WO2023221694A9 - 聚氨酯泡沫材料及其制备方法、冰箱和冰柜 - Google Patents

聚氨酯泡沫材料及其制备方法、冰箱和冰柜 Download PDF

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WO2023221694A9
WO2023221694A9 PCT/CN2023/087791 CN2023087791W WO2023221694A9 WO 2023221694 A9 WO2023221694 A9 WO 2023221694A9 CN 2023087791 W CN2023087791 W CN 2023087791W WO 2023221694 A9 WO2023221694 A9 WO 2023221694A9
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polyurethane foam
foaming agent
fluoroolefin
parts
foam material
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PCT/CN2023/087791
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English (en)
French (fr)
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WO2023221694A1 (zh
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曹立军
胡锋
刘莉
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海信容声(广东)冰箱有限公司
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Priority claimed from CN202210549493.9A external-priority patent/CN117126447A/zh
Priority claimed from CN202211499386.6A external-priority patent/CN118085212A/zh
Application filed by 海信容声(广东)冰箱有限公司 filed Critical 海信容声(广东)冰箱有限公司
Priority to CN202380013524.1A priority Critical patent/CN117940474A/zh
Publication of WO2023221694A1 publication Critical patent/WO2023221694A1/zh
Publication of WO2023221694A9 publication Critical patent/WO2023221694A9/zh

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    • 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
    • C08G18/08—Processes
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • 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
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08L75/08—Polyurethanes from polyethers

Definitions

  • the present disclosure relates to the technical field of polymer materials, in particular to a polyurethane foam material and its preparation method, refrigerators and freezers.
  • a polyurethane foam material including an organic polyisocyanate and a white material composition.
  • the white material composition includes 100 parts of polyol composition, 1.8-2.5 parts of water, 1.6-2.5 parts of foam stabilizer, 2-3 parts of catalyst, and 26-38 parts of composite foaming agent.
  • the composite foaming agent is composed of a high-boiling fluoroolefin foaming agent with a boiling point ⁇ 5°C and a low-boiling fluoroolefin foaming agent with a boiling point ⁇ -15°C, and the high-boiling fluoroolefin foaming agent is 25 ⁇ 35 parts, and the low-boiling point fluoroolefin foaming agent is 1-3 parts.
  • the polyurethane foam material in some embodiments of the present disclosure has high thermal insulation performance and good resistance to shrinkage and deformation.
  • the foaming system uses a composite foaming agent composed of a high-boiling fluoroolefin foaming agent with a boiling point ⁇ 5°C and a low-boiling fluoroolefin foaming agent with a boiling point ⁇ -15°C.
  • the original liquid has good fluidity and the foam is evenly filled.
  • the polyurethane foam material has low density, has small and uniform cells, its thermal conductivity is ⁇ 16.5Mw/mK, and has excellent thermal insulation performance; and the polyurethane foam material has strong resistance to shrinkage and deformation. , high dimensional stability under low temperature conditions and extremely low deformation.
  • a method for preparing polyurethane foam materials which includes: mixing a polyol composition, water, a foam stabilizer, and a catalyst at 20 to 30°C to obtain a first mixture;
  • the high boiling point fluoroolefin foaming agent is mixed through static premixing equipment at 15-20°C and 1.0-2.5MPa pressure to obtain a second mixture; the second mixture and the low boiling point fluoroolefin foaming agent are passed through static premixing equipment.
  • the mixing equipment is mixed at 15-20°C and 2.5-4.0MPa pressure to obtain a third mixture, that is, a white material composition; the white material composition and organic polyisocyanate are mixed and foamed in proportion through a high-pressure foaming gun head , the gun tip pressure is 110 to 160 bar, and the polyurethane foam material is obtained.
  • a refrigerator including an outer shell, an inner pot, and a heat insulation layer disposed between the outer shell and the inner pot.
  • the heat insulation layer is made of the polyurethane foam described in any of the above embodiments. Material.
  • a refrigerator including an outer shell, an inner pot, and a heat insulation layer disposed between the outer shell and the inner pot.
  • the material of the heat insulation layer includes the polyurethane foam described in any of the above embodiments. Material.
  • Figure 1 is an electron microscope photo of rigid polyurethane foam provided by some embodiments of the present disclosure
  • Figure 2 is an electron micrograph of conventional rigid polyurethane foam provided in some comparative examples of the present disclosure.
  • the ideal environmentally friendly foaming agents are alkanes (such as pentane, butane, etc.) and HFOs-like fluoroolefins (such as 1-chloro-3,3,3-trifluoropropene, cis-1,1, 1,4,4,4-hexafluoro-2-butene).
  • HFOs-based olefin foaming agents the currently technically mature ones are 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) and cis-1,1,1,4,4 , 4-hexafluoro-2-butene (HFO-1336mzz), but due to a single supply and exclusive monopoly, product production capacity is limited, resulting in high product prices. Refrigerator and freezer products are labor-intensive industries, and the supply of new foaming agents And high cost has become a major obstacle to the promotion and application in the field of home appliance insulation; and alkanes (such as hydrofluoroalkane low-boiling point foaming agents) have limited practical applications due to their high gas thermal conductivity.
  • alkanes such as hydrofluoroalkane low-boiling point foaming agents
  • polyether polyol A uses sucrose and glycerol as starting agents, with an average functionality of 6.0 and a hydroxyl value of 400 to 480 mgKOH/g;
  • polyether polyol B uses o-toluene di Amine is used as the initiator, with an average functionality of 3.9 and a hydroxyl value of 330-420 mgKOH/g;
  • polyether polyol C uses sorbitol as a initiator, with an average functionality of 4.4 and a hydroxyl value of 400-450 mgKOH/g;
  • Ester polyol is condensed from dicarboxylic acid and ethylene glycol, with an average functionality of 2.8 and a hydroxyl value of 250 to 350 mgKOH/g.
  • foam stabilizers The same types of foam stabilizers, catalysts, and organic polyisocyanates were used in each parallel experiment.
  • the reagents, methods and equipment used in this disclosure are conventional reagents, methods and equipment in this technical field. Unless otherwise stated, the reagents and materials used in this disclosure are commercially available.
  • a polyurethane foam material including components in parts by weight as shown in Table 1 and Table 2, and the preparation method includes steps S1 to S4.
  • step S1 according to the formula in Table 1, the polyol composition, water, foam stabilizer, and catalyst are mixed at 20 to 30°C to obtain a first mixture.
  • step S2 the first mixture and the high-boiling point fluoroolefin blowing agent are mixed in proportion through static premixing equipment at 15-20°C and 1.0-2.5MPa pressure to obtain a second mixture.
  • step S3 the second mixture and low-boiling fluoroolefin foaming agent are mixed in proportion through static premixing equipment at 15-20°C and 2.5-4.0MPa pressure to obtain a third mixture, that is, a white material composition .
  • step S4 the white material composition and the organic polyisocyanate are mixed and foamed in proportion through a high-pressure foaming gun head, and the pressure of the high-pressure foaming gun head is 110 to 160 bar to prepare the polyurethane foam material.
  • Comparative Examples 1 to 7 respectively provide a polyurethane foam material, including components in parts by weight as shown in Table 3, and the preparation method includes steps S11 to S14.
  • step S11 according to the formula in Table 3, the polyol composition, water, foam stabilizer, and catalyst are mixed at 20 to 30°C to obtain a first mixture.
  • step S12 the first mixture and the high-boiling point fluoroolefin blowing agent are mixed in proportion through static premixing equipment at 15-20°C and 1.0-2.5MPa pressure to obtain a second mixture.
  • step S13 the second mixture and low-boiling fluoroolefin foaming agent are mixed in proportion through static premixing equipment at 15-20°C and 2.5-4.0MPa pressure to obtain a third mixture, that is, a white material composition .
  • step S14 the white material composition and the organic polyisocyanate are mixed and foamed in proportion through a high-pressure foaming gun head, and the pressure of the high-pressure foaming gun head is 110 to 160 bar to prepare the polyurethane foam material.
  • the density distribution is the difference between the maximum molded core density and the minimum molded core density.
  • Cell pore size measured using a Scanning Electron Microscope (SEM).
  • test results of the examples are shown in Table 4, and the test results of the comparative examples are shown in Table 5.
  • the polyurethane foam materials prepared in each embodiment of the present disclosure have appropriate cell sizes, low density, low thermal conductivity, good thermal insulation performance, and excellent resistance to shrinkage and deformation. High dimensional stability at -20°C and -40°C.
  • the polyurethane foam material has better thermal insulation properties. performance and higher resistance to shrinkage and deformation.
  • Example 1 From the test results of Example 1 and Examples 9 to 12, taking into account the thermal insulation performance and shrinkage deformation resistance, it can be seen that the weight ratio of the high boiling point fluoroolefin foaming agent to the low boiling point fluoroolefin foaming agent is ( 12 ⁇ 15):1, the comprehensive performance of polyurethane foam is better.
  • Comparative Example 1 does not contain a low-boiling point fluoroolefin foaming agent, and the weight ratio of the two foaming agents in Comparative Example 2 exceeds the limited range of this disclosure. It is difficult to produce a polyurethane foam with both thermal insulation performance and shrinkage deformation resistance. Material. The amount of low-boiling point fluoroolefin foaming agent in Comparative Example 3 is too much, and it is difficult to mix evenly with other components under conventional processing conditions.
  • Both Application Example 1 and Application Example 3 use the polyurethane foam material of Example 1 as the material of the heat insulation layer to prepare a 400L refrigeration and freezing thin-walled refrigerator.
  • the thickness of the foam layer in the foam cavity of the refrigerator is between 20 and 65 mm.
  • the difference between Application Example 1 and Application Example 3 is that the refrigerator in Application Example 3 does not use VIP (Vacuum Insulation Panel) panels.
  • VIP Vauum Insulation Panel
  • Both Application Example 2 and Application Example 4 use the polyurethane foam material of Comparative Example 7 as the material of the thermal insulation layer to prepare a 400L refrigeration and freezing thin-walled refrigerator.
  • the thickness of the foam layer in the refrigerator foam cavity is between 20 and 65 mm.
  • the difference between Application Example 2 and Application Example 4 is that the refrigerator in Application Example 4 does not use a VIP board.
  • the above-mentioned refrigerators were tested for power consumption.
  • the test standards are GB/T8059-2016 household and similar refrigeration appliances and GB 12021.2-2015 household refrigerator power consumption limit values and energy efficiency levels.
  • the test results are shown in Table 6.
  • the polyurethane foam material of the present disclosure has excellent thermal insulation performance.
  • the polyurethane foam material of some embodiments of the present disclosure is used as a thin-walled refrigerator for refrigeration and freezing. Thermal insulation layer can reduce or eliminate the use of VIP boards.
  • the thickness of the insulation layer of ultra-thin refrigerators and freezers is about 20 to 60mm.
  • the wires, tube bundles and other components in the foam cavity of the refrigerator and freezer are distributed in this narrow space.
  • the flow channel of the foam raw material is narrow and the resistance of the flow channel increases, resulting in insufficient flow of the polyurethane raw material in the cavity.
  • the distribution of the polyurethane foam is not uniform, and the phenomenon of poor filling is increasing. This not only affects the appearance quality of the refrigerator, but more importantly, This can lead to poor insulation performance of the refrigerator or freezer.
  • Chinese patent application CN 115073694 A discloses a low-density and ultra-low thermal conductivity rigid polyurethane foam.
  • the foaming system used in this rigid polyurethane foam is LBA foaming agent, butane.
  • Foaming agent and methyl formate modifier By adding butane foaming agent, its saturated vapor pressure is large, which reduces the foam density; by adding methyl formate, the uniformity and fluidity of foam density are improved.
  • the storage stability of the foam formed by methyl formate foaming agent is poor, and butane has a high gas thermal conductivity.
  • the use of butane foaming agent will weaken the effect of fluoroolefin on reducing the thermal conductivity, and then The insulation performance of the refrigerator is not good enough.
  • Some embodiments of the present disclosure also provide a rigid polyurethane foam, including in parts by weight: 100 parts of combined polyether, 16 to 23 parts of foaming agent, 1 to 3 parts of foaming assistant, and organic polyisocyanate 144 to 160 parts; wherein, the foaming assistant is trifluoropropylene.
  • a rigid polyurethane foam is provided, which is based on the current cyclopentane foaming system (i.e., the cyclopentane system and the mixed foaming system with cyclopentane as the main body), and is introduced
  • An appropriate amount of trifluoropropylene is used as a foaming aid, that is, it forms a cyclopentane (or a mixed foaming system with cyclopentane as the main body) + trifluoropropylene mixed foaming system, which has the characteristics of low cost, low foam density, and ideal thermal conductivity.
  • the lower the thermal conductivity of the foam the better the insulation performance and the lower the energy consumption of the resulting product.
  • the solid thermal conductivity and foam matrix of polyurethane foam are relatively fixed, its thermal insulation performance is mainly affected by two aspects: (1) The type of foaming agent in the cells. The lower the gas phase thermal conductivity of the foaming agent, the better the thermal insulation performance; ( 2) Cell diameter. The finer the cells, the better the thermal conductivity of the foam.
  • fluoroolefin has a low gas thermal conductivity and contains multiple fluorine atoms, which can increase the nucleation rate of polyurethane foam during the foaming process. Therefore, the foam has excellent thermal insulation properties.
  • nucleating additives can also be added, such as 3M's perfluoroolefins (e.g., 5357, Fa-188, 5056, etc.), but these nucleating agents have obvious drawbacks-toxicity or global warming coefficient values (Global Warming Potential, GWP) is high and the cost is high.
  • 3M's perfluoroolefins e.g., 5357, Fa-188, 5056, etc.
  • Foaming density of foam is directly related to the cost of production. The lower the density of foam, the fewer production raw materials used and the lower the cost. Foaming of common fluoroolefins (e.g., 1-chloro-3,3,3-trifluoropropene, cis-1,1,1,4,4,4-hexafluoro-2-butene) can be obtained Foam has good thermal insulation properties, but its density exceeds 30.5kg/m3 and the cost is still high.
  • fluoroolefins e.g., 1-chloro-3,3,3-trifluoropropene, cis-1,1,1,4,4,4-hexafluoro-2-butene
  • a low boiling point foaming agent to the foam can reduce the foam density (as low as 27.5 ⁇ 29.0kg/m3) while ensuring the foam strength.
  • two types of low-boiling point blowing agents are used to add to the foam.
  • One type is alkanes, such as n-butane (boiling point -0.5°C), isobutane (boiling point -11.7°C); the other is hydrofluorocarbons.
  • Foaming agent such as HFC-134a (boiling point -26.2°C), HFC-152a (boiling point -25.7°C).
  • the former has a high gas thermal conductivity, which is not conducive to the thermal insulation performance of the foam after being added; the latter has a high GWP and is a HFCs (Hydrofluorocarbons) substance restricted by various countries' environmental regulations, so its application is gradually increasing. restricted.
  • this disclosure compared the performance of five low-boiling point foaming aids including trifluoropropylene and conducted related experiments. Finally, trifluoropropylene was selected as a foaming aid to be added to the current cyclopentane-based foaming aid. in the foaming system.
  • ODP Ozone Depletion Potential
  • the fluidity of the foam can be improved, the density distribution of the foam can be improved, and the quality of the product can be improved.
  • the polyfluorine atomic structure also has nucleation properties, making the prepared foam more fine and uniform, and can improve the thermal conductivity of the foam.
  • the organic polyisocyanate can specifically be selected from one or a mixture of PM2010 and PM200 of Yantai Wanhua Company, 44V20L of Covestro Company, M20s of BASF Company, Suprasec 5005 of Huntsman Company, and PAPI27 of DOW Company, preferably PM2010 .
  • the combined polyether includes at least a polyol composition, a foam stabilizer, a catalyst, and water.
  • the polyol composition is a polyether monomer selected from the group consisting of amine ethers, glyceryl polyethers, sucrose polyethers, mannitol polyethers, sorbitol polyethers, glyceryl sucrose polyethers, xylene polyethers Or at least one of polyester and polyether;
  • the foam stabilizer is an organosilicon compound;
  • the catalyst is a composite catalyst of tertiary amines and organotin.
  • the foam stabilizer is an organosilicon compound or an organosilicon compound, and its main structure is: polysiloxane-oxyalkylene block copolymer.
  • its main structure is: polysiloxane-oxyalkylene block copolymer.
  • the catalyst is The composite catalyst of tertiary amines and organotin can specifically select any one or a combination of TMR-2, PC-5 (or A-1), and PC-8.
  • the foaming agent includes pentane, with a weight ratio of 11 to 17, preferably 13 to 16, and the pentane is cyclopentane or cyclopentane and isopentane in a mass ratio of (7 to 9 ): (3 ⁇ 1) A mixture composed of.
  • the weight parts of pentane can be specifically selected from 11, 12, 13, 14, 15, 16, 17, or any value within the above limited range can be selected according to actual needs, all of which fall within the protection scope of the present disclosure.
  • the blowing agent also includes 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) or cis-1,1,1,4,4,4-hexafluoro-2- At least one kind of butene (HFO-1336mzz) has a weight portion of 0 to 10, preferably 0 to 8.
  • 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) or cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-
  • the weight parts of 1336mzz can be specifically selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 according to actual needs. Any value within the above limited range falls within the protection scope of the present disclosure. within.
  • the present disclosure also provides a method for preparing rigid polyurethane foam, including step S21 to step S23.
  • step S21 physically mix the polyol composition, foam stabilizer, catalyst and water at a temperature of 25 ⁇ 5°C according to the proportion by mass, and stir for 0.5 to 1.5 hours to obtain the first mixture;
  • step S22 the foaming agent, foaming assistant and the first mixture are uniformly mixed through a static mixer to obtain a second mixture;
  • step S23 under the temperature condition of 20 ⁇ 3°C, the second mixture and the organic polyisocyanate are mixed and foamed in proportion through a high-pressure gun head, and the pressure of the gun head is controlled to 110-150 bar to prepare rigid polyurethane foam.
  • this disclosure comprehensively compared five substances including trifluoropropylene, and finally selected trifluoropropylene as the most suitable foaming aid.
  • the specific screening process is as follows:
  • HFC-134a and HFC-152a have lower boiling points and higher vapor pressures, their global warming coefficient values are relatively high, and they belong to HFCs and are subject to increasingly stringent domestic regulations. Restricted by external environmental protection regulations; butane is environmentally friendly, but the gas thermal conductivity is relatively high, so the thermal insulation performance of the prepared polyurethane foam cannot achieve optimal results; while trifluoropropylene has a low boiling point, high vapor pressure, and is environmentally friendly It has good thermal conductivity, low gas thermal conductivity, and the polyfluorine atom-containing structure has nucleation properties, which can further improve the thermal insulation effect of the foam. Therefore, it is an ideal low-boiling point foaming aid.
  • This comparative example provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • the preparation method of rigid polyurethane foam includes the following steps:
  • This comparative example provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • rigid polyurethane foam is the same as that of Comparative Example 8. The difference is that in this comparative example, rigid polyurethane foam is prepared according to the above formula.
  • This comparative example provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • rigid polyurethane foam is the same as that of Comparative Example 8. The difference is that in this comparative example, rigid polyurethane foam is prepared according to the above formula.
  • This comparative example provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • rigid polyurethane foam is the same as that of Comparative Example 8. The difference is that in this comparative example, rigid polyurethane foam is prepared according to the above formula.
  • This embodiment provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • the preparation method of rigid polyurethane foam includes the following steps:
  • This embodiment provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • rigid polyurethane foam is the same as in Example 17, except that in this embodiment, rigid polyurethane foam is prepared according to the above formula.
  • This embodiment provides rigid polyurethane foam and its preparation method, specifically:
  • Rigid polyurethane foam in parts by weight, includes the following components:
  • rigid polyurethane foam is the same as in Example 17, except that in this embodiment, rigid polyurethane foam is prepared according to the above formula.
  • the rigid polyurethane foam prepared using the formula and preparation method provided by the present disclosure has smaller thermal conductivity, better thermal insulation performance, lower dimensional deformation rate, and better foam mechanical properties. good. After the molded core density of the foam is greatly reduced, the compressive strength of the foam is similar and the overall performance is excellent. It can be seen that the density of the rigid polyurethane foam core provided by the present disclosure can be as low as about 26.76kg/m3, which can reduce the amount of raw material injection while still maintaining good overall performance and meeting the needs of refrigerator manufacturers.
  • the polyurethane foam prepared using the foam composition formula provided by the present disclosure can effectively reduce the amount of raw material injection and reduce the Foam density, thereby achieving the purpose of reducing production costs.
  • the performance test standards in Table 8 are as follows:
  • Compressive strength GB/T 8813-2008 Determination of compression properties of rigid foam plastics.
  • Thermal conductivity GB/T 10295-2008 Determination of steady-state thermal resistance and related characteristics of thermal insulation materials using heat flow meter method.
  • This disclosure further conducted a complete machine energy consumption test on the rigid polyurethane foam obtained in Example 17 and Comparative Example 8 on a 300L refrigeration and freezer product. The measurement results are shown in Table 9.
  • this disclosure can make the cells finer and better solve the problem by introducing trifluoropropylene with good environmental protection and compounding it with the currently commonly used foaming system.
  • the defect of high thermal conductivity when cyclopentane is used alone reduces the density and thermal conductivity of polyurethane rigid foam.
  • it can solve the problem that butane low boiling point foaming systems cannot improve the thermal conductivity of foams such as HFC-134a and HFC-152a.
  • Low boiling point foaming system has high GWP value and is not environmentally friendly. question.
  • the method of preparing rigid polyurethane foam using the composition described in the present disclosure is particularly suitable for refrigerator and freezer products, and can better achieve environmental protection, energy saving and resource conservation of refrigerator and freezer products.
  • the present disclosure also provides a thermal insulation material prepared by using the low-density rigid polyurethane foam as described in any of the above embodiments.
  • the present disclosure also provides a refrigerator, which includes an insulation material prepared from the above-mentioned low-density rigid polyurethane foam.
  • the present disclosure also provides a freezer, which includes an insulation material prepared from the above-mentioned low-density rigid polyurethane foam.

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Abstract

公开了一种聚氨酯泡沫材料及其制备方法、冰箱和冰柜，属于高分子材料技术领域。本公开的聚氨酯泡沫材料，包括有机多异氰酸酯和白料组合物，白料组合物包括如下重量份的组分：多元醇组合物100份，水1.8～2.5份，泡沫稳定剂1.6～2.5份，催化剂2～3份，复合发泡剂26～38份；所述复合发泡剂由沸点≥5℃的高沸点氟代烯烃发泡剂和沸点≤-15℃的低沸点氟代烯烃发泡剂组成。本公开通过采用高、低沸点的氟代烯烃发泡体系，制得的聚氨酯泡沫材料密度低，具有细小均匀的泡孔，其导热系数≤16.5Mw/m.K，具有优异的保温性能；且聚氨酯泡沫材料的抗收缩变形能力强，在低温条件下尺寸稳定性高，变形程度极低。

Description

聚氨酯泡沫材料及其制备方法、冰箱和冰柜
相关申请的交叉引用
本公开要求在2022年11月28日提交中国专利局、申请号为202211499386.6的中国专利申请的优先权，以及在2022年5月20日提交中国专利局、申请号为202210549493.9的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及高分子材料技术领域，尤其是一种聚氨酯泡沫材料及其制备方法、冰箱和冰柜。
背景技术
冰箱或冰柜想要提高容积率，需通过减薄冰箱的保温层来达成，硬质聚氨酯泡沫作为冰箱冷柜的隔热保温材料，是直接影响冰箱冷柜重要使用性能指标的关键原料之一，对单台冰箱的生产效率、电能消耗起到举足轻重的作用。冰箱的保温层太薄，冰箱的保温性能就会下降。
发明内容
一方面，提供一种聚氨酯泡沫材料，包括有机多异氰酸酯和白料组合物。以重量份数计，所述白料组合物包括多元醇组合物100份，水1.8～2.5份，泡沫稳定剂1.6～2.5份，催化剂2～3份，复合发泡剂26～38份。所述复合发泡剂由沸点≥5℃的高沸点氟代烯烃发泡剂和沸点≤-15℃的低沸点氟代烯烃发泡剂组成，且所述高沸点氟代烯烃发泡剂为25～35份，所述低沸点氟代烯烃发泡剂为1～3份。
本公开一些实施例中的聚氨酯泡沫材料保温性能高、抗收缩形变好。在所述聚氨酯泡沫材料中，发泡体系采用由沸点≥5℃的高沸点氟代烯烃发泡剂和沸点≤-15℃的低沸点氟代烯烃发泡剂组成的复合发泡剂，泡料原液流动性好，泡沫充填均匀，制得的聚氨酯泡沫材料密度低，具有细小均匀的泡孔，其导热系数≤16.5Mw/m.K，具有优异的保温性能；且聚氨酯泡沫材料的抗收缩变形能力强，在低温条件下尺寸稳定性高，变形程度极低。
另一方面，提供一种聚氨酯泡沫材料的制备方法，包括：将多元醇组合物、水、泡沫稳定剂、催化剂在20～30℃下进行混合，得到第一混合物；将所述第一混合物、高沸点氟代烯烃发泡剂通过静态预混设备在15～20℃、1.0～2.5MPa压力下混合，得到第二混合物；将所述第二混合物、低沸点氟代烯烃发泡剂通过静态预混设备在15～20℃、2.5～4.0MPa压力下混合，得到第三混合物，即白料组合物；将所述白料组合物、有机多异氰酸酯按比例通过高压发泡枪头进行混合发泡，枪头压力为110～160bar，制得所述聚氨酯泡沫材料。
又一方面，提供一种冰箱，包括外壳、内胆及设置于所述外壳和所述内胆之间的隔热层，所述隔热层的材质包括上述任一实施例所述的聚氨酯泡沫材料。
又一方面，提供一种冰柜，包括外壳、内胆及设置于所述外壳和所述内胆之间的隔热层，所述隔热层的材质包括上述任一实施例所述的聚氨酯泡沫材料。
附图说明
图1为本公开的一些实施例所提供的硬质聚氨酯泡沫的电镜照片；
图2为本公开的一些对比例所提供的常规硬质聚氨酯泡沫的电镜照片。
具体实施方式
下面将结合附图，对本公开一些实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本公开一部分实施例，而不是全部的实施例。基于本公开所提供的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本公开保护的范围。
除非上下文另有要求，否则，在整个说明书和权利要求书中，术语“包括(comprise)”及其其他形式例如第三人称单数形式“包括(comprises)”和现在分词形式“包括(comprising)”被解释为开放、包含的意思，即为“包含，但不限于”。在说明书的描述中，术语“一个实施例(one embodiment)”、“一些实施例(some embodiments)”、“示例 性实施例(exemplary embodiments)”、“示例(example)”、“特定示例(specific example)”或“一些示例(some examples)”等旨在表明与该实施例或示例相关的特定特征、结构、材料或特性包括在本公开的至少一个实施例或示例中。上述术语的示意性表示不一定是指同一实施例或示例。此外，所述的特定特征、结构、材料或特点可以以任何适当方式包括在任何一个或多个实施例或示例中。
如本文所使用的那样，“约”、“大致”或“近似”包括所阐述的值以及处于特定值的可接受偏差范围内的平均值，其中所述可接受偏差范围如由本领域普通技术人员考虑到正在讨论的测量以及与特定量的测量相关的误差(即，测量系统的局限性)所确定。
目前，理想的环保型发泡剂为烷烃(如戊烷、丁烷等)、以及HFOs类氟代烯烃(如1-氯-3,3,3-三氟丙烯、顺式-1，1，1，4，4，4-六氟-2-丁烯)。其中，针对HFOs类烯烃发泡剂而言，目前技术上较成熟的是1-氯-3,3,3-三氟丙烯(HFO-1233zd)及顺式-1，1，1，4，4，4-六氟-2-丁烯(HFO-1336mzz)，但是由于货源单一、独家垄断，产品产能受限，导致产品价格昂贵，而冰箱冰柜产品属于劳动密集型产业，新发泡剂的货源和高成本成了在家电保温领域推广应用的重大障碍；而烷烃类(例如，氢氟烷烃类低沸点发泡剂)由于其本身具有较高的气体导热系数导致其实际应用受限。
因此，研制一款成本可控、导热系数低、泡沫低密度的环保型硬质聚氨酯泡沫是目前家电聚氨酯保温领域的重点研发方向。
在本公开的一些实施例和对比例中，聚醚多元醇A以蔗糖和甘油为起始剂，平均官能度为6.0、羟值为400～480mgKOH/g；聚醚多元醇B以邻甲苯二胺为起始剂，平均官能度为3.9、羟值为330～420mgKOH/g；聚醚多元醇C以山梨醇为起始剂，平均官能度为4.4、羟值为400～450mgKOH/g；聚酯多元醇由二甲酸与乙二醇缩合，平均官能度为2.8、羟值为250～350mgKOH/g。
各平行实验中泡沫稳定剂、催化剂、有机多异氰酸酯使用的种类相同。
除非特别说明，本公开采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。除非特别说明，本公开所用试剂和材料均为市购。
在一些实施例中分别提供一种聚氨酯泡沫材料，包括如表1和表2所示重量份的组分，制备方法包括步骤S1至步骤S4。
在步骤S1，按照表1的配方，将多元醇组合物、水、泡沫稳定剂、催化剂在20～30℃下进行混合，得到第一混合物。
在步骤S2，将所述第一混合物、高沸点氟代烯烃发泡剂按比例通过静态预混设备在15～20℃、1.0～2.5MPa压力下混合，得到第二混合物。
在步骤S3，将所述第二混合物、低沸点氟代烯烃发泡剂按比例通过静态预混设备在15～20℃、2.5～4.0MPa压力下混合，得到第三混合物，即白料组合物。
在步骤S4，将所述白料组合物、有机多异氰酸酯按比例通过高压发泡枪头进行混合发泡，所述高压发泡枪头的压力为110～160bar，制得所述聚氨酯泡沫材料。
表1实施例1～8聚氨酯泡沫材料的组分含量(重量份)
表2实施例9～16聚氨酯泡沫材料的组分含量(重量份)

对比例1～7
对比例1～7分别提供一种聚氨酯泡沫材料，包括如表3所示重量份的组分，制备方法包括步骤S11至步骤S14。
在步骤S11，按照表3的配方，将多元醇组合物、水、泡沫稳定剂、催化剂在20～30℃下进行混合，得到第一混合物。
在步骤S12，将所述第一混合物、高沸点氟代烯烃发泡剂按比例通过静态预混设备在15～20℃、1.0～2.5MPa压力下混合，得到第二混合物。
在步骤S13，将所述第二混合物、低沸点氟代烯烃发泡剂按比例通过静态预混设备在15～20℃、2.5～4.0MPa压力下混合，得到第三混合物，即白料组合物。
在步骤S14，将所述白料组合物、有机多异氰酸酯按比例通过高压发泡枪头进行混合发泡，所述高压发泡枪头的压力为110～160bar，制得所述聚氨酯泡沫材料。
表3对比例1～7聚氨酯泡沫材料的组分含量(重量份)

【性能测试】
对上述实施例和对比例得到的聚氨酯泡沫材料进行测试，具体测试项目及测试方法和结果如下：
模塑芯密度：按照GB/T 6343-2009聚氨酯泡沫塑料的密度测试，测试条件：采用排水法测定泡沫体积的方式测试，泡沫密度＝泡沫重量/泡沫体积，试样尺寸(50±1)mm×(50±1)mm×(50±1)mm，1台冰箱或冷柜产品的每个位置面至少取2个样品。
密度分布为最大模塑芯密度与最小模塑芯密度之差。
泡孔孔径：采用扫描电子显微镜(Scanning Electron Microscope，SEM)来测量。
导热系数(10℃)：按照GB/T 10295-2008绝热材料稳态热阻及有关特性的测定热流计法。
最小压缩强度(垂直方向)：按照GB/T 8813-2008硬质泡沫塑料压缩性能的测定。
尺寸稳定性：按照GB/T 8811-2008泡沫塑料与橡胶线性尺寸的测定，测试条件分别为-20℃、48h和-60℃、48h。
实施例的测试结果见表4，对比例的测试结果见表5。
表4实施例的测试结果

表5对比例的测试结果
需要说明的是，对比例3*中低沸点氟代烯烃发泡剂的量过多，在常规加工条件下难以与其他组分混合均匀。
根据表4和表5的测试结果，本公开各实施例所制备的聚氨酯泡沫材料均具有适宜的泡孔孔径，且密度低，导热系数低，保温性能好，同时具有优异的抗收缩变形能力，在-20℃和-40℃条件下的尺寸稳定性高。
由实施例1～8，可以看出，当高沸点氟代烯烃发泡剂为Z-HFO-1336mzz，低沸点氟代烯烃发泡剂为HFO-1243zf时，聚氨酯泡沫材料兼具更优的保温性能和更高的抗收缩变形能力。
由实施例1、实施例9～12的测试结果，综合考虑保温性能和抗收缩变形性能，可以看出，高沸点氟代烯烃发泡剂与低沸点氟代烯烃发泡剂的重量比为(12～15)∶1时，聚氨酯泡沫材料的综合性能更优。
对比例1中不含低沸点氟代烯烃发泡剂，对比例2中两种发泡剂的重量配比超出本公开限定范围，均难以制得兼具保温性能和抗收缩变形能力的聚氨酯泡沫材料。对比例3中低沸点氟代烯烃发泡剂的量过多，在常规加工条件下难以与其他组分混合均匀。
对比例4～7中采用非氟代烯烃类发泡剂，制得的聚氨酯泡沫材料泡孔均匀度差，材料的导热系数高，且低温下尺寸稳定性差。
应用例1～4
应用例1和应用例3均以实施例1的聚氨酯泡沫材料作为隔热层的材料，制备400L冷藏冷冻薄壁冰箱，冰箱发泡空腔内的泡层厚度在20～65mm之间。应用例1与应用例3的区别在于应用例3的冰箱不使用VIP(Vacuum Insulation Panel)板。
应用例2和应用例4均以对比例7的聚氨酯泡沫材料作为隔热层的材料，制备400L冷藏冷冻薄壁冰箱，冰箱发泡空腔内的泡层厚度在20～65mm之间。应用例2与应用例4的区别在于应用例4的冰箱不使用VIP板。
对上述冰箱进行耗电量测试，测试标准为GB/T8059-2016家用和类似用途制冷器具及GB 12021.2-2015家用电冰箱耗电量限定值及能效等级，测试结果见表6。
表6应用例的测试结果
根据表6的测试结果可以看出，本公开的聚氨酯泡沫材料具有优异的保温性能，采用本公开一些实施例的聚氨酯泡沫材料作为冷藏冷冻薄壁冰箱的 隔热层，可以减少或取消VIP板的使用。
同时，随着人们生活水平的提高和冰箱技术的发展，冰箱的容积越来越大，而城市里高昂的房价使人的居住空间面积有限，小体积大容积的产品就成为越来越多用户的需求，而这需要通过提高容积率来实现。冰箱或冰柜想要提高容积率，需通过减薄冰箱的保温层来达成，硬质聚氨酯泡沫作为冰箱冷柜的隔热保温材料，是直接影响冰箱冷柜重要使用性能指标的关键原料之一，对单台冰箱的生产效率、电能消耗起到举足轻重的作用。冰箱的保温层太薄，冰箱的保温性能就会下降，减薄之后，为了达到同样的保温性能，大多数冰箱通过真空绝热板(VIP板)来实现，而VIP的成本高昂，因此，含有VIP板的超薄冰箱冰柜的价格通常较普通冰箱的价格高很多。
目前，超薄冰箱冰柜保温层厚度约在20～60mm，如此薄的保温层，冰箱冷柜发泡空腔内的电线、管束等部件又分布在此狭窄的空间，聚氨酯发泡充填过程中，发泡原料的流道狭窄且流道阻力增大，导致聚氨酯原料在空腔中流动不够充分，从而聚氨酯泡沫分布不够均匀，出现填充不良的现象日益增多，不仅影响冰箱外观质量，更重要的是，会导致冰箱或冰柜的保温性能不良。
针对于聚氨酯泡沫分布不均的问题，中国专利申请CN 115073694 A公开了一种低密度超低导热系数的硬质聚氨酯泡沫，该硬质聚氨酯泡沫使用的发泡体系为LBA发泡剂、丁烷发泡剂和甲酸甲酯改良剂，通过加入丁烷发泡剂，利用其饱和蒸汽压较大，降低了泡沫密度；通过加入甲酸甲酯，改善了泡沫密度均匀性和流动性。但是，甲酸甲酯发泡剂所形成的泡料的存储稳定性较差，且丁烷由于具有较高的气体导热系数，使用丁烷发泡剂会减弱氟代烯烃降低导热系数的影响，进而使得冰箱的保温性能不够好。
此外，由于保温层更薄，聚氨酯泡沫的抗收缩变形的能力显得尤其重要，常规泡沫配方所制得的聚氨酯泡沫保温材料很容易在局部出现收缩，影响产品的外观质量。
因此，需要提供一种高保温性能、抗收缩变形能力好的聚氨酯泡沫材 料。
本公开的一些实施例还提供了一种硬质聚氨酯泡沫，以重量份数计，包括：组合聚醚100份、发泡剂16～23份、发泡助剂1～3份、有机多异氰酸酯144～160份；其中，所述发泡助剂为三氟丙烯。
在上述实施例中提供了一种硬质聚氨酯泡沫，该泡沫是在目前环戊烷发泡体系(即环戊烷体系及以环戊烷为主体的混合发泡体系)的基础上，再引入适量三氟丙烯作为发泡助剂，即组成环戊烷(或以环戊烷为主体的混合发泡体系)+三氟丙烯混合发泡体系，具有成本低廉、泡沫密度低、导热系数理想等特点。
需要说明的是，泡沫的导热系数越低，隔热性能就越好，所获得的产品能耗就越低。而聚氨酯泡沫由于其固体导热率及泡沫基体相对固定，因此，其隔热性能主要受两方面影响：(1)泡孔中发泡剂种类，发泡剂的气相导热系数越低保温性能越好；(2)泡孔孔径，泡孔越细密，泡沫的导热系数越好。
基于上述内容，氟代烯烃具有较低的气体导热系数，同时含有多个氟原子，可以提高发泡过程中聚氨酯泡沫的成核率，因此，泡沫具有优良的隔热性能。此外，还可以加入成核添加剂，如3M公司的全氟烯烃(例如，5357、Fa-188、5056等)，但是这些成核剂具有明显的缺陷——毒性或全球变暖系数值(Global Warming Potential，GWP)高，且成本高。
进一步地，泡沫的充填密度直接关系生产的成本，泡沫的密度越低，所用的生产原料越少，成本就越低。常见的氟代烯烃(例如，1-氯-3,3,3-三氟丙烯、顺式-1,1,1,4,4,4-六氟-2-丁烯)发泡虽然可以获得隔热性能良好的泡沫，但其密度超过30.5kg/m3，成本依旧较高。
需要说明的是，在泡沫中加入低沸点发泡剂能在保证泡沫强度的前提下实现泡沫密度的降低(可低至27.5～29.0kg/m3)。通常情况下，采用两类低沸点发泡剂加入泡沫中，一类是烷烃类，如正丁烷(沸点-0.5℃)、异丁烷(沸点-11.7℃)；另一类是氢氟烃发泡剂，如HFC-134a(沸点-26.2℃)、 HFC-152a(沸点-25.7℃)。然而，前者本身气体导热系数高，加入后不利于泡沫的隔热保温性能；后者由于具有较高GWP且为HFCs(氟氯烃，Hydrofluorocarbons)类受各国环保法规限制物质，使其应用上逐渐受到限制。基于此，本公开比对了包括三氟丙烯在内的5种低沸点发泡助剂性能并进行相关实验，最终选择三氟丙烯作为发泡助剂添加到目前的以环戊烷为主体的发泡体系中。
进一步地，本公开选择三氟丙烯作为发泡助剂的主要有以下几方面原因：
1、环保性能优异，其臭氧破坏潜能值(ODP，Ozone Depletion Potential)为0，GWP值为4。
2、低沸点、高蒸气压的特性，常温常压下是气体，在发泡过程中被包裹在泡孔中，可以大幅提高泡孔抗收缩变形的能力，从而降低泡沫密度。
3、在发泡过程中可以改善泡料的流动性，可以改善泡沫的密度分布，提升产品的质量。
4、多氟原子结构作为低沸点物质同时具有成核性，使制备的泡沫更加微细、均匀，可以改善泡沫的导热系数。
此外，有机多异氰酸酯具体可选自烟台万华公司的PM2010、PM200，Covestro公司的44V20L、BASF公司的M20s、Huntsman公司的Suprasec 5005、DOW公司的PAPI27中的一种或几种的混合物，优选PM2010。
在一些实施方式中，组合聚醚至少包括多元醇组合物、泡沫稳定剂、催化剂和水。
在一些实施方式中，多元醇组合物为聚醚单体，选自胺醚、甘油醇聚醚、蔗糖聚醚、甘露醇聚醚、山梨醇聚醚、甘油蔗糖聚醚、二甲苯胺聚醚或聚酯聚醚中的至少一种；所述泡沫稳定剂为有机硅化合物；催化剂为叔胺类与有机锡的复合催化剂。
在上述实施方式中，泡沫稳定剂为有机硅化合物或有机硅系化合物，其主要结构是：聚硅氧烷-氧化烯烃嵌段共聚物，具体可选择赢创德固赛的 B8460、B8461、B8462、B8465、B8471、B8474、B8476、B8481等；美思德公司的AK8805、AK8815、AK8812、AK8809等；迈图公司的L6900、L6863等中的一种或几种混合物；催化剂为叔胺类与有机锡的复合催化剂具体可选择TMR-2，PC-5(或A-1)，PC-8中的任意一种或几种进行组合。
在一些实施例中，发泡剂包括戊烷，其重量份数为11～17，优选13～16，所述戊烷为环戊烷或环戊烷与异戊烷按质量比(7～9)：(3～1)组成的混合物。
在上述实施方式中，戊烷的重量份数具体可选择11、12、13、14、15、16、17或根据实际需要选择上述限定范围内的任一数值均落在本公开的保护范围之内。
在一些实施例中，发泡剂还包括1-氯-3,3,3-三氟丙烯(HFO-1233zd)或顺式-1，1，1，4，4，4-六氟-2-丁烯(HFO-1336mzz)中的至少一种，其重量份数为0～10，优选0～8。
在上述实施方式中，1-氯-3,3,3-三氟丙烯(HFO-1233zd)或顺式-1，1，1，4，4，4-六氟-2-丁烯(HFO-1336mzz)的重量份数具体可选取0、1、2、3、4、5、6、7、8、9、10根据实际需要选择上述限定范围内的任一数值均落在本公开的保护范围之内。
本公开还提供了一种硬质聚氨酯泡沫的制备方法，包括步骤S21至步骤S23。
在步骤S21，按照质量份数配比，将多元醇组合物、泡沫稳定剂、催化剂和水，在25±5℃温度条件下物理混合，搅拌0.5～1.5h，得第一混合物；
在步骤S22，将发泡剂、发泡助剂及所述第一混合物通过静态混合器均匀混合，得第二混合物；
在步骤S23，在20±3℃温度条件下，通过高压枪头将所述第二混合物与有机多异氰酸酯按比例混合发泡，控制枪头压力为110～150bar，制得硬质聚氨酯泡沫。
为了更清楚详细地介绍本公开的一些实施例所提供的硬质聚氨酯泡沫、 制备方法及包含聚氨酯泡沫的保温材料、冰箱或冰柜，下面将结合具体实施例进行描述。
【发泡助剂低沸点物质筛选实验】
本公开为了获得最适用于硬质聚氨酯发泡剂的低沸点发泡助剂，综合比对了包含三氟丙烯在内的五种物质，最终选择三氟丙烯作为最适宜的发泡助剂使用，具体的筛选过程如下：
表7低沸点物质性能比对
从表格中可以看出，虽然HFC-134a及HFC-152a具有较低的沸点及较高的蒸汽压，但其全球变暖系数值偏高，且属于HFCs类物质，受到越来越严的国内外环保法规的限制；丁烷环保性好，但气体导热系数相对较高，制备得到的聚氨酯泡沫的保温性能也因此达不到较佳的效果；而三氟丙烯沸点低、蒸汽压高，环保性好，气体导热系数低，且含多氟原子结构具有成核性可进一步改善泡沫的保温效果，因此，是较理想的低沸点发泡助剂。
对比例8
本对比例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水1.9份、发泡剂-戊烷16份、有机多异氰酸酯147份。
硬质聚氨酯泡沫的制备方法包括以下步骤：
(1)按照质量份数配比，将多元醇组合物、泡沫稳定剂、泡沫催化剂和水，在25±5℃温度条件下物理混合，搅拌0.5～1.5h，得第一混合物；
(2)将发泡剂与第一混合物通过静态混合器均匀混合，得第二混合物；
(3)在20±3℃温度条件下，通过高压枪头将所述第二混合物与有机多异氰酸酯按比例混合发泡，控制枪头压力为110～150bar，制得硬质聚氨酯泡沫。
对比例9
本对比例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水2.1份、发泡剂-戊烷12.5份、有机多异氰酸酯151份。
硬质聚氨酯泡沫的制备方法同对比例8，不同之处在于本对比例按照上述配方进行硬质聚氨酯泡沫的制备。
对比例10
本对比例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水2.2份、发泡剂-戊烷12.5份、发泡剂-HFO-1336mzz为7份、发泡剂-正丁烷2份、有机多异氰酸酯153份。
硬质聚氨酯泡沫的制备方法同对比例8，不同之处在于本对比例按照上述配方进行硬质聚氨酯泡沫的制备。
对比例11
本对比例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水2.2份、发泡剂-戊烷12.5份、发泡剂-HFO-1336mzz为7份、有机多异氰酸酯 151份。
硬质聚氨酯泡沫的制备方法同对比例8，不同之处在于本对比例按照上述配方进行硬质聚氨酯泡沫的制备。
实施例17
本实施例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水1.9份、发泡剂-戊烷16份、发泡助剂-三氟丙烯3.0份、有机多异氰酸酯150份。
硬质聚氨酯泡沫的制备方法包括以下步骤：
(1)按照质量份数配比，将多元醇组合物、泡沫稳定剂、泡沫催化剂和水，在25±5℃温度条件下物理混合，搅拌0.5～1.5h，得第一混合物；
(2)将发泡剂、发泡助剂及第一混合物通过静态混合器均匀混合，得第二混合物；
(3)在20±3℃温度条件下，通过高压枪头将第二混合物与有机多异氰酸酯按比例混合发泡，控制枪头压力为110～150bar，制得硬质聚氨酯泡沫。
实施例18
本实施例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水2.1份、发泡剂-戊烷13.5份、发泡剂-HFO-1233zd为7份、三氟丙烯2.0份、有机多异氰酸酯155份。
硬质聚氨酯泡沫制备方法同实施例17，不同之处在于本实施例按照上述配方进行硬质聚氨酯泡沫的制备。
实施例19
本实施例提供了硬质聚氨酯泡沫及其制备方法，具体为：
硬质聚氨酯泡沫，以重量份数计，包括以下组分：
多元醇组合物100份、泡沫催化剂2.1份、泡沫稳定剂2.2份、水2.2份、发泡剂-戊烷13.5份、发泡剂-HFO-1336mzz为7份、发泡助剂-三氟丙烯2.0份、有机多异氰酸酯155份。
硬质聚氨酯泡沫制备方法同实施例17，不同之处在于本实施例按照上述配方进行硬质聚氨酯泡沫的制备。
【性能测试】
本公开针对上述对比例与实施例制备得到的硬质聚氨酯泡沫分别进行了自由泡密度、平均导热系数(10℃、0℃)、平均压缩强度、尺寸稳定性等多项性能测试，具体的测试结果见下表：
表8实施例与对比例的原料配比及泡沫性能
由表8数据可知，与对比例相比，采用本公开所提供的配方及制备方法制备得到的硬质聚氨酯泡沫的导热系数更小，隔热性能更佳，尺寸变形率更低，泡沫力学性能良好。泡沫的模塑芯密度大幅度降低之后，泡沫的压缩强度相近，综合性能优异。可见，本公开所提供的硬质聚氨酯泡沫芯密度可低至约26.76kg/m3，能够在降低原料灌注量的同时，仍旧能保持良好的综合性能，满足冰箱厂商的需求。由此可见，在相同工艺参数下，采用本公开所提供的泡沫组合物配方制备得到的聚氨酯泡沫能够有效减少原料灌注量，降低 泡沫密度，从而达到降低生产成本的目的。注：表8中各项性能测试标准如下：
自由泡密度、模塑芯密度：GB/T 6343-95聚氨酯泡沫塑料的密度测试。
压缩强度：GB/T 8813-2008硬质泡沫塑料压缩性能的测定。
导热系数：GB/T 10295-2008绝热材料稳态热阻及有关特性的测定热流计法。
尺寸稳定性：GB/T 8811-2008泡沫塑料与橡胶线性尺寸的测定。
【硬质聚氨酯泡沫在300L冷藏冷冻冰箱产品上整机能耗测试】
本公开进一步对实施例17和对比例8所得硬质聚氨酯泡沫在300L冷藏冷冻冰箱产品上进行了整机能耗测试，测定结果见表9。
表9整机能耗测试数据
上述整机性能测试均按照中国标准(GB/T8059-2016家用和类似用途制冷器具及GB 12021.2-2015家用电冰箱耗电量限定值及能效等级)进行测定，由表格数据可知，与对比例8相比，采用了本公开的一些实施例的冰箱产品整机能耗降低了3.24％，负载温升时间提升了16.39％。同时，本公开还对实施例17与对比例8的聚氨酯泡沫进行电镜拍照(如图1～2所示)，从图中可知，本公开制备得到的硬质聚氨酯泡沫的泡沫更为细密，且泡孔更细小、均匀。
基于表8和表9以及图2的结果，本公开通过引入采用环保性好的三氟丙烯，与目前常用的发泡体系进行复配，可以使制得的泡孔更细密，能较好解决环戊烷单独体系使用时导热率高的缺陷，降低了聚氨酯硬质泡沫的密度和导热系数，同时能解决丁烷类低沸点发泡体系不能改善泡沫导热系数，HFC-134a、HFC-152a类低沸点发泡体系GWP值高、对环境不友好的问 题。利用本公开所述的组合物制备硬质聚氨酯泡沫的方法尤其适用于冰箱、冰柜产品，能较好实现冰箱冰柜产品的环保节能及节约资源。
本公开还提供了一种保温材料，该材料利用如上述任一实施例所述的低密度硬质聚氨酯泡沫制备得到。
本公开同时还提供了一种冰箱，其包含由上述低密度硬质聚氨酯泡沫制备得到保温材料。
本公开也提供了一种冰柜，其包含由上述低密度硬质聚氨酯泡沫制备得到保温材料。
应当说明的是，以上实施例仅用以说明本公开的技术方案而非对本公开保护范围的限制，尽管参照较佳实施例对本公开作了详细说明，本领域的普通技术人员应当理解，可以对本公开的技术方案进行修改或者等同替换，而不脱离本公开技术方案的实质和范围。
在本公开的描述中，需要理解的是，术语“上”、“下”、“左”、“右”、“前”、“后”、“顶”、“底”、“内”、“外”、“中”、“竖直”、“水平”、“横向”、“纵向”、“X轴方向”、“Y轴方向”、“Z轴方向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本公开和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本公开的限制。并且，上述部分术语除了可以用于表示方位或位置关系外，还可能用于表示其他含义，例如术语“上”在某些情况下也可能用于表示某种依附关系或连接关系。对于本领域普通技术人员而言，可以根据具体情况理解这些术语在本公开中的具体含义。
以上所述仅是本公开的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开技术原理的前提下，还可以做出若干改进和替换，这些改进和替换也应视为本公开的保护范围。

Claims (11)

  1. 一种聚氨酯泡沫材料，包括：有机多异氰酸酯和白料组合物；
    所述白料组合物包括如下重量份的组分：
    所述复合发泡剂由沸点≥5℃的高沸点氟代烯烃发泡剂和沸点≤-15℃的低沸点氟代烯烃发泡剂组成，且所述高沸点氟代烯烃发泡剂为25～35份，所述低沸点氟代烯烃发泡剂为1～3份。
  2. 根据权利要求1所述的聚氨酯泡沫材料，其中，所述高沸点氟代烯烃发泡剂与低沸点氟代烯烃发泡剂的重量比为(12～15)∶1。
  3. 根据权利要求1或2所述的聚氨酯泡沫材料，其中，所述高沸点氟代烯烃发泡剂为1-氯-3,3,3-三氟丙烯、顺式-1,1,1,4,4,4-六氟-2-丁烯、反式-1,1,1,4,4,4-六氟-2-丁烯中的至少一种。
  4. 根据权利要求1至3中任一项所述的聚氨酯泡沫材料，其中，所述低沸点氟代烯烃发泡剂为3,3,3-三氟丙烯、反式-1,3,3,3-四氟丙烯、2,3,3,3-四氟丙烯、1,2,3,3,3-五氟丙烯中的至少一种。
  5. 根据权利要求1至4中任一项所述的聚氨酯泡沫材料，其中，所述复合发泡剂中高沸点氟代烯烃发泡剂为为顺式-1,1,1,4,4,4-六氟-2-丁烯，且低沸点氟代烯烃发泡剂为3,3,3-三氟丙烯。
  6. 根据权利要求1至5中任一项所述的聚氨酯泡沫材料，其中，所述多元醇组合物包括聚醚多元醇和/或聚酯多元醇；所述聚醚多元醇的平均官能度≥3.5，羟值为330～480mgKOH/g；所述聚酯多元醇的平均官能度为2.8～3，羟值为250-350mgKOH/g。
  7. 根据权利要求1至6中任一项所述的聚氨酯泡沫材料，满足如下(a)～(c)中的至少一者：
    (a)所述泡沫稳定剂为有机硅氧烷聚氧化烯烃接枝共聚物；
    (b)所述催化剂包括发泡催化剂、凝胶催化剂和三聚催化剂；
    (c)所述有机多异氰酸酯为多亚甲基多苯基多异氰酸酯。
  8. 根据权利要求1至7中任一项所述的聚氨酯泡沫材料，其中，所述白料组合物与有机多异氰酸酯的重量比为1：(1.08～1.3)。
  9. 权利要求1至8中任一项所述的聚氨酯泡沫材料的制备方法，包括：
    将多元醇组合物、水、泡沫稳定剂、催化剂在20～30℃下进行混合，得到第一混合物；
    将所述第一混合物、高沸点氟代烯烃发泡剂通过静态预混设备在15～20℃、1.0～2.5MPa压力下混合，得到第二混合物；
    将所述第二混合物、低沸点氟代烯烃发泡剂通过静态预混设备在15～20℃、2.5～4.0MPa压力下混合，得到第三混合物，即白料组合物；
    将所述白料组合物、有机多异氰酸酯按比例通过高压发泡枪头进行混合发泡，枪头压力为110～160bar，制得所述聚氨酯泡沫材料。
  10. 一种冰箱，包括外壳、内胆及设置于所述外壳和所述内胆之间的隔热层，所述隔热层的材质包括权利要求1至8中任一项所述的聚氨酯泡沫材料。
  11. 一种冰柜，包括外壳、内胆及设置于所述外壳和所述内胆之间的隔热层，所述隔热层的材质包括权利要求1至8中任一项所述的聚氨酯泡沫材料。
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