组分A)和B)组成。
根据本发明的最优选方案，提供一种发泡剂组合物(FC)，其中：所述特定C4-C9二醇胺是由二乙醇胺和二异丙醇胺按照1:(0.15-3)，优选1:(0.2-1.5)，更优选1:(0.22-1.2)，更优选1:(0.24-0.9)，更优选1:(0.25-0.5)，更优选1:(0.27-0.4)，更优选1:(0.29-0.45)的摩尔比所组成的混合物。优选，化学发泡剂(F1)的pH是9.2-10，优选9.3-9.7，更优选9.4-9.6。更优选，组分(D)C2-C9醇胺碳酸氢盐的含量是0-5wt％，0-4wt％，0-3wt％，0-2wt％，0-1wt％，0-0.5wt％，最优选0wt％。使用这种发泡剂组合物(FC)所获得的聚氨酯硬质泡沫(密度在25-38Kg/cm 3范围)的兰芝模(Lance)导热系数λ(mW/m·K，10℃)低于18.30或低于18.20或低于18.10，甚至低于18.05。在由二乙醇胺和二异丙醇胺组成的化学发泡剂(F1)中少量存在的二异丙醇胺起着相容或增溶作用，能够提高发泡剂组合物(FC)与干白料中的聚合物多元醇之间的相容性，能够形成透明、均匀的白料，改善了聚氨酯硬质泡沫的微观结构和闭孔率，因而能够将泡沫的导热系数λ(mW/m·K，10℃)降低至例如低于18.05。
本发明提供一种聚氨酯发泡用白料，它包括：(1)包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料，其中所述其它助剂包括聚氨酯催化剂、泡沫稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂；和(2)上述的碳酸醇胺盐发泡剂组合物(FC)。
优选，所述干白料中的聚合物多元醇类包含8-52wt％(优选9-50wt％，优选10-48wt％，优选12-47wt％，优选15-45wt％，优选16-40wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇、聚间苯二甲酸乙二醇酯多元醇或聚对苯二甲酸二乙醇酯多元醇)和/或甲苯二胺聚氧化丙烯多元醇和92-48wt％(优选91-50wt％，优选90-52wt％，优选88-53wt％，优选85-55wt％，优选84-60wt％，更优选82-65wt％)的(非甲苯二胺型或非甲苯二胺引发的)聚氧化丙烯多元醇，即，除甲苯二胺聚氧化丙烯多元醇以外的聚氧化丙烯多元醇。
本发明还提供一种聚氨酯发泡用组合物(或混合物)，它包括：
(1)作为黑料的多异氰酸酯(优选，多亚甲基多苯基多异氰酸酯或聚合MDI)；
(2)包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料；和
(3)以上所述的碳酸醇胺盐发泡剂组合物(FC)。
优选，黑料(1)与干白料(2)和发泡剂组合物(3)的质量之和的比例(即，物料比)是1.1-1.36:1，优选1.13-1.35:1，优选1.15-1.30:1，优选1.17-1.27:1，优选1.18-1.25:1，最优选1.2:1。
本申请中芳族/半芳族聚酯多元醇是指芳族聚酯多元醇和/或半芳族聚酯多元醇，通常具有低粘度(25℃)(例如3000-8000厘泊，如3200-5000或3500-4000)。
对于干白料中的聚合物多元醇类，由于它包含少量的芳族聚酯多元醇(即PET多元醇)，优选，聚邻苯二甲酸乙二醇酯和聚间苯二甲酸乙二醇酯多元醇，更优选聚邻苯二甲酸乙二醇酯。
甲苯二胺聚氧化丙烯多元醇是指甲苯二胺引发或起始的聚氧化丙烯多元醇。
优选，当使用芳族/半芳族聚酯多元醇时，减少甲苯二胺聚氧化丙烯多元醇的用量或不用。
一方面，二乙醇胺类(例如二乙醇胺或N-甲基二乙醇胺)具有较低粘度，但它们与包括聚氧化丙烯多元醇和少量的聚酯多元醇和/或甲苯二胺聚醚多元醇的干白料之间的相容性稍差(通过在搅拌下混合干白料和含有二乙醇胺类的发泡剂所获得的白料随后通过离心处理来快速消泡，发现物料有分层现象，即，底部有较薄的一层物料)，所获得的聚氨酯硬质泡沫的绝热性能不是最理想的。
另一方面，二异丙醇胺类(例如二异丙醇胺、乙醇异丙醇胺、和N-甲基二异丙醇胺)和乙醇异丙醇胺类具有较高的粘度(在通过手工搅拌下混合干白料和含有二异丙醇胺类的发泡剂以便获得白料时，明显感觉白料的搅拌更困难而且白料有更高的粘度)，导致白料与黑料的混合程度不太均匀，所获得的聚氨酯硬质泡沫的绝热性能也不是最理想的。然而，出乎预料的是，这些(二异丙醇胺类和/或乙醇异丙醇胺类)与二乙醇胺类的相结合使用能够显著改善所获得的发泡剂与干白料之间的相容性，能够形成均匀、透明的白料，进而改进了所制备泡沫的微观结构和提高了闭孔率，使得泡沫的导热系数几乎达到最低的极限值(例如λ值低至18.10或甚至低于18.02)。上述两种类型的醇胺相结合使用可能导致掺杂作用，相互降低粘度。
本发明还提供上述碳酸醇胺盐发泡剂组合物(FC)用于配制聚氨酯发泡用组合物的用途。
本发明还提供制备聚氨酯硬质泡沫的方法，该方法包括：将包含上述的发泡剂组合物(FC)的聚合物多元醇组合物白料与作为黑料的多异氰酸酯(优选，多亚甲基多苯基多异氰酸酯或聚合MDI)进行混合和发泡；优选地，进行使用浇注机来进行浇注发泡。
本发明还提供由上述的制备聚氨酯硬质泡沫的方法所获得的聚氨酯硬质泡沫，其中，聚氨酯硬质泡沫的密度是在25-38Kg/cm 3范围，优选26-37Kg/cm 3，优选27-36.5Kg/cm 3，优选28-36Kg/cm 3，优选28.5-35.5Kg/cm 3，优选29-35Kg/cm 3，例如30、31、32、33或34Kg/cm 3。
聚氨酯硬质泡沫的兰芝模(Lance)导热系数λ(mW/m·K，10℃)低于18.50，优选低于18.40，更优选低于18.30，更优选低于18.20，更优选低于18.05。
水与醇胺之间有较强的氢键作用，大于醇胺与碳酸根之间的化学键。
对于发泡剂组合物(FC)在冰箱、冰柜、热水器和冷藏车行业的聚氨酯硬质泡沫的制备中的应用来说，当发泡剂(FC)中环戊烷的相对用量进一步提高至22重量份以上时，将会在所配制的白料中导致形成两相体系(相分离现象)。其中，在白料被搅拌时发现有油滴的存在，另 外，在静置时发生分层，这意味着过多的环戊烷摆脱了水和聚合物多元醇的束缚(或者说，环戊烷在白料中的溶解度是有限的)，它不再参与形成多元复合物。因而，在发泡反应中无法形成均相的发泡体系，所得泡沫中泡孔直径尤其不均匀(其中油滴成为汽化中心，在油滴的位置产生大孔或超大孔)，泡孔的直径通常大于300微米或甚至大于350微米，泡沫的绝热性能显著下降。
所述的相分离现象表明，只有当物理发泡剂(F2)和/或环戊烷在发泡组合物(FC)中的含量是在一定的范围内时，物理发泡剂(F2)和环戊烷与干白料之间有良好的相容性，能够形成透明和均匀的白料。
发明人通过实验已发现，由于在干白料中存在了一部分的含苯环的聚酯多元醇和甲苯二胺聚醚多元醇，这样的干白料的使用能够提高环戊烷在白料体系中的相容性或溶解度，同时，也能够提高HFC-245fa、HFC-365mfc、LBA和六氟丁烯在白料体系中的相容性。但是，由于六氟丁烯具有较高的分子量、更高的密度和更高极性，而较高的密度会影响六氟丁烯在白料中的密度分布，因此，它在白料体系中的相容性比HFC-245fa、HFC-365mfc、LBA在白料中的相容性更差，因此，在本发明中，六氟丁烯的使用不是优选的。
另外，在冰箱、冰柜、热水器和冷藏车行业，当发泡剂(FC)中环戊烷的相对用量进一步减少至低于8重量份时，将会导致所形成的白料的流动性下降，在冰箱的生产过程中无法在较短的时间内浇注填充满模具，而且还影响发泡后模具的脱模性，导致冰箱生产流水线的生产效率大幅度降低，而且还降低冰箱的绝热性能。
当化学发泡剂(F1)中水的含量低于9wt％或甚至低于8wt％或低于7wt％时，将会导致所形成的发泡剂的粘度提高，发泡剂在白料中相容性变差，(由于多元醇的脱水作用)醇胺类以固体或粘稠物从白料中析出，发泡剂的活性增高，导致在冰箱生产的发泡过程中泡沫的起发时间大幅度缩短(例如至1-3秒)，发泡的速度太快而失控。
发泡用混合物的合适的起发时间和流动性对于冰箱、冰柜、热水器或冷藏车领域的模具内浇注发泡而言是非常重要的，因为发泡用混合物经由单个注料口被注入模具的具有复杂结构的内腔。如果起发时间太短或流动性太差，则发泡用混合物在模具内靠近注料口的区域中发泡和硬化，发泡用混合物无法到达更远的区域中，因此，无法均匀地填充满整个模具内腔，这导致硬质泡沫的开模性能太差，泡沫在模具内的整体密度分布不均匀。
例如，在冰箱制造工业生产线上的聚氨酯硬质泡沫的制备中，模具的打开时间常常是大约180秒，因此，拉丝时间同样也是重要的。
另外，当化学发泡剂(F1)中水的含量高于38wt％或甚至高于40wt％或高于45wt％时，将会 在发泡反应中消耗更多的黑料(多异氰酸酯，例如多亚甲基多苯基多异氰酸酯或聚合MDI)，在泡沫材料中产生更多的脲键，导致所得泡沫体的尺寸稳定性下降并且闭孔率降低而降低了泡沫材料的绝热性能。
当化学发泡剂(F1)的pH低于8.6时，化学发泡剂(F1)的活性低和碱性降低，发泡剂(F1)束缚酸性CO 2气体的能力下降，在发泡过程中将白料与黑料搅拌混合时，在反应初始阶段因反应热导致白料稍稍升温而使得CO 2迅速从发泡混合物中逃逸，CO 2气体无法充分地发挥发泡作用，导致所得泡沫的泡孔的尺寸减少。
另外，当化学发泡剂(F1)的pH高于10.4或甚至高于10.5时，化学发泡剂(F1)的活性高和碱性高，意味着发泡剂(F1)中存在更多的碱性醇胺，过量存在的这些碱性醇胺迅速发挥前期催化的作用，导致发泡反应的速度失控(例如起发时间为1-3秒，发泡反应物料迅速膨胀、上升)，此外，前期催化的发泡反应(链增长反应)太快，这还会严重干扰了叔胺催化剂的后期催化交联的作用，降低所得泡沫的强度和抗变形性能。
化学发泡剂(F1)中多余的组分(C)游离C2-C9醇胺(主要包括特定C4-C9二醇胺(Ia+IIa)和任选的仲胺型C3-C6单醇胺(Ib+IIb))一方面用于调节化学发泡剂(F1)的pH值并减少醇胺碳酸氢盐的含量，另一方面它用作前期催化剂以调节发泡反应中的发泡速度(例如起发时间)和用作交联剂，组分(C)C2-C9醇胺(主要包括(Ia+IIa)和任选的(Ib+IIb))与水一起用作发泡反应的中后期交联剂，以提高泡孔内壁的强度，进而提高泡沫的强度和抗变形性能。
更优选，当化学发泡剂(F1)中的全部的C2-C9醇胺由二乙醇胺与二异丙醇胺按照摩尔比为2.8-3.2:1(尤其3:1)组成时，导致由白料和黑料混合所得的发泡用混合物能够在最佳的发泡速度(起发时间和拉丝时间)平稳地进行，其中发泡用混合物具有较高的流动性并且能够均匀地填充满整个模具的内腔，所得聚氨酯硬质泡沫的兰芝模(Lance)导热系数λ(mW/m·K，10℃)低于18.05或18.03，几乎达到了绝热性能的极限值，这体现了泡沫的绝热性能的巨大进步。
另外，如果物理发泡剂(F2)的沸点低于15℃或高于41℃，会影响发泡过程的平稳进行。在本发明中,希望首先由化学发泡剂(F1)与多异氰酸酯反应产生CO 2气体来发挥前期的成核和发泡作用，然后随着反应混合物的温度的升高，依次由物理发泡剂和环戊烷发挥发泡的作用，有利于发泡过程的平稳进行。
如果物理发泡剂(F2)的沸点低于15℃，则在将发泡剂组合物(FC)与干白料混合时低沸点的发泡剂立即挥发、逃逸，另外，早期的起泡作用还会导致发泡反应混合物的组成变得不均匀。
如果物理发泡剂(F2)的沸点高于41℃，则物理发泡剂(F2)的起泡作用稍滞后，影响 了发泡反应的平稳进行，另外，当泡沫被冷却至室温后，泡孔内的高沸点的物理发泡剂(F2)因为冷凝变成液体而失去了对泡孔的支撑作用，导致泡沫在以后的使用中发生收缩和变形。
当在化学发泡剂(F1)中的全部C2-C9醇胺包含低于70mol％的特定C4-C9二醇胺时，意味着所谓全部C2-C9醇胺包含更多的其它C2-C9醇胺类，例如，(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺和(IIb)仅仅具有羟基异丙基的仲胺型C4-C6单醇胺，以及上述所谓的“杂质醇胺类IA”。
由于小分子的伯胺型C2-C9单醇胺具有更高的碱性和更高的反应活性，当含有较多量的小分子伯胺的白料与黑料混合时，发泡混合物的起发时间大幅度缩短(例如1-2秒)，而且反应迅速、泡沫快速膨胀，导致发泡过程失控，不可能以平稳的速度进行发泡反应，对于所生产硬质泡沫的微观结构和闭孔率有不利的影响。因此，在发泡剂组合物(FC)中，伯胺型C2-C9单醇胺的含量越低越好。
另外，由于叔胺型C4-C7单醇胺类和叔胺型C6-C9三醇胺类具有催化作用，同样影响发泡反应的速度。例如，发明人发现，当化学发泡剂(F1)中的C2-C9醇胺包含较大量(例如大于40mol％)的三乙醇胺时会导致泡沫存在“烧芯”现象，即泡沫的芯部呈现深黄色或焦黄色。
根据本发明，提供由上述方法所获得的聚氨酯硬质泡沫，尤其，当聚氨酯硬质泡沫的密度在25-38Kg/cm 3范围时，它的兰芝模(Lance)导热系数λ(mW/m·K，10℃)是低于18.80，优选低于18.70、低于18.60、低于18.50或低于18.40，更优选低于18.30，18.20，18.10，18.04。
本申请的发明人通过大量的实验发现，通过对发泡剂的组成进行优化，能够优化硬质泡沫的微观结构和闭孔率，从而能够理想地降低聚氨酯硬质泡沫的导热系数，甚至能够降低到目前的极限值。当本发明获得的聚氨酯硬质泡沫的密度(芯密度，ASTM D 1622-03)在25-38Kg/cm 3范围，优选26-37Kg/cm 3，优选27-36.5Kg/cm 3，优选28-36Kg/cm 3，优选28.5-35.5Kg/cm 3，优选29-35Kg/cm 3，平均泡孔直径在170-230微米(优选180-220微米，更优选170-210)范围内时，一般，聚氨酯硬质泡沫的导热系数(Mw/m·k,10℃)低于18.40，更优选低于18.30，更优选低于18.20，更优选低于18.05或18.03。
本发明的优点
1、本申请的发明人发现了醇胺碳酸氢盐在浇注型聚氨酯硬质泡沫的制备中的有害作用，因此，尽可能减少化学发泡剂(F1)中醇胺碳酸氢盐的含量，例如在醇胺中通入CO 2气体的中和反应中针对不同碱性的醇胺选择合适的CO 2气体的压力。另外，通过对醇胺的类型和相对用量进行选择，提高了发泡剂组合物的性能(例如组合物与干白料之间的相容性)，使得由黑料和白料混合后的发泡混合物具有理想的流动性以便均匀地填充满整个模具并且使得发泡用混合物具有合适的起发时间和拉丝时间，适合于冰箱、冷柜、热水器和冷藏车领域的单口浇注 方式的聚氨酯硬质泡沫生产。所制备的泡沫具有良好的开模性能。
2、本发明的(浇注型)聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物(FC)与发泡用的干白料之间具有良好的相容性，能够形成均匀透明和具有良好流动性的发泡体系并能够用于获得具有良好的泡孔微观结构和闭孔率的聚氨酯硬质泡沫，尤其，当干白料中的聚合物多元醇类包含10-52wt％(优选15-45wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇和/或甲苯二胺聚氧化丙烯多元醇和90-48wt％(即余量)(优选85-55wt％，更优选82-65wt％)的聚氧化丙烯多元醇(例如，蔗糖引发的聚氧化丙烯多元醇，或季戊四醇引发的聚氧化丙烯多元醇)时。
3、优选，化学发泡剂(F1)是通过在C2-C9醇胺和水的混合物中通入CO 2气体的中和方法来制备的，其中C2-C9醇胺含有主要量(70-100mol％)的所述特定C4-C9二醇胺。根据特定C4-C9二醇胺的碱性来选择合适的CO 2气体的压力，该压力足以使得醇胺与CO 2按照形成碳酸盐的化学计量进行中和反应，另一方面CO 2压力不应太高以至于形成太多的醇胺碳酸氢盐。合适的CO 2的压力应使得，通过向醇胺和水的(饱和或接近饱和)混合物中通入CO 2气体的中和方法所制备的化学发泡剂(F1)含有少量(0.1-20wt％，优选0.1-14wt％)的未中和的C2-C9醇胺(尤其特定C4-C9二醇胺)，因此，通过使用该化学发泡剂(F1)所形成的硬质泡沫具有非常优异的绝热性能。
4、本发明的(浇注型)聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物(FC)与冰箱、冰柜、热水器和冷链保温(冷藏车)行业中的工业化在线发泡反应的工艺非常匹配，对现有的生产流水线不做任何改动，在浇注发泡的流水线上发泡反应的速度是相对平稳的，所获得的泡沫材料的绝热性能和抗变形性能都十分优异。
5、本发明的发泡剂具有明显的成本优势，与第三、四代含氟的发泡剂相比而言。
6、在冰箱、冰柜、热水器和冷藏车(冷链保温)行业中用于制备(浇注型)聚氨酯硬质泡沫的聚合物多元醇通常包含8-52wt％的芳族聚酯多元醇和/或甲苯二胺聚醚多元醇和余量的非甲苯二胺型聚氧化丙烯多元醇，环戊烷和化学发泡剂在此类的体系能够形成透明和具有良好流动性的均相体系，使得发泡均匀，形成细密的泡孔和泡孔尺寸均匀。
附图说明
图1A和1B是实施例1的泡沫的SEM照片。
图2是对比例1的泡沫的SEM照片。
图3是实施例3的泡沫的SEM照片。
图4是对比例2的泡沫的SEM照片。
图5是实施例4的泡沫的SEM照片。
图6是对比例3的泡沫的SEM照片。
图7是实施例5的泡沫的SEM照片。
图8A、8B和8C是实施例6的泡沫的SEM照片。
图9是对比例4的泡沫的SEM照片。
图10是对比例6的泡沫的SEM照片。
图11和图12是实施例8的两种泡沫的SEM照片。
具体实施方式
本发明通过如下实施例对技术方案作进一步详细说明，但本发明不限于这些实施例。
在实施例中所使用的设备都是本领域通常使用的并且可在市场上商购的设备，除非另有规定。对于不同应用领域的聚氨酯硬质泡沫来说，需要相应的合适的发泡速度。一般来说，相关领域的发泡速度如前面的表A中所示。
对于冰箱、冰柜、热水器或冷藏车生产过程的发泡反应，起发时间一般是6-7秒，拉丝时间一般是30-45秒(优选35-40秒)。
本发明针对在冰箱、冰柜、热水器、冷链保温(冷藏车)行业中的应用的聚氨酯硬质泡沫，设计特定的发泡剂组合物。
在本申请中，用于制备聚氨酯泡沫体或用于发泡组合物中的常用聚醚多元醇(聚氧化丙烯多元醇)和(芳族)聚酯多元醇选自下列品种：聚醚多元醇(聚氧化丙烯多元醇)，例如，滨化集团股份有限公司(BEFAR GROUP CO.,LTD.)的聚醚多元醇4110(蔗糖起始剂聚氧化丙烯多元醇)，南京红宝丽股份有限公司的聚醚450(山梨醇起始剂聚氧化丙烯多元醇)，山东蓝星东大化工有限责任公司的MN500(甘油起始剂聚氧化丙烯多元醇)和SA 460(山梨醇起始剂聚氧化丙烯多元醇)，淄博诺立化工有限公司的SA 460(山梨醇起始剂聚氧化丙烯多元醇)、SU380(蔗糖起始剂氧化丙烯多元醇)和SA380(山梨醇起始剂聚氧化丙烯多元醇)，河北亚东化工集团有限公司的YD8260(以蔗糖和二甘醇为起始剂的聚氧化丙烯多元醇)、YD403(乙二胺起始剂聚氧化丙烯多元醇)和YD460(甲苯二胺型聚氧化丙烯多元醇)，和，上海东大化学有限公司的SD7100(甲苯二胺型聚氧化丙烯多元醇)；(芳族)聚酯多元醇类，例如，南京金陵斯泰潘化学有限公司的PS4051、PS4027或PS3152，江苏富盛新材料有限公司的聚酯多元醇CF6320、CF6245、CF6200、CF6300和CF6255，和，北京东方美龙化工科技有限公司的聚酯多元醇DM2003。
常用催化剂选自：33LV(A-33)：33％三乙烯二胺的二丙二醇溶液、N,N-二甲基乙醇胺、N,N-二甲基苄胺、70％双(二甲胺基乙基)醚的二丙二醇溶液、70％辛酸钾于二乙二醇溶液、二 月桂酸二丁基锡、PT303、PT304、醋酸钾、PC-8(N,N-二甲基环己胺)、PC-5(N,N,N,N,N-五甲基二亚乙基三胺)、PC-41(三(二甲氨基丙基)六氢三嗪)、三乙醇胺、JXP-508、JXP-509、TMR-2(2-羟基-N,N,N-三甲基-1-丙胺甲酸盐)、TMR-3、TMR-4。常用的硅油型泡沫稳定剂或硅烷表面活性剂：赢创德固赛(中国)投资有限公司的B8525和B8408，江苏美思德化学股份有限公司的AK-158、AK-8805、AK-8812、AK-8809、AK-8818和AK-8860，气体与化学品公司的DC8545、DC1990、DC5188、DC6070、DC3042和DC3201，以及，上海麦豪化工科技有限公司的硅油8841。非硅烷表面活性剂：气体与化学品公司的LK-221和LK-443。常用阻燃剂：TCPP、TCEP、DMMP、氯化铵、氢氧化铝粉末、DM1201、DM1301、四溴苯酐二醇。
下面介绍CO 2通气的方法制备碳酸醇胺盐化学发泡剂(F1)(CFA)，即下面实施例中的碳酸醇胺盐水合物。
由卡尔费休法所测量的碳酸醇胺盐水合物的水含量＝水合物中的游离水的量+由该碳酸盐和碳酸氢盐分解所生产的水的量。因此，在碳酸醇胺盐化学发泡剂(F1)(即，碳酸醇胺盐水合物)中游离水的含量(wt％)＝(由卡尔费休法所测量的碳酸醇胺盐水合物的水含量)–(由该碳酸盐和碳酸氢盐分解所生产的水的量)。
制备实施例1
将2744g(24mol)的二乙醇胺(Mw 105.14)和二异丙醇胺(Mw 133.2)混合物(二乙醇胺和二异丙醇胺比例为摩尔比3:1，18mol:6mol)和914g水混合后加入到5升透明的石英玻璃高压反应器中，开启搅拌，密封反应器，然后在不断搅拌下，控制温度在40-65℃之间，将二氧化碳通入到反应器中，控制CO 2气体的表压力不高于0.3MPa(即0.28-0.3MPa范围)，控温反应10小时，降温到40℃以下后放掉压力、放出产物即可。获得碳酸醇胺盐水合物1，它被称作“化学发泡剂”(CFA)或称作碳酸醇胺盐化学发泡剂(F1)。由pH计(雷磁PHS-3C型，上海仪电科学仪器股份有限公司，Shanghai Yidian Science Instrument Co.，Ltd.)测得碳酸醇胺盐水合物1的pH＝9.522，水含量＝21.12％(卡尔费休法)，粘度为360厘泊(25℃)，分解温度在42℃-70℃。通过增重法分析，测定醇胺-水混合物吸收了约514g(约11.68mol)的CO 2(分子量44)。有0.544摩尔(2.2666mol％，基于全部醇胺的mol)的醇胺未被中和。11.7mol(210.6g)水参与了中和反应。水合物1中游离水的量为703.76g(16.86％)。
另外，作为参考，重复以上过程，只是改变二乙醇胺与二异丙醇胺的摩尔比，进一步获得碳酸醇胺盐水合物1A、1B和1C：
碳酸醇胺盐水合物No 1A 1 1B 1C
二乙醇胺与二异丙醇胺的摩尔比 5:1 3:1 1:1 1:2
制备实施例2(参考)
将3kg(40mol)的MMEA(甲基一乙醇胺)(分子量75)和1kg水混合后加入到5升透明的石英玻璃高压反应器中，开启搅拌，密封反应器，然后在不断搅拌下，控制温度在40-65℃之间，将二氧化碳通入到反应器中，控制压力不高于0.1MPa(即0.09-0.1MPa范围)，控温反应10小时，降温到40℃以下后放掉压力、放出产物即可。获得碳酸醇胺盐水合物2(CFA)。pH＝9.972，水含量＝20.39％(卡尔费休法)，粘度为286厘泊(25℃)，分解温度在42℃-70℃。通过增重法分析，测定醇胺-水混合物吸收了约913g(约20.75mol)的CO 2。混合物(水合物2)中形成了部分(约1.5mol，按照mol％为3.75mol％，基于全部醇胺的mol，或大约204g)的醇胺碳酸氢盐(分子量136)，后者的含量wt％是大约4.2wt％。20.75摩尔(373.5克)的水参与了中和反应。水合物2中游离水的量626.5g(12.75wt％)。
尽管在向甲基一乙醇胺的水溶液中通入CO 2气体的过程中控制CO 2的压力不高于0.1MPa，但仍然生成了少量的不稳定的醇胺碳酸氢盐，这说明甲基一乙醇胺的碱性较高。
制备实施例3
将3.57kg(30mol)的N-甲基二乙醇胺(分子量119)、1kg的水加入到5升透明的石英玻璃高压反应器中，搅拌溶解，密封反应器，然后在不断搅拌下，控制温度在40-65℃之间，将二氧化碳通入到反应器中，控制压力不高于0.3MPa(如0.275-0.289MPa范围)，控温反应10小时，降温到40℃以下后放掉压力、放出产物即可，获得碳酸醇胺盐水合物3(CFA)。pH＝9.53，水含量＝19.14％(卡尔费休法)，粘度为641厘泊(25℃)，分解温度在42℃-70℃。通过增重法分析，测定醇胺-水混合物吸收了约640g(约14.5mol)的CO 2。29.09mol醇胺参与了中和反应，另外，大约0.91mol(3.03mol％，基于全部醇胺的mol)的醇胺未被中和。大约14.5mol(约261g)的水参与了中和反应。水合物3中游离水的量为大约738g(14.4176％)。
制备实施例4
将3192g(24mol)的二异丙醇胺(分子量133.2)、0.932kg水加入到5升透明的石英玻璃高压反应器中，搅拌溶解，密封反应器，然后在不断搅拌下，控制温度在40-65℃之间，将二氧化碳通入到反应器中，控制压力不高于0.3MPa(如0.29-0.3MPa范围)，控温反应10小时，降温到40℃以下后放掉压力、放出产物即可。获得碳酸醇胺盐水合物4(CFA)。pH＝9.222，水含量＝20.12％，粘度为1510厘泊(25℃)，分解温度在42℃-70℃。通过增重法分析，测定醇胺-水混合物吸收了约510g(约11.5909mol)的CO 2。0.818mol的二异丙醇胺未被CO 2中和。11.5909mol水(208.636克水)参与中和反应。复合物4中游离水721.3638g(15.57wt％)。
与实施例1产品的粘度(360厘泊)相比，实施例4的产品的粘度(1510厘泊)高得多。
制备实施例5(参考)
重复制备实施例2，只是在所获得的醇胺水合物2中进一步添加213g(1.6mol)的二异丙醇胺和120g的水，搅拌混合物以便让其中的醇胺碳酸氢盐转化为醇胺碳酸盐，获得醇胺水合物5，pH＝9.8512。
制备实施例6(参考)
将3kg(40mol)的单异丙醇胺(分子量75)和1kg水混合后加入到5升透明的石英玻璃高压反应器中，开启搅拌，密封反应器，然后在不断搅拌下，控制温度在40-65℃之间，将二氧化碳通入到反应器中，控制压力不高于0.1MPa，控温反应10小时，降温到40℃以下后放掉压力、放出产物即可。获得碳酸醇胺盐水合物6。pH＝9.970，水含量＝20.38％(卡尔费休法)，粘度为290厘泊(25℃)，分解温度在42℃-70℃。通过增重法分析，测定醇胺-水混合物吸收了约912g(约20.73mol)的CO 2。混合物中形成了部分的醇胺碳酸氢盐。
制备实施例7(参考)
将制备实施例6(参考)的水合物6和制备实施例4中的水合物4按照单异丙醇胺:二异丙醇胺的6.5:3.5摩尔比(单醇胺的mol％是65mol％)进行混合，获得水合物7A，粘度为大约1044厘泊(25℃)。
将制备实施例6(参考)的水合物6和制备实施例4中的水合物4按照单异丙醇胺:二异丙醇胺的1:1摩尔比(单醇胺的mol％是50mol％)进行混合，获得水合物7B，粘度为大约1182厘泊(25℃)。
制备实施例8
将制备实施例3的水合物3和制备实施例4中的水合物4按照N-甲基二乙醇胺:二异丙醇胺的3:1摩尔比进行混合，获得水合物8，粘度为大约915厘泊(25℃)。
制备实施例9
将制备实施例6(参考)的水合物6和制备实施例4中的水合物4按照单异丙醇胺:二异丙醇胺的0.36:1摩尔比(单醇胺的mol％是约26mol％)进行混合，获得水合物9，粘度为大约1255厘泊(25℃)。
制备实施例10
将制备实施例6(参考)的水合物6和制备实施例1中的水合物1按照单异丙醇胺:(乙醇胺胺+二异丙醇胺)的0.36:1摩尔比(单醇胺的mol％是约26mol％)进行混合，获得水合物10，粘度为大约532厘泊(25℃)。
应用实施例
实施例1
1、所使用的组分和相对用量：
发泡剂：6重量份的作为发泡剂的由以上实施例1制备的碳酸醇胺盐水合物1(CFA)和18重量份环戊烷。
干白料：它由以下组分所组成：40重量份的聚醚多元醇SD-7100(甲苯二胺型聚氧化丙烯多元醇，由上海东大化学有限公司生产)、20重量份的聚醚多元醇SA-460(山梨醇起始剂聚氧化丙烯多元醇，淄博诺立化工有限公司(Nolly Chemical)生产)、10重量份的芳族聚酯多元醇PS-4051(PET多元醇，由南京金陵斯泰潘化学有限公司生产)、20重量份的聚醚多元醇YD-8260(以蔗糖和二甘醇为起始剂的聚氧化丙烯多元醇，由河北亚东化工贸易有限公司生产)、10重量份的聚醚多元醇YD-403(乙二胺起始剂聚氧化丙烯多元醇，由河北亚东化工贸易有限公司生产)、3重量份的泡沫稳定剂8841(硅油，由上海麦豪化工科技有限公司生产)、0.1重量份的N,N,N,N,N-五甲基二亚乙基三胺(代号PC-5，由美国赢创德固赛有限公司生产)、0.5重量份的胺类催化剂BX-405(由美国赢创德固赛有限公司生产)和1重量份三(二甲氨基丙基)六氢三嗪(代号PC-41，由美国赢创德固赛有限公司生产)。
黑料：156份作为黑料的多异氰酸酯MDI(PM200，烟台万华化学集团股份有限公司)。
对白料的透明度和相容性的观察：将上述发泡剂和干白料在搅拌下进行混合，获得透明的白料，表明发泡剂与干白料(聚合物多元醇)之间具有良好的相容性。
分层现象的观察：在搅拌下混合干白料和全部发泡剂而获得白料，所得白料然后通过离心处理(转速4500rpm，离心时间5分钟)来快速消泡，然后观察物料是否有分层现象(即，底部是否有较薄的一层物料)，结果是：白料在离心消泡处理后没有发现分层现象。
2、发泡反应过程：
使用与上述的配方(或组成)相同的配方，通过高压浇注发泡机(RSC16/16，克劳斯玛菲公司，德国)进行浇注发泡。其中，发泡剂、干白料和黑料经由各自的物料管路输入浇注发泡机中进行搅拌和混合，然后混合后的发泡物料由喷枪浇注到兰芝模中进行发泡。具体操作如下：首先设定浇注机的第一次浇注的发泡物料量为大约200g，然后将该设定量的发泡物料由喷枪浇注到塑料袋中进行自由发泡，测得发泡物料的起发时间为6秒和喷枪口拉丝时间为35秒，然后根据兰芝模的容积设定浇注物料量将相应设定量的发泡物料浇注到兰芝模中进行发泡。180秒之后开模(即打开内、外夹模)。取泡沫的样品，用于分析泡沫的微观结构和绝热性能。从两个批次的泡沫产品中取2个泡沫样品用于SEM分析。两个样品的SEM照片示于图1A和图1B。
从SEM照片可以清楚地看出，单位面积的泡孔数量是较多的，两个泡沫样品的泡孔的平均孔直径较小(约217μm和约210μm)并且泡孔的尺寸大小比较均匀。
测得发泡过程的启发时间为6秒，拉丝时间为35秒。启发时间和拉丝时间与冰箱的工业生产流水线上的时间范围非常符合，因此，该泡沫适合用于冰箱。
对比例1
重复实施例1，只是发泡剂(水+CP)的用量如表1中所示。泡沫的SEM照片示于图2。泡沫的平均泡孔直径为约346微米。
对白料的透明度和相容性的观察：将发泡剂(水+CP)和干白料在搅拌下进行混合，获得混浊的白料(有油滴)，表明发泡剂与干白料(聚合物多元醇)之间具有差的相容性。
混浊现象归因于不含碳酸醇胺盐或醇胺的发泡剂(水+CP)与干白料之间的相容性较差。
实施例2(对比)
1、所使用的组分和相对用量：
发泡剂：7重量份的作为发泡剂的由以上实施例2制备的碳酸醇胺盐水合物2(CFA)和18重量份环戊烷(CP)。
干白料：它由以下组分所组成：40重量份的甲苯二胺聚醚多元醇SD-7100、20重量份聚醚多元醇的SA-460、10重量份的芳族聚酯多元醇PS-4051、20重量份的聚醚多元醇YD-8260、10重量份的聚醚多元醇YD-403、3重量份的硅油类泡沫稳定剂8841(由上海麦豪化工科技有限公司生产)、0.1重量份的N,N,N,N,N-五甲基二亚乙基三胺(代号PC-5，由美国赢创德固赛有限公司生产)、0.5重量份的胺类催化剂BX-405(由美国赢创德固赛有限公司生产)和1重量份三(二甲氨基丙基)六氢三嗪(代号PC-41，由美国赢创德固赛有限公司生产)。
黑料：156份作为黑料的多异氰酸酯MDI(PM200，烟台万华化学集团股份有限公司)。
对白料的透明度和相容性的观察：将上述发泡剂和干白料在搅拌下进行混合，获得稍混浊的白料，表明发泡剂与干白料(聚合物多元醇)之间具有稍低的相容性。
2、发泡反应过程：
使用与上述的配方(或组成)相同的配方，通过高压浇注发泡机(RSC16/16，克劳斯玛菲公司，德国)进行浇注发泡。测得发泡物料的起发时间为3秒和喷枪口拉丝时间为27秒，然后根据兰芝模的容积设定浇注物料量将相应设定量的发泡物料浇注到兰芝模中进行发泡。180秒之后开模(即打开内、外夹模)。发现泡沫集中在浇注口的附近区域，模具内腔的远区域没有泡沫，也就是说泡沫没有填充满整个模具内腔。泡沫在模具的密度分布不均匀。
上述结果表明浇注发泡失败。原因是N-甲基单乙醇胺碳酸盐具有较强的碱性和反应活 性，并且少量存在的伯胺的碳酸氢盐对于浇注发泡有严重的影响，因此，其中醇胺仅仅含有N-甲基单乙醇胺的水合物2导致发泡过程的前期反应太剧烈。
实施例3
1、所使用的组分和相对用量：
发泡剂：3重量份的作为发泡剂的由以上实施例3制备的碳酸醇胺盐水合物3(CFA)、1.8重量份的水、3重量份的HFC-245fa和17重量份环戊烷。
干白料：它由以下组分所组成：40重量份的聚醚多元醇SD-7100、20重量份的聚醚多元醇SA-460、10重量份的聚酯多元醇PS-4051、20重量份的聚醚多元醇YD-8260、10重量份的聚醚多元醇YD-403、3重量份的泡沫稳定剂8841(由上海麦豪化工科技有限公司生产)、0.1重量份的N,N,N,N,N-五甲基二亚乙基三胺(代号PC-5，由美国赢创德固赛有限公司生产)、0.5重量份的胺类催化剂BX-405(由美国赢创德固赛有限公司生产)和1重量份三(二甲氨基丙基)六氢三嗪(代号PC-41，由美国赢创德固赛有限公司生产)。
黑料：157份作为黑料的多异氰酸酯MDI(PM200，烟台万华化学集团股份有限公司)。
对白料的透明度和相容性的观察：将上述发泡剂和干白料在搅拌下进行混合，获得透明的白料，表明发泡剂与干白料(聚合物多元醇)之间具有良好的相容性。
分层现象的观察：白料在离心消泡处理后，没有发现分层现象。
2、发泡反应过程：
重复与实施例1中相同的发泡反应过程。测得发泡物料的起发时间为6秒和喷枪口拉丝时间为35秒。硬质泡沫的SEM照片示于图3。
从SEM照片可以清楚地看出，泡孔的平均孔直径较小(约228um，比实施例1的平均泡孔直径稍大)并且泡孔的尺寸大小比较均匀。
将实施例1的结果与实施例3的结果对比，能够发现：二异丙醇胺类与二乙醇胺的相结合使用能够改善发泡剂组合物与干白料之间的相容性。
对比例2
重复实施例3，只是发泡剂(245fa+CP)的用量如表1中所示。泡沫的SEM照片示于图4。泡沫的泡孔粗大且其尺寸不均匀。
对白料的透明度和相容性的观察：将发泡剂(245fa+CP)和干白料在搅拌下进行混合，获得混浊的白料(有油滴)，表明发泡剂与干白料(聚合物多元醇)之间具有差的相容性。
混浊现象归因于不含碳酸醇胺盐的发泡剂(245fa+CP)与干白料之间的相容性较差。
实施例4
1、所使用的组分和相对用量：
发泡剂：3重量份的作为发泡剂的由以上实施例4制备的碳酸醇胺盐水合物4、1.8重量份的水、3重量份的LBA和17重量份CP(环戊烷)。
干白料：它由以下组分所组成：40重量份的聚醚多元醇SD-7100、20重量份的聚醚多元醇SA-460、10重量份的聚酯多元醇PS-4051、20重量份的聚醚多元醇YD-8260、10重量份的聚醚多元醇YD-403、3重量份的泡沫稳定剂8841(由上海麦豪化工科技有限公司生产)、0.1重量份的N,N,N,N,N-五甲基二亚乙基三胺(代号PC-5，由美国赢创德固赛有限公司生产)、0.5重量份的胺类催化剂BX-405(由美国赢创德固赛有限公司生产)和1重量份三(二甲氨基丙基)六氢三嗪(代号PC-41，由美国赢创德固赛有限公司生产)。
黑料：157份作为黑料的多异氰酸酯MDI(PM200，烟台万华化学集团股份有限公司)。
对白料的透明度和相容性的观察：将上述发泡剂和干白料在搅拌下进行混合，获得透明、均相的白料，表明发泡剂与干白料(聚合物多元醇)之间具有非常好的相容性。
分层现象的观察：白料在离心消泡处理后，没有发现分层现象。
2、发泡反应过程：
重复与实施例1中相同的发泡反应过程。测得发泡物料的起发时间为6秒和喷枪口拉丝时间为35秒。硬质泡沫的SEM照片示于图5。
从SEM照片可以清楚地看出，泡孔的平均孔直径较小(约239um比实施例1的平均泡孔直径稍大)并且泡孔的尺寸大小比较均匀。
本实施例4的结果表明，化学发泡剂(F1)的粘度有可能影响泡沫的微观结构和性能。
对比例3
重复实施例4，只是发泡剂为(LBA+CP)，其中发泡剂(LBA+CP)的用量如表1中所示。泡沫的SEM照片示于图6。泡沫的泡孔粗大且其尺寸不均匀。
对白料的透明度和相容性的观察：将发泡剂(LBA+CP)和干白料在搅拌下进行混合，获得混浊的白料(油滴)，表明发泡剂与干白料(聚合物多元醇)之间具有差的相容性。
实施例5
重复实施例3，只是用3重量份的实施例1中的碳酸醇胺水合物1替代3重量份的碳酸醇胺盐水合物3。所得硬质泡沫的SEM照片示于图7。
从SEM照片可以清楚地看出，泡孔的平均孔直径较小(约220um，比实施例1的平均泡孔直径稍大)并且泡孔的尺寸大小比较均匀。
表1-发泡组成和泡沫的性能参数对比：
Figure PCTCN2021082825-appb-000002
Figure PCTCN2021082825-appb-000003
注1：表中CFA是指高含水碳酸有机醇胺盐发泡剂；λ值(或K factor)测定按照GB/T 10295-2008，泡沫尺寸20*20*2.5cm。表中的“膨胀率(180s)”是指从开始向兰芝模中注料时开始计时至180秒(3分钟)为止，打开兰芝模后所测量的膨胀率。
注2：Lance模具大小为1600*300*80mm。整体泡沫以长边为方向，平均分为左右两个部分(即，左右两侧)，每个部分从下至上的方向，每隔20cm取一个密度点(密度测量点)，左右两侧共取16个密度点，取密度最高值与最低值之差为密度极差。这16个密度点密度的平均数为平均密度。
上表1可以看出，高含水量、低醇胺碳酸氢盐含量的碳酸有机醇胺盐水合物作为化学发泡剂与环戊烷相结合使用，或该水合物与氢氟烃类物理发泡剂和环戊烷相结合使用，制备的聚氨酯泡沫材料整体性能优良，导热系数低，保温性能好。尤其，实施例1和实施例5中使用包含(二乙醇胺类+二异丙醇胺类)的发泡组合物所获得的聚氨酯硬质泡沫具有非常优异的绝热性能。
实施例6
重复实施例1，只是用同样用量的实施例1中制备的碳酸醇胺盐水合物1A、1B和1C分别代替实施例1制备的碳酸醇胺盐水合物1。获得聚氨酯硬质泡沫6A-6C。与实施例1的泡沫进行对比。
表2-聚氨酯硬质泡沫的平均泡孔直径和导热系数(兰芝模λ，Mw/m·k(10℃))
Figure PCTCN2021082825-appb-000004
Figure PCTCN2021082825-appb-000005
从表2中的数据对比看出，实施例1的泡沫(其中二乙醇胺与二异丙醇胺的摩尔比为3:1)的导热系数最低。
泡沫6A-6C的SEM照片示于图8A、图8B和图8C。可以看出，二乙醇胺与二异丙醇胺的摩尔比影响泡沫的平均泡孔直径，以及在同等的泡沫密度下平均泡孔直径的大小对于绝热性能有一定的影响。
对比例4
重复实施例1，只是环戊烷的量(18份)改为24重量份的环戊烷。
对白料的透明度和相容性的观察：将发泡剂组合物和干白料在搅拌下进行混合，获得混浊的白料并且在白料中发现有清晰的油滴，表明环戊烷从白料中离析，发生了相分离。这说明环戊烷在白料中的溶解度是有限的。
发泡反应过程：测得发泡物料的起发时间为7秒和喷枪口拉丝时间为43秒。
泡沫的SEM照片示于图9。从SEM照片可以清楚地看出，泡孔的平均孔直径较大(约330微米)并且泡孔的尺寸大小是不均匀的。另外，在SEM照片中可以看见多个超大尺寸的泡孔。这些超大泡孔可能是在发泡过程中由油滴(环戊烷)作为起泡中心所形成的。
对比例5
重复实施例1，进行实验1a、2a、3a和4a，只是分别采用同样用量的制备实施例5(参考)、制备实施例6(参考)和制备实施例7(参考)的水合物5、水合物6、水合物7A和水合物7B代替实施例1中的水合物1，进行浇注发泡，获得聚氨酯硬质泡沫5、6、7A和7B。主要在于考察发泡过程的起发时间和拉丝时间。
表3-发泡过程的起发时间和拉丝时间
实验No 1a 2a 3a 4a
醇胺水合物No 5 6 7A 7B
起发时间(s) 4 3 4.5 5
枪口拉丝时间(秒)(料温22℃，环境温度30℃) 31 28 30 33
在实验1a中，与实施例2(对比)中的起发时间(3秒)和拉丝时间(27秒)相比，使用降低了醇胺碳酸氢盐含量的水合物6(制备实施例6)的实验1a的起发时间和拉丝时间分别延长，但仍然无法满足冰箱浇注发泡的要求。
实验2a与实施例2(对比)一样，浇注发泡失败，说明使用仅仅包含伯胺(异丙醇胺)的水 合物6，导致发泡剂组合物的碱性和反应活性太高。伯胺碳酸氢盐对于浇注发泡有严重影响。
实验3a和实验4a的结果表明，当伯胺(异丙醇胺)的mol％高于30mol％时，起发时间和拉丝时间无法满足冰箱浇注发泡的要求。
实施例7
重复实施例1，只是分别采用同样用量的制备实施例8、制备实施例9和制备实施例10中的水合物8、水合物9和水合物10代替实施例1中的水合物1。浇注发泡，获得聚氨酯硬质泡沫8、9和10。主要在于考察发泡过程的起发时间和拉丝时间。
表3-发泡过程的起发时间和拉丝时间
Figure PCTCN2021082825-appb-000006
实验1b的结果表明，N-甲基二乙醇胺替代二乙醇胺，几乎获得相同的结果。
实验2b和实验3b的结果表明，当伯胺(异丙醇胺)的mol％低于30mol％时，浇注发泡过程的起发时间和拉丝时间能够满足冰箱浇注发泡的要求。
对比例6
重复实施例1，只是白料中仅仅包含非甲苯二胺型聚醚多元醇，但不包含聚酯多元醇和甲苯二胺型聚醚多元醇。即，干白料的组成如下所述；
干白料：它由以下组分所组成：40重量份的聚醚多元醇SA-460(山梨醇起始剂)、30重量份的聚醚多元醇YD-8260(以蔗糖和二甘醇为起始剂)、30重量份的聚醚多元醇YD-403(乙二胺起始剂)、3重量份的泡沫稳定剂8841(由上海麦豪化工科技有限公司生产)、0.1重量份的N,N,N,N,N-五甲基二亚乙基三胺(代号PC-5，由美国赢创德固赛有限公司生产)、0.5重量份的胺类催化剂BX-405(由美国赢创德固赛有限公司生产)和1重量份三(二甲氨基丙基)六氢三嗪(代号PC-41，由美国赢创德固赛有限公司生产)。
所形成的泡沫的SEM照片示于图10。有粗大的泡孔，导致泡沫的导热系数是较高的。泡沫的λ(Mw/m·k，10℃)为18.95。尽管非甲苯二胺型的聚氧化丙烯多元醇具有良好的流动性，但是，本发明的含环戊烷的发泡剂组合物与不含聚酯多元醇或甲苯二胺型聚氧化丙烯多元醇的干白料(非甲苯二胺型聚氧化丙烯多元醇)之间的相容性不太好。
实施例8
重复实施例3，进行实验1a和2d，只是，在实验1d中使用1重量份的实施例1中的碳酸醇胺水合物1作为CFA(化学发泡剂)和5重量份的245fa，另外，在实验2d中使用2重量份的实施例1中的碳酸醇胺水合物1作为CFA(化学发泡剂)和4重量份的245fa。
实验1d的泡沫的λ(Mw/m·k，10℃)为18.59。实验2d的泡沫的λ(Mw/m·k，10℃)为18.52。实验1d和实验2d所获得的硬质泡沫的SEM照片分别示于图11和图12。
从SEM照片可以看出，尽管使用了较低量(1或2重量份)的水合物1，但是，它们能够在发泡过程的前期阶段中发挥成核作用，因而有利于提高泡孔的均匀度和降低泡孔的平均尺寸(与对比例2的图4和对比例3的图6相比)，泡沫的导热系数能够降低至低于18.60。
实施例9-用于热水器的泡沫材料
重复实施例1，只是CP为12重量份和CFA为4重量份。所得泡沫材料的产品密度(即，打开浇注模具后所测量的泡沫产品的密度)是40.5Kg/cm 3和导热系数K factor(mW/m·K，22.5℃)为19.49。

Claims (11)

  1. 用于制备聚氨酯硬质泡沫的碳酸醇胺盐发泡剂组合物(FC)，它包括以下组分：
    (1)高水含量的碳酸醇胺盐化学发泡剂(F1)；和
    (2)环戊烷；
    (3)任选的，沸点在15-41℃范围内的氢氟烃类物理发泡剂(F2)，其中物理发泡剂(F2)是选自于HFC-245fa、HFC-365mfc、LBA和六氟丁烯中的一种或多种(两种或三种)；
    (4)任选的，水(F3)；
    其中，各种组分的相对用量是：水(F3)的量是0-2重量份，0-1.5重量份，更优选0-1重量份，进一步优选0-0.5重量份，更优选0-0.1重量份；物理发泡剂(F2)的量是0-7重量份，优选0-6.5重量份，优选0-6重量份，优选0-5.5重量份，优选0-5重量份，更优选0-4.5重量份，优选0-4重量份，更优选0-3.5重量份，更优选0-3重量份，更优选0-2.5重量份，最优选0重量份；化学发泡剂(F1)的量是1-10重量份，优选1.2-9.5重量份，优选1.3-9重量份，优选1.4-8.5重量份，优选1.5-8重量份，优选2.8-8重量份，优选3-8重量份，优选3.5-7.5重量份，优选4-7重量份，优选4.5-6.5重量份，优选5-6.5重量份，更优选5-6重量份；和，环戊烷的量是10-20重量份，优选10.5-19.5重量份，优选10.5-19重量份，优选11-18.5重量份，优选11.5-18重量份；
    以及，水(F3)+物理发泡剂(F2)+化学发泡剂(F1)的质量之和与环戊烷的质量之比或相对用量是(4-10):(10-20)，优选(4-9.5):(10-20)，(4-9):(10-20)，(4-9):(10-18)，(4-9):(10-16)，优选(4.5-10):(10-20)，(5-9.5):(10-20)，(5-9.5):(10-18)，(5-9.5):(10-16)，(5-9):(10-20)，(5-9):(10-18)，(5-9):(10-16)，更优选(5.5-9):(10-20)，(5.5-8.5):(10-20)，优选(5.5-8):(10-20)，优选(5.5-8):(10.5-19.5)，(5.5-8):(11-19)，(5.5-8):(11.5-18.8)，(5.5-8):(12-18.5)，(5.5-8):(13-18)，优选(5.6-8):(10.5-19.5)，优选(5.7-8):(11-19)，优选(5.8-7.8):(11.5-18.8)，优选(5.9-7.6):(12-18.5)，优选(6-7):(13-18)；
    和
    其中，化学发泡剂(F1)包括以下成分：
    (A)67-90wt％的碳酸二(C2-C9醇胺)盐；该含量优选是68-89.5wt％，更优选69-89wt％，70-88.5wt％，71-88wt％，72-87.5wt％，73-87wt％；
    (B)10-33wt％的水；该水含量优选是10.5-32wt％，优选11-31wt％，11.5-30wt％，12-29wt％，12.5-28wt％，13-27wt％；
    (C)0-20wt％的C2-C9醇胺；该含量优选是0.01-19wt％，优选0.02-18wt％，更优选 0.03-17wt％，更优选0.04-16wt％，优选0.06-15wt％；例如0.08、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、10.5、11、12、13或14wt％；
    和
    (D)0-10wt％的C2-C9醇胺碳酸氢盐；该含量优选是0-9wt％，优选0-8wt％，0-7wt％，0-6wt％，0-5wt％，0-4wt％，0-3wt％，0-2wt％，0-1wt％，0-0.5wt％，最优选0wt％；
    上述百分比是基于化学发泡剂(F1)的总重量；
    其中，组分(A)、(B)、(C)和(D)的重量之和是基于化学发泡剂(F1)的总重量的90-100wt％，优选92-100wt％，优选93-100wt％，优选95-100wt％，优选98-100wt％，优选98.5-100wt％，优选99-100wt％，优选99.5-100wt％，优选99.8-100wt％，更优选100wt％；
    其中，在化学发泡剂(F1)中的全部C2-C9醇胺包含或主要包含70-100mol％，优选72-100mol％，优选75-100mol％，优选77-100mol％，优选80-100mol％，优选82-100mol％，优选85-100mol％，优选87-100mol％，优选90-100mol％，优选92-100mol％，优选95-100mol％，优选97-100mol％，优选98-100mol％)的特定C4-C9二醇胺，所述特定C4-C9二醇胺是(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)、(II)具有羟基异丙基的C5-C9二醇胺类(IIa)或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物，该mol％是基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量，并且，(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)是选自于二乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和N-丙基二乙醇胺中的一种或多种，和，(II)具有羟基异丙基的C5-C9二醇胺类(IIa)是选自于二异丙醇胺、乙醇异丙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-丙基二异丙醇胺、N-甲基乙醇异丙醇胺、N-乙基乙醇异丙醇胺和N-丙基乙醇异丙醇胺中的一种或多种；
    和
    其中，化学发泡剂(F1)的pH是8.6-10.4，优选8.8-10.2，优选9-10.1，更优选9.2-10，优选9.3-9.7，更优选9.4-9.6。
  2. 根据权利要求1所述的发泡剂组合物(FC)，其特征在于：所述重量份是相对于或基于80-115重量份(优选85-110重量份，优选90-100重量份)的包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料，其中所述其它助剂包括聚氨酯催化剂，发泡稳定剂和任选的阻燃剂；其中发泡剂组合物(FC)用于与干白料和作为黑料的多异氰酸酯混合来进行发泡反应，从而制备聚氨酯硬质泡沫；
    和/或
    在化学发泡剂(F1)中的全部C2-C9醇胺包含或主要包含90-100mol％(优选92-100mol％，优选95-100mol％，优选97-100mol％，优选98-100mol％)的特定C4-C9二醇胺，所述特定C4-C9二醇胺是(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)、(II)具有羟基异丙基的C5-C9二醇胺类(IIa)或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物；
    和/或
    当发泡剂组合物(FC)不包含物理发泡剂(F2)时，化学发泡剂(F1)和环戊烷分别装在单独的容器中，或，当发泡剂组合物(FC)进一步包含物理发泡剂(F2)时，化学发泡剂(F1)装在单独的容器中，而物理发泡剂(F2)和环戊烷分别被装在不同的容器中或被装在同一容器中；
    和/或
    发泡剂组合物(FC)用于浇注型聚氨酯硬质泡沫的制备，更优选用于在冰箱、冰柜、热水器或冷藏车生产过程中的浇注型聚氨酯硬质泡沫的制备；
    和/或
    所述特定C4-C9二醇胺是(I)醇胺类(Ia)，或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物，其中组分(I)醇胺类(Ia)与组分(II)醇胺类(IIa)的摩尔比是1:(0-2.5)，优选1:(0.1-2.5)，优选1:(0.1-2)，更优选1:(0.2-1.5)，更优选1:(0.22-1.2)，更优选1:(0.24-0.9)，更优选1:(0.25-0.5)，更优选1:(0.27-0.4)，更优选1:(0.29-0.45)，最优选3:1；
    和/或
    在化学发泡剂(F1)中的全部C2-C9醇胺还包含0-30mol％，优选0-28mol％，优选0-25mol％，优选0-23mol％，优选0-20mol％，优选0-18mol％，优选0-15mol％，优选0-13mol％，优选0-10mol％，优选0-8mol％，优选0-5mol％，优选0-3mol％，优选0-2mol％的除了上述特定C4-C9二醇胺之外的其它C2-C9醇胺类，这些其它C2-C9醇胺类是选自于(Ib)仅仅具有羟乙基的仲胺型C3-C5单醇胺类和(IIb)仅仅具有羟基异丙基的仲胺型C4-C6单醇胺类中的一种或多种；其中，仅仅具有羟乙基的仲胺型C3-C5单醇胺类(Ib)是选自于N-甲基单乙醇胺、N-乙基单乙醇胺和N-丙基单乙醇胺中的一种或多种；和,仅仅具有羟基异丙基的仲胺型C4-C6单醇胺类(IIb)是选自于N-甲基单异丙醇胺、N-乙基单异丙醇胺和N-丙基单异丙醇胺中的一种或多种；该mol％是基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量(或基于在组分(A)、(C)和(D)中存在的C2-C9醇胺类的总摩尔量)。
  3. 根据权利要求1或2所述的发泡剂组合物(FC)，其特征在于：
    其中，相对于或基于80-115重量份(优选85-110重量份，更优选90-100重量份)的干 白料，发泡剂组合物(FC)的用量足以使得所制备的聚氨酯硬质泡沫的密度是在25-38Kg/cm 3范围，优选26-37Kg/cm 3，优选27-36.5Kg/cm 3，优选28-36Kg/cm 3，优选28.5-35.5Kg/cm 3，优选29-35Kg/cm 3，例如30、31、32、33或34Kg/cm 3；
    和/或；
    组分(1)高水含量的碳酸醇胺盐化学发泡剂(F1)和组分(4)任选的水(F3)两者的水量之和是1.2-3.5wt％(优选1.25-3wt％)，相对于或基于100重量份的干白料；
    和/或；
    化学发泡剂(F1)由组分A)、B)、任选的C)和任选的D)组成；优选，化学发泡剂(F1)由组分A)、B)和任选的C)组成或由组分A)、B)和任选的D)组成；更优选，化学发泡剂(F1)由组分A)和B)组成；
    和/或
    所述特定C4-C9二醇胺是(III)由组分(I)醇胺类(Ia)和(II)醇胺类(IIa)组成的结合物或混合物，并且醇胺类(Ia)与醇胺类(IIa)的摩尔比是1:(0.2-1.5)，更优选1:(0.22-1.2)，更优选1:(0.24-0.9)，更优选1:(0.25-0.5)，更优选1:(0.27-0.4)，更优选1:(0.29-0.45)，最优选3:1。
  4. 根据权利要求1-3中任何一项所述的发泡剂组合物(FC)，其中化学发泡剂(F1)是通过在C2-C9醇胺和水的混合物中通入CO 2气体的中和方法来制备的；优选，该中和方法包括：在C2-C9醇胺和水的混合物中通入表压力为0.09-0.4MPa(优选0.09-0.35MPa或0.1-0.3MPa)的CO 2气体至饱和为止，任选地，在所得中和产物中进一步添加上述C2-C9醇胺(优选，以上所述的特定C4-C9二醇胺，例如二乙醇胺和/或二异丙醇胺)，以使得产物的pH值在8.8-10.2范围(优选9-10.1，更优选9.2-10，优选9.2-9.7，更优选9.4-9.6)，获得化学发泡剂(F1)；优选，其中在C2-C9醇胺和水的混合物中水的量应使得所制备的化学发泡剂(F1)中的游离水含量为10-33wt％的水，优选10.5-32wt％，优选11-31wt％，11.5-30wt％，12-29wt％，12.5-28wt％，13-27wt％；优选，向C2-C9醇胺和水的混合物中通入的CO 2气体的压力应该进行选择，该压力足以使得C2-C9醇胺尽可能按照形成碳酸二(C2-C9醇胺)盐的化学计量被CO 2中和但形成不超过10wt％(例如0-10wt％，优选0-9wt％，优选0-5wt％，0-4wt％，0-3wt％)的C2-C9醇胺碳酸氢盐，该wt％基于所形成的碳酸醇胺盐水合物(F1)的重量；
    优选，为了制备包含两种或两种以上的不同碱性的醇胺并且所形成醇胺碳酸氢盐的含量较低的一种化学发泡剂(F1)，能够通过分别在不同的CO 2气体的压力下向每一种醇胺中通入CO 2气体来制备每一种醇胺的几乎不含醇胺碳酸氢盐的碳酸醇胺盐，然后将几乎不含醇胺碳酸氢盐的两种或多种的中和产物碳酸醇胺盐按照相应的比例进行混合，以获得含有多种醇胺 碳酸盐和含有较少量的醇胺碳酸氢盐的一种化学发泡剂(F1)。
  5. 根据权利要求1-4中任何一项所述的发泡剂组合物(FC)，其中：
    仅仅具有羟乙基的C4-C7二醇胺类(Ia)是选自于二乙醇胺和N-甲基二乙醇胺中的一种或多种，和，具有羟基异丙基的C5-C9二醇胺类(IIa)是选自于二异丙醇胺、乙醇异丙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-甲基乙醇异丙醇胺和N-乙基乙醇异丙醇胺中的一种或多种；更优选，仅仅具有羟乙基的C4-C7二醇胺类(Ia)是选自于二乙醇胺和N-甲基二乙醇胺中的一种或多种，和，具有羟基异丙基的C5-C9二醇胺类(IIa)是选自于二异丙醇胺、乙醇异丙醇胺、N-甲基二异丙醇胺和N-甲基乙醇异丙醇胺中的一种或多种；更优选，仅仅具有羟乙基的C4-C7二醇胺类(Ia)是二乙醇胺，和，具有羟基异丙基的C5-C9二醇胺类(IIa)是二异丙醇胺；
    和/或
    发泡剂组合物(FC)仅仅包括组分(1)化学发泡剂(F1)和组分(2)环戊烷，即，组分(2)物理发泡剂(F2)和组分(3)水(F3)的用量均为0重量份，并且，化学发泡剂(F1)与环戊烷的质量之比或相对用量是(4-10):(10-20)，优选(4-9.5):(10-20)，(4-9):(10-20)，(4-9):(10-18)，(4-9):(10-16)，优选(4.5-10):(10-20)，(5-9.5):(10-20)，(5-9.5):(10-18)，(5-9.5):(10-16)，(5-9):(10-20)，(5-9):(10-18)，(5-9):(10-16)，更优选(5.5-9):(10-20)，(5.5-8.5):(10-20)，优选(5.5-8):(10-20)，优选(5.5-8):(10.5-19.5)，(5.5-8):(11-19)，(5.5-8):(11.5-18.8)，(5.5-8):(12-18.5)，(5.5-8):(13-18)，优选(5.6-8):(10.5-19.5)，优选(5.7-8):(11-19)，优选(5.8-7.8):(11.5-18.8)，优选(5.9-7.6):(12-18.5)，优选(6-7):(13-18)，更优选(6-7):(14-18)，更优选(6-7):(15-18)，更优选(6-7):(16-18)。
  6. 根据权利要求1-5中任何一项所述的发泡剂组合物(FC)，其中：发泡剂组合物(FC)用于与干白料混合来制备用于聚氨酯硬质泡沫的白料，优选，所述白料用于在冰箱、冰柜、热水器或冷藏车生产过程中的浇注型聚氨酯硬质泡沫的制备；
    优选，所述干白料中的聚合物多元醇类包含8-52wt％(优选9-50wt％，优选10-48wt％，优选12-47wt％，优选15-45wt％，优选16-40wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇、聚间苯二甲酸乙二醇酯多元醇或聚对苯二甲酸二乙醇酯多元醇)和/或甲苯二胺聚氧化丙烯多元醇和92-48wt％(优选91-50wt％，优选90-52wt％，优选88-53wt％，优选85-55wt％，优选84-60wt％，更优选82-65wt％)的(非甲苯二胺型或非甲苯二胺引发的)聚氧化丙烯多元醇。
  7. 根据权利要求1-6中任何一项所述的发泡剂组合物(FC)，其中：所述特定C4-C9二醇 胺是由二乙醇胺和二异丙醇胺按照1:(0.1-2)，优选1:(0.2-1.5)，更优选1:(0.22-1.2)，更优选1:(0.24-0.9)，更优选1:(0.25-0.5)，更优选1:(0.27-0.4)，更优选1:(0.29-0.45)的摩尔比所组成的混合物。
  8. 一种含水的碳酸醇胺盐化学发泡剂(F1)，它包括以下成分：
    (A)67-90wt％的碳酸二(C2-C9醇胺)盐；该含量优选是68-89.5wt％，更优选69-89wt％，70-88.5wt％，71-88wt％，72-87.5wt％，73-87wt％；
    (B)10-33wt％的水；该水含量优选是10.5-32wt％，优选11-31wt％，11.5-30wt％，12-29wt％，12.5-28wt％，13-27wt％；
    (C)0-20wt％的C2-C9醇胺；该含量优选是0.01-19wt％，优选0.02-18wt％，更优选0.03-17wt％，更优选0.04-16wt％，优选0.06-15wt％；例如0.08、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、10.5、11、12、13或14wt％；
    和
    (D)0-10wt％的C2-C9醇胺碳酸氢盐；该含量优选是0-9wt％，优选0-8wt％，0-7wt％，0-6wt％，0-5wt％，0-4wt％，0-3wt％，0-2wt％，0-1wt％，0-0.5wt％，最优选0wt％；
    上述百分比是基于化学发泡剂(F1)的总重量；
    其中，组分(A)、(B)、(C)和(D)的重量之和是基于化学发泡剂(F1)的总重量的90-100wt％，优选92-100wt％，优选93-100wt％，优选95-100wt％，优选98-100wt％，优选98.5-100wt％，优选99-100wt％，优选99.5-100wt％，优选99.8-100wt％，更优选100wt％；
    其中，在化学发泡剂(F1)中的全部C2-C9醇胺包含或主要包含70-100mol％，优选72-100mol％，优选75-100mol％，优选77-100mol％，优选80-100mol％，优选82-100mol％，优选85-100mol％，优选87-100mol％，优选90-100mol％，优选92-100mol％，优选95-100mol％，优选97-100mol％，优选98-100mol％)的特定C4-C9二醇胺，所述特定C4-C9二醇胺是(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)、(II)具有羟基异丙基的C5-C9二醇胺类(IIa)或(III)由组分(I)醇胺类(Ia)和组分(II)醇胺类(IIa)组成的结合物或混合物，该mol％是基于在化学发泡剂(F1)中存在的C2-C9醇胺类的总摩尔量，并且，(I)仅仅具有羟乙基的C4-C7二醇胺类(Ia)是选自于二乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和N-丙基二乙醇胺中的一种或多种，和，(II)具有羟基异丙基的C5-C9二醇胺类(IIa)是选自于二异丙醇胺、乙醇异丙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-丙基二异丙醇胺、N-甲基乙醇异丙醇胺、N-乙基乙醇异丙醇胺和N-丙基乙醇异丙醇胺中的一种或多种；
    和
    其中，化学发泡剂(F1)的pH是8.6-10.4，优选8.8-10.2，优选9-10.1，更优选9.2-10，优选9.3-9.7，更优选9.4-9.6。
  9. 聚氨酯发泡用白料，它包括：(1)包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料，其中所述其它助剂包括聚氨酯催化剂、泡沫稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂；和
    (2)根据权利要求1-7中任何一项所述的碳酸醇胺盐发泡剂组合物(FC)；
    优选，所述干白料中的聚合物多元醇类包含8-52wt％(优选9-50wt％，优选10-48wt％，优选12-47wt％，优选15-45wt％，优选16-40wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇、聚间苯二甲酸乙二醇酯多元醇或聚对苯二甲酸二乙醇酯多元醇)和/或甲苯二胺聚氧化丙烯多元醇和92-48wt％(优选91-50wt％，优选90-52wt％，优选88-53wt％，优选85-55wt％，优选84-60wt％，更优选82-65wt％)的(非甲苯二胺型或非甲苯二胺引发的)聚氧化丙烯多元醇。
  10. 聚氨酯发泡用组合物，它包括：
    (1)作为黑料的多异氰酸酯(优选，多亚甲基多苯基多异氰酸酯或聚合MDI)；
    (2)包含聚合物多元醇类和除发泡剂之外的其它助剂的聚氨酯发泡用干白料，其中所述其它助剂包括聚氨酯催化剂、泡沫稳定剂以及任选的阻燃剂、任选的扩链剂和任选的交联剂；和
    (3)根据权利要求1-7中任何一项所述的碳酸醇胺盐发泡剂组合物(FC)；
    优选，黑料(1)与干白料(2)和发泡剂组合物(3)的质量之和的比例(即，物料比)是1.1-1.36:1，优选1.13-1.35:1，优选1.15-1.30:1，更优选1.17-1.27:1，更优选1.18-1.25:1，最优选1.2:1；
    优选，所述干白料中的聚合物多元醇类包含8-52wt％(优选9-50wt％，优选10-48wt％，优选12-47wt％，优选15-45wt％，优选16-40wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇、聚间苯二甲酸乙二醇酯多元醇或聚对苯二甲酸二乙醇酯多元醇)和/或甲苯二胺聚氧化丙烯多元醇和92-48wt％(优选91-50wt％，优选90-52wt％，优选88-53wt％，优选85-55wt％，优选84-60wt％，更优选82-65wt％)的(非甲苯二胺型或非甲苯二胺引发的)聚氧化丙烯多元醇。
  11. 制备聚氨酯硬质泡沫的方法，该方法包括：将包含根据权利要求1-7中任何一项所述的发泡剂组合物(FC)的聚合物多元醇组合物白料与作为黑料的多异氰酸酯(优选，多亚甲基 多苯基多异氰酸酯或聚合MDI)进行混合和发泡；优选地，使用浇注机来进行浇注发泡；
    优选，所述干白料中的聚合物多元醇类包含8-52wt％(优选9-50wt％，优选10-48wt％，优选12-47wt％，优选15-45wt％，优选16-40wt％，更优选18-35wt％)的芳族/半芳族聚酯多元醇(例如聚邻苯二甲酸乙二醇酯多元醇、聚间苯二甲酸乙二醇酯多元醇或聚对苯二甲酸二乙醇酯多元醇)和/或甲苯二胺聚氧化丙烯多元醇和92-48wt％(优选91-50wt％，优选90-52wt％，优选88-53wt％，优选85-55wt％，优选84-60wt％，更优选82-65wt％)的(非甲苯二胺型或非甲苯二胺引发的)聚氧化丙烯多元醇。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605607A (zh) * 2022-04-07 2022-06-10 中国矿业大学 一种相变水合盐聚合充填材料及其制备方法、使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422912A (zh) * 2017-08-24 2019-03-05 补天新材料技术有限公司 碱性多胺醇胺发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途
CN109679130A (zh) * 2017-10-19 2019-04-26 山东理工大学 包含六氟丁烯和有机醇胺盐化合物的复合发泡剂
CN109867767A (zh) * 2017-12-05 2019-06-11 补天新材料技术有限公司 二氧化碳与有机胺相结合使用的聚氨酯发泡方法
CN112029134A (zh) * 2019-06-04 2020-12-04 毕戈华 含有碳酸二烷基酯和醇胺盐的聚氨酯复合发泡剂

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5789451A (en) * 1996-07-29 1998-08-04 The Dow Chemcial Company Alkanolamine/carbon dioxide adduct and polyurethane foam therewith
CN109422907B (zh) * 2017-08-24 2021-04-13 补天新材料技术有限公司 包含多胺和醇胺盐的发泡剂及用于聚氨酯连续板泡沫体材料中的用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422912A (zh) * 2017-08-24 2019-03-05 补天新材料技术有限公司 碱性多胺醇胺发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途
CN109679130A (zh) * 2017-10-19 2019-04-26 山东理工大学 包含六氟丁烯和有机醇胺盐化合物的复合发泡剂
CN109867767A (zh) * 2017-12-05 2019-06-11 补天新材料技术有限公司 二氧化碳与有机胺相结合使用的聚氨酯发泡方法
CN112029134A (zh) * 2019-06-04 2020-12-04 毕戈华 含有碳酸二烷基酯和醇胺盐的聚氨酯复合发泡剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BI GEHUA, LI XIN-CHAO;WEI WEI;HUANG JUN-FENG;BI YU-SUI: "Research On the Properties of Novel Chemical Foaming Agent CFA8 in Rigid PU Foam Field", JOURNAL OF SHANDONG UNIVERSITY OF TECHNOLOGY (NATURAL SCIENCE EDITION), vol. 31, no. 5, 25 September 2017 (2017-09-25), pages 1 - 5, XP055953403, ISSN: 1672-6197, DOI: 10.13367/j.cnki.sdgc.2017.05.001 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605607A (zh) * 2022-04-07 2022-06-10 中国矿业大学 一种相变水合盐聚合充填材料及其制备方法、使用方法
CN114605607B (zh) * 2022-04-07 2023-03-03 中国矿业大学 一种相变水合盐聚合充填材料及其制备方法、使用方法

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