WO2016150016A1 - 聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱 - Google Patents

聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱 Download PDF

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WO2016150016A1
WO2016150016A1 PCT/CN2015/081692 CN2015081692W WO2016150016A1 WO 2016150016 A1 WO2016150016 A1 WO 2016150016A1 CN 2015081692 W CN2015081692 W CN 2015081692W WO 2016150016 A1 WO2016150016 A1 WO 2016150016A1
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weight
parts
polyether polyol
polyurethane foam
polyol
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PCT/CN2015/081692
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English (en)
French (fr)
Inventor
赵士虎
李彩侠
程发祥
琚绍成
朱洪阳
张静静
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Hefei Hualing Co Ltd
Midea Group Co Ltd
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Hefei Hualing Co Ltd
Midea Group Co Ltd
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Definitions

  • the invention belongs to the technical field of refrigerators, and in particular to a polyurethane composition, a polyurethane foam, a preparation method thereof and a refrigerator.
  • LBA new environmentally-friendly and high-efficiency foaming agent - trans-1-chloro-3,3,3-trifluoropropene
  • LBA has strong corrosiveness to the inner tank of the refrigerator. After high and low temperature test, the inner liner will be corroded and cracked.
  • a HIPS/PE alloy liner was invented. However, the surface of the alloy liner has a low surface polarity and a small adhesion to the foamed material. Because the adhesion of the rigid polyurethane foam is related to the foam density, the lower the density, the worse the adhesion.
  • the foam density prepared is small, generally between 30.5 and 32 kg/m 3 , so that the foam and the inner liner of the refrigerator are less adhesive.
  • the foaming agent volatilizes, taking away the heat of the foam surface, thereby reducing the adhesion of the foam to the surface of the liner. Therefore, after the HIPS/PE alloy liner is foamed or after the high and low temperature test, the foamed layer is easily debonded from the liner.
  • the measures that can be taken include: performing secondary corona on the one hand and increasing the corona value of the plate, but the secondary corona will increase the cost, increase the working hours, and reduce the production efficiency of the refrigerator liner and the refrigerator;
  • the thickness of the foamed alloy layer produced by this measure is uneven, and there may be no phenomenon of alloy layer locally, which does not achieve the anti-corrosion effect;
  • the foam density is increased because Adhesion is affected by the density of the foam, and the greater the density, the better the adhesion. But this kind of measure will increase the cost of the refrigerator.
  • an object of the present invention is to provide a polyurethane composition, a polyurethane foam, a preparation method thereof and a refrigerator using the polyurethane composition
  • the resulting polyurethane foam has a low density and good bonding properties, and is also low in production cost.
  • the invention proposes a polyurethane composition.
  • the polyurethane composition comprises:
  • isocyanate has an index of from 0.95 to 1.10.
  • the polyurethane foam obtained by using the polyurethane composition according to the embodiment of the present invention has a low density and good bonding property, and is also low in production cost.
  • polyurethane composition according to the above embodiment of the present invention may further have the following additional technical features:
  • the polyurethane composition comprises: 25 to 50 parts by weight of the sorbitol polyol; 15 to 30 parts by weight of the composite polyether polyol; 5 to 25 parts by weight The diphenylmethanediamine polyether polyol; 3 to 10 parts by weight of the glycerin polyether polyol; 5 to 15 parts by weight of the aromatic polyester polyol; 2 to 4 parts by weight The composite crosslinking agent; 1 to 55 parts by weight of the blowing agent; 1.0 to 5.0 parts by weight of the foam stabilizer; 1.2 to 1.9 parts by weight of the water; 1.0 to 3.5 parts by weight of the composite catalyst And 120 to 160 parts by weight of the isocyanate.
  • the density and production cost of the obtained polyurethane foam can be further reduced while improving the bonding property.
  • the sorbitol polyol has a hydroxyl value of 380 to 470 mgKOH/g, and the sorbitol polyol has a viscosity of 8000 to 15000 mPa ⁇ s, the sorbitol.
  • the polyol has a functionality of 6.
  • the composite polyether polyol is polymerized from sucrose, triethanolamine, and propylene oxide, wherein a weight ratio of the sucrose to the triethanolamine is from 1 to 4:1.
  • the complex polyether polyol has a functionality of 4-6, the complex polyether polyol has a hydroxyl value of 360-420 mgKOH/g, and the composite polyether polyol has a viscosity of 5000-14000 mPa ⁇ s. Thereby, the adhesive property of the obtained polyurethane foam can be remarkably improved.
  • the diphenylmethanediamine polyether polyol is oxidized by diphenylmethanediamine a polymerization of propylene and ethylene oxide, wherein the weight ratio of the propylene oxide to the ethylene oxide is 1-4:1, and the hydroxyl value of the diphenylmethanediamine polyether polyol is 380-440 mgKOH/g.
  • the viscosity of the diphenylmethanediamine polyether polyol is 15,000 to 25,000 mPa ⁇ s.
  • the glycerol polyether polyol has a hydroxyl value of from 160 to 300 mgKOH/g, and the glycerol polyether polyol has a viscosity of from 200 to 600 mPa ⁇ s.
  • the aromatic polyester polyol has a hydroxyl value of 200 to 350 mgKOH/g, and the aromatic polyester polyol has a viscosity of 1000 to 2000 mPa ⁇ s, the aromatic polyester.
  • the polyol has a functionality of 2.7. Thereby, the adhesive property of the polyurethane foam can be further improved.
  • the aromatic polyester polyol is a phthalic anhydride polyester.
  • the blowing agent comprises trans-1-chloro-3,3,3-trifluoropropene, wherein the trans-1-chloro-3,3,3-tri
  • the amount of fluoropropene used is from 1 to 55 parts by weight.
  • the blowing agent further comprises at least one of cyclopentane and pentafluoropropane, wherein the cyclopentane is used in an amount of 0 to 15 parts by weight, the pentafluoropropane The amount used is 0 to 20 parts by weight. Thereby, the foam production cost can be reduced.
  • the foam stabilizer is a silicone oil.
  • the adhesive property of the polyurethane foam can be further improved.
  • the complex crosslinking agent comprises ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine, and diphenylmethanediamine. At least two of them. Thereby, the adhesive property of the polyurethane foam can be further improved.
  • the isocyanate is a polymethylpolyphenyl polyisocyanate.
  • the invention proposes a polyurethane foam.
  • the polyurethane foam is made from the polyurethane composition described above.
  • the obtained polyurethane foam can be made to have a low density, good adhesion property, and low production cost.
  • polyurethane foam according to the above embodiment of the present invention may further have the following additional technical features:
  • the polyurethane foam has a density of less than 28.5 kg/m 3 .
  • the polyurethane foam has a thermal conductivity of less than 17.5 mW/m ⁇ k.
  • the polyurethane foam has a compressive strength greater than 150 kPa.
  • the polyurethane foam has a bond strength greater than 280 kPa.
  • the invention proposes a refrigerator.
  • the refrigerator comprises the polyurethane foam described above.
  • the refrigerator has the characteristics of good heat preservation effect and low energy consumption.
  • the invention provides a process for the preparation of the polyurethane foam described above. According to an embodiment of the invention, the method comprises:
  • a premix comprising a sorbitol polyol, a composite polyether polyol, a diphenylmethane diamine polyether polyol, a glycerin polyether polyol, an aromatic polyester polyol, a composite blend a binder, a blowing agent, a foam stabilizer, water, and a composite catalyst;
  • the premix and isocyanate are injected into a mold for aging treatment to obtain the polyurethane foam.
  • the above-mentioned polyurethane foam having low density, good bonding property and low production cost can be prepared, and by using a low vapor phase thermal conductivity, a low GWP, and a zero ODP foaming agent, not only can Meet energy-saving requirements, and be environmentally friendly and green.
  • the method for producing a polyurethane foam according to the above embodiment of the present invention may further have the following additional technical features:
  • a refrigerator liner having a predetermined shape is disposed in the mold.
  • the mold is a refrigerator cavity.
  • the mold has a temperature of 38 to 45 °C.
  • the preset pressure is 130 to 150 bar.
  • the predetermined time is 178-181 s.
  • the present invention provides a polyurethane composition.
  • the present invention provides a polyurethane foam and a method of preparing the same.
  • the present invention provides a refrigerator having a polyurethane foam prepared by the above-described method for preparing a polyurethane foam.
  • a polyurethane composition which is prepared by the following raw materials in a ratio by weight: sorbitol polyether 25 to 60 parts by weight 15 to 40 parts by weight of the composite polyether polyol, 3 to 30 parts by weight of the diphenylmethanediamine polyether polyol, 3 to 15 parts by weight of the glycerin polyether polyol, and 3 to 20 parts by weight of the aromatic polyester polyol.
  • the composite crosslinking agent 0 to 5 parts by weight of the composite crosslinking agent, 1 to 55 parts by weight of the foaming agent, 1.0 to 5.0 parts by weight of the foam stabilizer, 0.5 to 2.0 parts by weight of water, 1.0 to 3.5 parts by weight of the composite catalyst, and isocyanate 120 to 160 Parts by weight; wherein the isocyanate has an index of from 0.95 to 1.10.
  • the viscosity of the ether polyol is 5,000 to 12,000 mPa ⁇ s; the diphenylmethane diamine polyether polyol is formed by polymerizing diphenylmethane diamine, the propylene oxide and ethylene oxide, the diphenylmethane
  • the amine is a starter, wherein the diphenylmethanediamine polyether polyol is 5 to 25 heavy
  • the weight ratio of the propylene oxide to the ethylene oxide is 1-4:1, and the hydroxyl value of the diphenylmethanediamine polyether polyol is 380-440 mgKOH/g, the diphenylmethanediamine
  • the polyether polyol has a viscosity of 15000 to 25000 mPa ⁇ s; the glycerin polyether polyol is formed by polymerizing glycerin and the propylene oxide, and the glycerin is a starter, wherein the glycerol polyether polyol 3 to 10
  • the composite catalyst is composed of pentamethyldiethylenetriamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine, tetramethylhexamethylenediamine, dimethyl
  • the foam stabilizer is Si- a C-structured silicone oil
  • the composite crosslinking agent is composed of ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine, diphenylmethanediamine
  • the water is 1.2 to 1.9 parts by weight
  • the organic isocyanate is a plurality of primary polyphenyl polyisocyan
  • the polyurethane composition provided by the embodiment of the invention has low viscosity, mild reaction speed, good fluidity and adhesion; wherein the sorbitol polyol uses sorbitol as a starting agent, not only can improve the strength of the foam,
  • the prepared foam cells are fine and can reduce the thermal conductivity of the foam;
  • the composite polyether polyol has the characteristics of high-functionality polyether and amine-based polyether, and the prepared foam has high strength and reacts with organic isocyanate. It has high activity and fast curing speed after foaming, effectively improves the shortness of the foam skin and is easy to crisp, and improves the bonding strength; while the diphenylmethanediamine polyether polyol is composed of diphenylmethanediamine.
  • the glycerin polyether polyol is added to the polyurethane composition because the glycerin polyether polyol has good fluidity, which is advantageous for improving the adhesion, but the amount cannot be too much, and if it is too much, the strength of the foam is affected.
  • the glycerin polyether polyol is 3 to 10 parts by weight; wherein the aromatic polyester polyol in the polyurethane composition contains a benzene ring, which can improve the strength of the foam, lower the thermal conductivity of the foam, and has a small viscosity and good fluidity. It is advantageous to improve the adhesion of the foam, but because the functionality is small, the amount is not excessive, and preferably, the aromatic polyester polyol is preferably used in an amount of 5 to 15 parts by weight; wherein the composite crosslinking of the polyurethane composition The agent can meet the foam performance requirements and increase the bond strength of the foam.
  • the physical foaming agent and the chemical foaming agent and water should be controlled within a proper ratio range, so that the combined polyether has a moderate viscosity, and the heat generated by the reaction of water and isocyanate can make up for the heat taken away by the vaporization of the physical foaming agent, thereby increasing the foam.
  • the effect of bonding strength is preferably from 1.2 to 1.9 parts by weight.
  • a polyurethane foam is proposed, wherein the polyurethane foam is made of the polyurethane composition described above.
  • the polyurethane foam has a thermal conductivity of less than 17.5 mW/m ⁇ k, the polyurethane foam has a compressive strength of more than 150 kPa, and the polyurethane foam has a bond strength of greater than 280 kPa.
  • the polyurethane foam provided according to the embodiment of the present invention is prepared by the polyurethane composition described above, wherein the polyurethane foam has a density of less than 28.5 kg/m 3 , a thermal conductivity of less than 17.5 mW/m ⁇ k, and a compressive strength of more than 150 kPa.
  • the bond strength is greater than 280 kPa, so that the polyurethane foam has strong adhesiveness, and the foam and the liner do not detach after foaming or high and low temperature impact.
  • a refrigerator comprising the polyurethane foam of any of the above embodiments.
  • the refrigerator provided according to the embodiment of the invention has good heat preservation effect and low energy consumption. Further, other refrigeration devices including the above polyurethane foam also have the advantageous effects of the above refrigerator.
  • a method for producing a polyurethane foam comprising: mixing a sorbitol polyether polyol, a composite polyether polyol, and a diphenylmethane diamine polyether polyol by a stirring pressure tank; Alcohol, glycerin polyether polyol, aromatic polyester polyol, composite crosslinking agent, foaming agent, foam stabilizer, water, composite catalyst to obtain a premix; transfer the premix to a foaming machine by a pump The first working tank, making it the second work with the foaming machine The isocyanate in the can is injected into the mold having the vent hole at the top by a high pressure mixing head; the mixture of the premix in the mold and the isocyanate is aged for a predetermined time, and is formed after demolding The polyurethane foam; wherein the sorbitol polyether polyol is 25 to 60 parts by weight, the composite polyether polyol is 15 to 40 parts by weight, and
  • the foam stabilizer is 1.0 to 5.0 parts by weight
  • the water is 0.5 to 2.0 parts by weight
  • the composite catalyst is 1.0 to 3.5 parts by weight
  • the isocyanate is 120 to 160 parts by weight
  • the isocyanate has an index of 0.95 to ⁇ . 1.10.
  • the temperature of the mold is 38 to 45 ° C
  • the preset pressure is in the range of 130 to 150 bar
  • the predetermined time is in the range of 178 to 181 s.
  • the sorbitol polyether polyol, the composite polyether polyol, the diphenylmethanediamine polyether polyol, the glycerin polyether polyol, the aromatic polyester are mixed in the stirring pressure tank.
  • the composite crosslinking agent, the foaming agent, the foam stabilizer, the water, and the composite catalyst are obtained as a premix, the inner liner material of the refrigerator is cut into a sample piece and attached to the mold.
  • the raw material used is the polyurethane composition described above, and the polyurethane foam prepared by the method has a small density of less than 28.5 kg/m 3 but has strong bonding. Sex, and after foaming or high and low temperature impact, the foam and the liner will not be separated; in addition, the polyurethane foam prepared by the method has a low thermal conductivity of less than 17.5 mW/m ⁇ k, high compressive strength and minimum compressive strength. More than 150Kpa.
  • polyurethane foam provided by the invention and the preparation method thereof adopt low-gas phase thermal conductivity, low GWP and zero ODP foaming agent, not only meet the energy-saving requirements, but also are environmentally friendly and environmentally friendly.
  • a method for producing a polyurethane foam according to an embodiment of the fifth aspect of the present invention comprising: step 102, mixing a sorbitol polyether polyol, a composite polyether polyol, and a second by a stirring pressure tank Phenylmethanediamine polyether polyol, glycerin polyether polyol, aromatic polyester polyol, composite crosslinking agent, foaming agent, foam stabilizer, water, composite catalyst to obtain a premix; step 104, The premix is transferred by a pump to a first working tank of the foaming machine, and the isocyanate in the second working tank of the foaming machine is injected into the top through a high pressure mixing head at a preset pressure.
  • step 106 aging the mixture of the premix and the isocyanate in the mold for a predetermined time to form the polyurethane foam after demolding; wherein the sorbitol polyol 25-60 Parts by weight, 15 to 40 parts by weight of the composite polyether polyol, 3 to 30 parts by weight of the diphenylmethanediamine polyether polyol, 3 to 15 parts by weight of the glycerin polyether polyol, and the fragrance Group polyester polyol 3 ⁇ 20 weight 0 to 5 parts by weight of the composite crosslinking agent, 1 to 55 parts by weight of the foaming agent, 1.0 to 5.0 parts by weight of the foam stabilizer, 0.5 to 2.0 parts by weight of the water, and 1.0 to 1.0 of the composite catalyst.
  • the isocyanate is 120 to 160 parts by weight, and the isocyanate has an index of 0.95 to 1.10.
  • the raw material used is the polyurethane described above
  • the composition the preparation method is different from the preparation method described above only in that the premix and the foamed isocyanate in the foaming machine are mixed by high pressure, and the injected cavity is different in type, and one is injected into the cavity of the polyurethane foam. Inside, the other is injected directly into the cavity of the refrigerator.
  • FIG. 1 is a schematic flow chart of a method for preparing a polyurethane foam according to an embodiment of the present invention
  • FIG. 2 is a schematic flow chart of a process for preparing a polyurethane foam according to still another embodiment of the present invention.
  • the present invention proposes a polyurethane composition.
  • the polyurethane polymer comprises: 25 to 60 parts by weight of a sorbitol polyol; 15 to 40 parts by weight of a composite polyether polyol; and 3 to 30 parts by weight of diphenylmethane diamine.
  • a polyether polyol 3 to 15 parts by weight of a glycerin polyether polyol; 3 to 20 parts by weight of an aromatic polyester polyol; 0 to 5 parts by weight of a composite crosslinking agent; and 1 to 55 parts by weight of a foaming agent 1.0 to 5.0 parts by weight of a foam stabilizer; 0.5 to 2.0 parts by weight of water; 1.0 to 3.5 parts by weight of a composite catalyst; and 120 to 160 parts by weight of an isocyanate, wherein the isocyanate has an index of from 0.95 to 1.10.
  • sorbitol polyol can not only improve the strength of the foam, but also the fineness of the prepared polyurethane foam, and also reduce the thermal conductivity of the polyurethane foam;
  • the composite polyether polyol has both a high functionality polyether and The characteristics of the amino polyether make the obtained polyurethane foam have high strength, and have high activity in reacting with isocyanate, and at the same time, the curing speed after foaming is fast, effectively improving the shortcoming of the polyurethane foam skin, and thus Significantly improve the bonding performance;
  • diphenylmethane diamine polyether polyol can significantly improve the strength and release of polyurethane foam, and at the same time improve its bonding properties;
  • glycerol polyether polyol can effectively improve the flow of polyurethane composition To improve the bonding property of the obtained polyurethane foam, and the excessive use of the glycerin polyether polyol can significantly reduce the strength of the obtained polyurethane foam; the aromatic polyester polyol can significantly
  • aromatic polyester polyol has a small viscosity and flows.
  • Good which is beneficial to improve the bonding performance of polyurethane foam; composite crosslinking agent can meet the performance requirements of polyurethane foam and improve its bonding performance; too much water or too little water will make the surface of the obtained polyurethane foam crisp.
  • the viscosity of the combined polyether is moderate, and the heat generated by the reaction of water and isocyanate can make up for the heat taken away by the vaporization of the physical foaming agent, thereby achieving the effect of improving the bonding strength of the foam.
  • the polyurethane foam obtained by selecting the polyurethane composition of the formulation of the present invention has the characteristics of low density and good bonding property.
  • the polyurethane composition comprises: 25 to 50 parts by weight of sorbitol polyol; 15 to 30 parts by weight of the composite polyether polyol; and 5 to 25 parts by weight of diphenylmethane diamine Polyether polyol; 3 to 10 parts by weight of glycerin polyether polyol; 5 to 15 parts by weight of aromatic polyester polyol; 2 to 4 parts by weight of composite crosslinking agent; 1 to 55 parts by weight of blowing agent 1.0 to 5.0 parts by weight of a foam stabilizer; 1.2 to 1.9 parts by weight of water; 1.0 to 3.5 parts by weight of a composite catalyst; and 120 to 160 parts by weight of an isocyanate.
  • the density and production cost of the obtained polyurethane foam can be further reduced while improving the bonding property.
  • the specific type of the sorbitol polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected to be 380 ⁇ . 470 mg KOH/g, sorbitol polyether polyol having a viscosity of 8000 to 15000 mPa ⁇ s (25 ° C) and a functionality of 6.
  • a sorbitol polyol polymer obtained by polymerizing sorbitol as a starting agent and propylene oxide can be selected.
  • the sorbitol obtained by using sorbitol as a starting agent can not only significantly increase the strength of the polyurethane foam, but also the resulting polyurethane foam cells are more delicate, and the resulting polyurethane foam has a lower thermal conductivity.
  • the specific type of the composite polyether polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite polyether polyol can be made from sucrose. And triethanolamine and propylene oxide are polymerized, wherein the weight ratio of sucrose to triethanolamine is 1-4:1, the functionality of the composite polyether polyol is 4-6, and the hydroxyl value of the composite polyether polyol is 360-420 mgKOH. /g, the composite polyether polyol has a viscosity of 5,000 to 12,000 mPa ⁇ s (25 ° C).
  • this type of composite polyether polyol can make the obtained polyurethane foam have higher strength, and has higher activity in reaction with isocyanate, and at the same time, the curing speed after foaming is fast, and the polyurethane foam skin is effectively improved. It is easy to crispy, which further improves its bonding performance.
  • the specific type of the diphenylmethanediamine polyether polyol is not particularly limited, and those skilled in the art may select according to actual needs.
  • diphenylmethane The diamine polyether polyol can be polymerized from diphenylmethanediamine, propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide to ethylene oxide is from 1 to 4:1, and diphenylmethanediamine polyether polyol
  • the hydroxyl value is 380 to 440 mgKOH/g, and the viscosity of the diphenylmethanediamine polyether polyol is 15,000 to 25,000 mPa ⁇ s (25 ° C).
  • diphenylmethanediamine can significantly increase the strength of the resulting polyurethane foam by using two benzene rings in the molecule, and is used together with a polyether polyol.
  • the strength and mold release property of the polyurethane foam can be remarkably improved while further improving the bonding property.
  • the specific type of the glycerin polyether polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected from 160 to 300 mg KOH. / g, a glycerin polyether polyol having a viscosity of 200 to 600 mPa ⁇ s (25 ° C). The inventors have found that this type of polyether polyol has a higher fluidity, thereby further improving the bonding properties of the resulting polyurethane foam.
  • the specific type of the aromatic polyester polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected to be 200- 350 mg KOH/g, an aromatic polyester polyol having a viscosity of 1000 to 2000 mPa ⁇ s and a functionality of 2.7.
  • the inventors have found that this type of aromatic polyester polyol can significantly increase the strength of the polyurethane foam, and can significantly reduce the thermal conductivity of the resulting polyurethane foam, while having a small viscosity and high fluidity, thereby further improving the resulting polyurethane foam. Bonding performance.
  • the aromatic polyester polyol is a phthalic anhydride polyester.
  • the specific type of the foaming agent is not particularly limited, and those skilled in the art may select according to actual needs.
  • the foaming agent may include trans-1- Chloro-3,3,3-trifluoropropene, wherein trans-1-chloro-3,3,3-trifluoropropene is used in an amount of from 1 to 55 parts by weight. Thereby, the density of the obtained polyurethane foam can be further reduced.
  • the blowing agent may further include at least one of cyclopentane and pentafluoropropane, wherein the amount of the cyclopentane is 0 to 15 parts by weight, and the amount of the pentafluoropropane is 0 to 20 parts by weight.
  • the density of the obtained polyurethane foam can be further reduced.
  • the specific type of the composite catalyst is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite catalyst may be selected from the group consisting of pentamethyldivinylene. Triamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine and tetramethylhexamethylenediamine, dimethylcyclohexylamine, 1,2-dimethylimidazole and dimethylbenzylamine At least one of ammonium trimethylformate, ethyl quaternary ammonium salt and octaquat ammonium salt. The inventors have found that this type of composite catalyst can significantly increase the ripening efficiency of the polyurethane composition.
  • the specific type of the foam stabilizer is not particularly limited, and those skilled in the art can select according to actual needs.
  • the foam stabilizer may be a silicone oil. The inventors have found that the use of silicone oil as a foam stabilizer can significantly promote the formation of polyurethane foam in the polyurethane foaming process, and the resulting polyurethane foam cells are fine, thereby effectively preventing foam collapse.
  • the specific type of the composite crosslinking agent is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite crosslinking agent may be selected from the group consisting of At least two of diol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine and diphenylmethanediamine, preferably a mixture of glycerin and ethylenediamine, according to the present invention
  • the mass ratio of glycerin to ethylenediamine may be 1:1. The inventors have found that this type of composite crosslinker can give the resulting polyurethane foam a density Low and good bonding properties.
  • the specific type of isocyanate is not particularly limited, and those skilled in the art can select according to actual needs.
  • the isocyanate may be a polymethylpolyphenyl polyisocyanate. .
  • the isocyanate can significantly improve the bonding properties of the polyurethane foam.
  • the invention proposes a polyurethane foam.
  • the polyurethane foam is made from the polyurethane composition described above.
  • the obtained polyurethane foam can be made to have a low density, good adhesion property, and low production cost. It should be noted that the advantages and features described above for the polyurethane composition are equally applicable to the polyurethane foam, and are not described herein again.
  • the polyurethane foam has a density of less than 28.5 kg/m 3 .
  • the polyurethane foam has a compressive strength of more than 150 kPa.
  • the polyurethane foam has a bond strength of more than 280 kPa.
  • the polyurethane foam according to the embodiment of the present invention is prepared by using the polyurethane composition described above to have a density of less than 28.5 kg/m 3 , a thermal conductivity of less than 17.5 mW/m ⁇ k, a compressive strength of more than 150 kPa, and a bonding strength greater than 280 kPa, thereby making the polyurethane foam have strong adhesion, and the foam and the liner do not detach after foaming or high and low temperature impact.
  • the invention proposes a refrigerator.
  • the refrigerator comprises the polyurethane foam described above.
  • the refrigerator has the characteristics of good heat preservation effect and low energy consumption. It should be noted that the features and advantages described above for the polyurethane foam are also applicable to the refrigerator, and are not described herein again.
  • the invention provides a method of making a polyurethane foam.
  • the method comprises: providing a premix comprising a sorbitol polyol, a composite polyether polyol, a diphenylmethanediamine polyether polyol, a glycerol polyether polyol An alcohol, an aromatic polyester polyol, a composite crosslinking agent, a blowing agent, a foam stabilizer, water, and a composite catalyst; and injecting the premix and the isocyanate into a mold for aging treatment to obtain the polyurethane foam .
  • the inventors have found that the method can prepare the above-mentioned polyurethane foam having low density, good bonding property and low production cost, and can not only meet the energy saving requirement by adopting low gas phase thermal conductivity, low GWP and zero ODP foaming agent, and Environmentally friendly and green.
  • the method comprises:
  • the premix comprises a sorbitol polyol, a composite polyether polyol, a diphenylmethane diamine polyether polyol, a glycerin polyether polyol, an aromatic polyester polyol, a composite cross Coupling agent, foaming agent, foam stabilization Agent, water and composite catalyst.
  • the sorbitol polyether polyol, the composite polyether polyol, the diphenylmethane diamine polyether polyol, the glycerin polyether polyol, the aromatic polyester polyol, and the composite crosslinking agent can be mixed by stirring the pressure tank. , a blowing agent, a foam stabilizer, water and a composite catalyst, so that a premix can be obtained.
  • the premix comprises 25 to 60 parts by weight of sorbitol polyhydric alcohol; 15 to 40 parts by weight of the composite polyether polyol; and 3 to 30 parts by weight of diphenylmethane diamine.
  • sorbitol polyol can not only improve the strength of the foam, but also the fineness of the prepared polyurethane foam, and also reduce the thermal conductivity of the polyurethane foam;
  • the composite polyether polyol has both a high functionality polyether and The characteristics of the amino polyether make the obtained polyurethane foam have high strength, and have high activity in reacting with isocyanate, and at the same time, the curing speed after foaming is fast, effectively improving the shortcoming of the polyurethane foam skin, and thus Significantly improve the bonding performance;
  • diphenylmethane diamine polyether polyol can significantly improve the strength and release of polyurethane foam, and at the same time improve its bonding properties;
  • glycerol polyether polyol can effectively improve the flow of polyurethane composition To improve the bonding property of the obtained polyurethane foam, and the excessive use of the glycerin polyether polyol can significantly reduce the strength of the obtained polyurethane foam; the aromatic polyester polyol can significantly
  • the amount of the physical foaming agent is large, and the vaporization of the physical foaming agent during the foaming will take away a large amount of reaction heat, thereby affecting Curing performance, and if there is too much water, water reacts with isocyanate to produce a large amount of allophanate, which causes the surface of the foam to be crisp and affects the bond strength. Therefore, the physical foaming agent and chemical foaming agent and water need to be controlled at an appropriate ratio.
  • the viscosity of the combined polyether is moderate, and the heat generated by the reaction of water and isocyanate can make up for the heat taken away by the vaporization of the physical foaming agent, thereby achieving the effect of improving the bonding strength of the foam.
  • the polyurethane foam obtained by selecting the premix of the composition of the present invention has the characteristics of low density and good bonding property.
  • the premix comprises: 25 to 50 parts by weight of sorbitol polyhydric alcohol; 15 to 30 parts by weight of the composite polyether polyol; and 5 to 25 parts by weight of diphenylmethane diamine Polyether polyol; 3 to 10 parts by weight of glycerin polyether polyol; 5 to 15 parts by weight of aromatic polyester polyol; 2 to 4 parts by weight of composite crosslinking agent; 1 to 55 parts by weight of blowing agent 1.0 to 5.0 parts by weight of a foam stabilizer; 1.2 to 1.9 parts by weight of water and 1.0 to 3.5 parts by weight of a composite catalyst.
  • the density and production cost of the obtained polyurethane foam can be further improved while improving the bonding property.
  • the specific type of the sorbitol polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected to be 380 ⁇ . 470 mg KOH/g, sorbitol polyether polyol having a viscosity of 8000 to 15000 mPa ⁇ s (25 ° C) and a functionality of 6.
  • a sorbitol polyol polymer obtained by polymerizing sorbitol as a starting agent and propylene oxide can be selected.
  • the sorbitol obtained by using sorbitol as a starting agent can not only significantly increase the strength of the polyurethane foam, but also the resulting polyurethane foam cells are more delicate, and the resulting polyurethane foam has a lower thermal conductivity.
  • the specific type of the composite polyether polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite polyether polyol can be made from sucrose. And triethanolamine and propylene oxide are polymerized, wherein the weight ratio of sucrose to triethanolamine is 1-4:1, the functionality of the composite polyether polyol is 4-6, and the hydroxyl value of the composite polyether polyol is 360-420 mgKOH. /g, the composite polyether polyol has a viscosity of 5,000 to 12,000 mPa ⁇ s (25 ° C).
  • this type of composite polyether polyol can make the obtained polyurethane foam have higher strength, and has higher activity in reaction with isocyanate, and at the same time, the curing speed after foaming is fast, and the polyurethane foam skin is effectively improved. It is easy to crispy, which further improves its bonding performance.
  • the specific type of the diphenylmethanediamine polyether polyol is not particularly limited, and those skilled in the art may select according to actual needs.
  • diphenylmethane The diamine polyether polyol can be polymerized from diphenylmethanediamine, propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide to ethylene oxide is from 1 to 4:1, and diphenylmethanediamine polyether polyol
  • the hydroxyl value is 380 to 440 mgKOH/g, and the viscosity of the diphenylmethanediamine polyether polyol is 15,000 to 25,000 mPa ⁇ s (25 ° C).
  • diphenylmethanediamine can significantly increase the strength of the resulting polyurethane foam by containing two benzene rings in the molecule, and can be used together with the polyether polyol to significantly increase the strength and release property of the polyurethane foam. At the same time, the bonding performance is further improved.
  • the specific type of the glycerin polyether polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected from 160 to 300 mg KOH. / g, a glycerin polyether polyol having a viscosity of 200 to 600 mPa ⁇ s (25 ° C). The inventors have found that this type of polyether polyol has a higher fluidity, thereby further improving the bonding properties of the resulting polyurethane foam.
  • the specific type of the aromatic polyester polyol is not particularly limited, and those skilled in the art can select according to actual needs.
  • the hydroxyl value can be selected to be 200- 350 mg KOH/g, an aromatic polyester polyol having a viscosity of 1000 to 2000 mPa ⁇ s and a functionality of 2.7.
  • the inventors have found that this type of aromatic polyester polyol can significantly increase the strength of the polyurethane foam, and can significantly reduce the thermal conductivity of the resulting polyurethane foam, while having a small viscosity and high fluidity, thereby further improving the resulting polyurethane foam. Bonding performance.
  • the aromatic polyester polyol is a phthalic anhydride polyester.
  • the specific type of the foaming agent is not particularly limited, and those skilled in the art may select according to actual needs.
  • the foaming agent may include trans-1- Chloro-3,3,3-trifluoropropene, wherein trans-1-chloro-3,3,3-trifluoropropene is used in an amount of from 1 to 55 parts by weight. Thereby, the density of the obtained polyurethane foam can be further reduced.
  • the blowing agent may further include at least one of cyclopentane and pentafluoropropane.
  • the cyclopentane is used in an amount of 0 to 15 parts by weight
  • the pentafluoropropane is used in an amount of 0 to 20 parts by weight.
  • the specific type of the composite catalyst is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite catalyst may be selected from the group consisting of pentamethyldivinylene. Triamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine and tetramethylhexamethylenediamine, dimethylcyclohexylamine, 1,2-dimethylimidazole and dimethylbenzylamine At least one of ammonium trimethylformate, ethyl quaternary ammonium salt and octaquat ammonium salt. The inventors have found that this type of composite catalyst can significantly increase the ripening efficiency of the polyurethane composition.
  • the specific type of the foam stabilizer is not particularly limited, and those skilled in the art can select according to actual needs.
  • the foam stabilizer may be a silicone oil. The inventors have found that the use of silicone oil as a foam stabilizer can significantly promote the formation of polyurethane foam in the polyurethane foaming process, and the resulting polyurethane foam cells are fine, thereby effectively preventing foam collapse.
  • the specific type of the composite crosslinking agent is not particularly limited, and those skilled in the art can select according to actual needs.
  • the composite crosslinking agent may be selected from the group consisting of At least two of diol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine and diphenylmethanediamine, preferably a mixture of glycerin and ethylenediamine, according to the present invention
  • the mass ratio of glycerin to ethylenediamine may be 1:1. The inventors have found that this type of composite crosslinking agent can provide the resulting polyurethane foam with low density and good bonding properties.
  • the premix and the isocyanate are injected into a mold for aging treatment, whereby a polyurethane foam can be obtained.
  • the premix is transferred to the first working tank of the foaming machine by a pump, the isocyanate is injected into the second working tank of the foaming machine, and then the premix is mixed under a preset pressure by a high pressure mixing head.
  • the isocyanate is injected into a mold having a vent hole at the top, and then the premix and the isocyanate in the mold are aged for a predetermined time and then released to obtain a polyurethane foam.
  • the isocyanate may be used in an amount of from 120 to 160 parts by weight, wherein the isocyanate has an index of from 0.95 to 1.10.
  • the specific type of isocyanate is not particularly limited, and those skilled in the art can select according to actual needs.
  • the isocyanate may be a polymethylpolyphenyl polyisocyanate. .
  • the isocyanate can significantly improve the bonding properties of the polyurethane foam.
  • the mold may be a mold provided with a predetermined shape of the refrigerator liner, specifically, the refrigerator liner material is cut into a sample piece, and then the sample piece is pasted in the mold, or the mold may be The cavity of the refrigerator.
  • the temperature of the mold may be 38 to 45 ° C, preferably 40 ° C, the preset pressure is 130 to 150 bar, and the predetermined time is 178 to 181 s.
  • Raw material formula 40 parts by weight of sorbitol polyether polyol, 21.4 parts by weight of composite polyether polyol, 15 parts by weight of diphenylmethane diamine polyether polyol, 5 parts by weight of glycerol polyether polyol, 10 Parts by weight of aromatic polyester polyol, 3 parts by weight of a composite crosslinking agent (weight ratio of glycerin to ethylenediamine: 1:1), 0.5 part by weight of a foaming catalyst (PC-12), and 1.8 parts by weight of a gel Catalyst (PC-8), 0.5 part by weight of a polymerization catalyst (TMR-2), 2.0 parts by weight of a silicone oil-based foam stabilizer, 1.6 parts by weight of water, 38 parts by weight of trans-1-chloro-3,3, 3-Trifluoropropene, 133.9 parts by weight of Yantai Wanhua PM2010 (isocyanate index 0.97).
  • a composite crosslinking agent weight ratio of glycerin to ethylened
  • Preparation method 1 pre-mixing components other than isocyanate in the above raw material formula in a stirring pressure tank, and after the pre-mixing is finished, transferring the pre-mixed material to the white working tank of the foaming machine through the pump, and mounting it in black
  • the isocyanate in the working tank was injected into the top I-Mould mold with venting holes (mold size 1100 ⁇ 300 ⁇ 50 mm) or H-Mould mold (mold size 700 ⁇ ) by a high pressure mixing head under a pressure of 140 ⁇ 10 bar. 500 ⁇ 100mm), the mold temperature is 40° C., and then matured for 180 s, and the foam material is obtained after demolding;
  • Preparation method 2 The refrigerator liner material was cut into 100 ⁇ 40 mm sample pieces, uniformly coated on the I-Mould mold, and the raw materials were mixed in the same manner as in the preparation method 1, and then the I-Mould mold was used (the mold size was The molding was carried out at 700 ⁇ 500 ⁇ 100 mm), the mold temperature was 40° C., the aging was performed for 180 s, and the foam was obtained after demolding.
  • Raw material formula 40 parts by weight of sorbitol polyether polyol, 21.4 parts by weight of composite polyether polyol, 15 parts by weight of diphenylmethane diamine polyether polyol, 5 parts by weight of glycerol polyether polyol, 10 Parts by weight of aromatic polyester polyol, 3 parts by weight of a composite crosslinking agent (weight ratio of glycerin to ethylenediamine: 1:1), 0.6 parts by weight of a foaming catalyst (PC-12), 1.5 parts by weight of a gel Catalyst (PC-8), 0.5 part by weight of a polymerization catalyst (TMR-2), 2.0 parts by weight of a silicone oil-based foam stabilizer, 1.8 parts by weight of water, and 8 parts by weight of trans-1-chloro-3,3, 3-trifluoropropene, 12 parts by weight of cyclopentane, 5 parts by weight of pentafluoropropane (HFC-245fa), and 137.5 parts by weight of Yantai Wanh
  • Raw material composition same as in the first embodiment
  • Preparation method components other than isocyanate in the raw material formula are premixed in a stirring pressure tank, and after premixing, the premix is transferred to a white working tank of the foaming machine by a pump, and is installed in a black working tank.
  • the isocyanate was injected into the cavity of the refrigerator through a high pressure mixing head at a pressure of 140 ⁇ 10 bar.
  • the refrigeration equipment selected for testing was a door-to-door air-cooled refrigerator with a foam chamber with a foam thickness of 90 mm, a refrigerator with a foam thickness of 65 mm, a greenhouse with a foam thickness of 65 mm, and a liner material of HIPS/PE alloy. .
  • Raw material composition same as in the embodiment 2;
  • Raw material formula 20 parts by weight of sorbitol polyether polyol, 21.8 parts by weight of composite polyether polyol, 15 parts by weight of diphenylmethane diamine polyether polyol, 20 parts by weight of glycerol polyether polyol, 15 Parts by weight of aromatic polyester polyol, 3 parts by weight of ethylene glycol crosslinking agent, 0.5 parts by weight of foaming catalyst (PC-12), 1.6 parts by weight of gel catalyst (PC-8), 0.5 parts by weight Polymerization catalyst (TMR-2), 2.0 parts by weight of a silicone-based foam stabilizer, 1.6 parts by weight of water, 38 parts by weight of trans-1-chloro-3,3,3-trifluoropropene, 127.0 parts by weight Yantai Wanhua's PM2010 (isocyanate index is 0.92).
  • Raw material formula 40 parts by weight of sorbitol polyether polyol, 21.9 parts by weight of composite polyether polyol, 20 parts by weight of diphenylmethane diamine polyether polyol, and 3 parts by weight of polyether polyol D, 5 Parts by weight of aromatic polyester polyol, 3 parts by weight of ethylenediamine crosslinking agent, 0.5 parts by weight of foaming catalyst (PC-12), 1.6 parts by weight of gel catalyst (PC-8), 0.5 parts by weight Polymerization catalyst (TMR-2), 2.0 parts by weight of a silicone-based foam stabilizer, 2.5 parts by weight of water, 24 parts by weight of trans-1-chloro-3,3,3-trifluoropropene, 142.6 parts by weight Yantai Wanhua's PM2010 (isocyanate index is 1.15).
  • Raw material composition the same as the comparative example 2;
  • Determination of the density of the molded core The density of the foamed foam in the same mold except for the skin, measured in accordance with ASTM1622-88, in units of kg/m3.
  • bond strength adhesion / sample cross-sectional area, unit KPa.
  • the bond strength of the present invention is the average bond strength of 15 samples.
  • High and low temperature impact test after foaming, the box is placed for 12h, high and low temperature cycle for 4 cycles (high temperature +70 °C, low temperature -40 °C), 12 hours per cycle, high temperature and low temperature stabilization time should be ⁇ 2.5 hours (generally 4 hours), the heating time is within 2 hours, and the cooling time is within 5 hours.
  • the polyurethane foam prepared by using the proper ratio of the polyol composition and the auxiliary agent in Examples 1 and 2 has low density and low thermal conductivity, and has high compressive strength, and is also between the substrate and the substrate. The bonding strength is higher.
  • Comparative Example 1 a high proportion of low-functionality polyether, low-functionality cross-linking agent and a lower isocyanate index were used. Although the adhesive strength was high, the thermal conductivity of the foam was high and the compressive strength was low. In accordance with the production process requirements; Comparative Example 2 uses a high proportion of chemical blowing agent water, a high functionality crosslinking agent and a high isocyanate index, although the compression strength is higher, but the bonding strength of the foam is significantly lower.
  • the foams of the refrigerators prepared in Examples 3 to 4 had a lower molded core density, a lower thermal conductivity, and a higher bond strength than the refrigerator prepared in Comparative Example 3.
  • the polyurethane composition of the present invention has small viscosity, mild reaction speed, good fluidity and good adhesion; and the polyurethane foam prepared by using the polyurethane composition of the invention, on the one hand, has a small density (density is less than 28.5).
  • the thermal conductivity is low (less than 17.5mW / m ⁇ k) high compressive strength (minimum compressive strength greater than 150Kpa); at the same time, the refrigeration device produced by the polyurethane foam of the invention, such as a refrigerator, has good heat preservation effect and low energy consumption; in addition, the invention adopts low gas phase thermal conductivity, low GWP, Zero ODP foaming agent not only meets energy saving requirements, but also is environmentally friendly and environmentally friendly.

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Abstract

提供了聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱，该聚氨酯组合物包括：25～60重量份的山梨醇聚醚多元醇；15～40重量份的复合聚醚多元醇；3～30重量份的二苯基甲烷二胺聚醚多元醇；3～15重量份的甘油聚醚多元醇；3～20重量份的芳香族聚酯多元醇；0～5重量份的复合交联剂；1～55重量份的发泡剂；1.0～5.0重量份的泡沫稳定剂；0.5～2.0重量份的水；1.0～3.5重量份的复合催化剂；以及120～160重量份的异氰酸酯，其中，所述异氰酸酯的指数为0.95～1.10。

Description

聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱
优先权信息
本申请请求2015年03月24日向中国国家知识产权局提交的、专利申请号为201510130859.9的专利申请的优先权和权益，并且通过参照将其全文并入此处。
技术领域
本发明属于冰箱技术领域，具体而言，本发明涉及一种聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱。
背景技术
目前，国家对节能和环保越来越重视，因此产生了第四代新型环保高效发泡剂—反式-1-氯-3,3,3-三氟丙烯(以下简称LBA)，但是，LBA对冰箱内胆具有很强的腐蚀性，高低温试验后，内胆出现腐蚀、开裂现象。为解决这一问题，实际生产中，发明了一种HIPS/PE合金内胆。但该类合金内胆表面极性低，与发泡料之间的粘接力小。因为，硬质聚氨酯泡沫的粘接性与泡沫密度有关，密度越小，粘接性越差。使用LBA作为发泡剂的聚氨酯组合物，为满足低制造成本的需求，制备的泡沫密度较小，一般在30.5～32kg/m3之间，从而使得泡沫与冰箱内胆粘结力偏小。此外，由于HIPS/PE合金内胆使用了大量的低沸点发泡剂，发泡后，发泡剂挥发，带走泡沫表面热量，故而降低了泡沫与内胆表面的附着力。因此，该HIPS/PE合金内胆发泡后或高低温试验后，发泡层容易与内胆失粘。为解决这个问题，所能采取的措施包括：一方面进行二次电晕，增加板材电晕值，但二次电晕会增加成本，增加工时，降低冰箱内胆及冰箱的生产效率；再一方面减小PE含量，增加内胆极性，但该种措施产生的泡沫合金层厚度不均，局部可能出现没有合金层的现象，达不到抗腐蚀的效果；另一方面增加泡沫密度，因为粘接性受泡沫密度影响，密度越大，粘接性越好。但该种措施会增加冰箱的成本。
因此，如何设计出一种密度低，成本低，且粘结性能好的泡沫材料及具有该泡沫材料的冰箱成为目前亟待解决的问题。
发明内容
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出一种聚氨酯组合物、聚氨酯泡沫及其制备方法和冰箱，采用该聚氨酯组合物 所得聚氨酯泡沫的密度较低且粘结性能良好，另外生产成本较低。
在本发明的一个方面，本发明提出了一种聚氨酯组合物。根据本发明的实施例，该聚氨酯组合物包括：
25～60重量份的山梨醇聚醚多元醇；
15～40重量份的复合聚醚多元醇；
3～30重量份的二苯基甲烷二胺聚醚多元醇；
3～15重量份的甘油聚醚多元醇；
3～20重量份的芳香族聚酯多元醇；
0～5重量份的复合交联剂；
1～55重量份的发泡剂；
1.0～5.0重量份的泡沫稳定剂；
0.5～2.0重量份的水；
1.0～3.5重量份的复合催化剂；以及
120～160重量份的异氰酸酯，
其中，所述异氰酸酯的指数为0.95～1.10。
由此，采用根据本发明实施例的聚氨酯组合物所得聚氨酯泡沫的密度较低且粘结性能良好，另外生产成本较低。
另外，根据本发明上述实施例的聚氨酯组合物还可以具有如下附加的技术特征：
在本发明的一些实施例中，所述聚氨酯组合物包括：25～50重量份的所述山梨醇聚醚多元醇；15～30重量份的所述复合聚醚多元醇；5～25重量份的所述二苯基甲烷二胺聚醚多元醇；3～10重量份的所述甘油聚醚多元醇；5～15重量份的所述芳香族聚酯多元醇；2～4重量份的所述复合交联剂；1～55重量份的所述发泡剂；1.0～5.0重量份的所述泡沫稳定剂；1.2～1.9重量份的所述水；1.0～3.5重量份的所述复合催化剂；以及120～160重量份的所述异氰酸酯。由此，可以进一步降低所得聚氨酯泡沫的密度和生产成本，同时提高其粘结性能良好。
在本发明的一些实施例中，所述山梨醇聚醚多元醇的羟值为380～470mgKOH/g，所述山梨醇聚醚多元醇的粘度为8000～15000mpa·s，所述山梨醇聚醚多元醇的官能度为6。由此，不仅可以提高所得聚氨酯泡沫的强度，而且可以显著降低所得聚氨酯泡沫的导热系数。
在本发明的一些实施例中，所述复合聚醚多元醇由蔗糖、三乙醇胺和氧化丙烯聚合而成，其中，所述蔗糖与所述三乙醇胺的重量比为1～4：1，所述复合聚醚多元醇的官能度4～6，所述复合聚醚多元醇的羟值为360～420mgKOH/g，所述复合聚醚多元醇的粘度为5000～12000mpa·s。由此，可以显著提高所得聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述二苯基甲烷二胺聚醚多元醇由二苯基甲烷二胺、氧化 丙烯和氧化乙烯聚合而成，其中，所述氧化丙烯与所述氧化乙烯重量比为1～4：1，所述二苯基甲烷二胺聚醚多元醇的羟值380～440mgKOH/g，所述二苯基甲烷二胺聚醚多元醇的粘度为15000～25000mpa·s。由此，可以显著提高所得聚氨酯泡沫的强度和脱模性，同时可以改善其粘接性能。
在本发明的一些实施例中，所述甘油聚醚多元醇的羟值为160～300mgKOH/g，所述甘油聚醚多元醇的粘度为200～600mpa·s。由此，可以进一步提高所得聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述芳香族聚酯多元醇的羟值为200～350mgKOH/g，所述芳香族聚酯多元醇的粘度为1000～2000mpa·s，所述芳香族聚酯多元醇的官能度为2.7。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述芳香族聚酯多元醇为苯酐聚酯。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述发泡剂包括反式-1-氯-3,3,3-三氟丙烯，其中，所述反式-1-氯-3,3,3-三氟丙烯的用量为1～55重量份。由此，在显著降低所得聚氨酯泡沫密度的同时进一步提高聚氨酯泡沫的保温性能。
在本发明的一些实施例中，所述发泡剂进一步包括环戊烷和五氟丙烷中的至少一种，其中，所述环戊烷的用量为0～15重量份，所述五氟丙烷的用量为0～20重量份。由此，可以降低泡沫生产成本。
在本发明的一些实施例中，所述复合催化剂包括五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺和四甲基己二胺、二甲基环已胺、1,2-二甲基咪唑和二甲基苄胺、三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述泡沫稳定剂为硅油。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述复合交联剂包括乙二醇、丙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、三乙醇胺、乙二胺和二苯基甲烷二胺中的至少两种。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的一些实施例中，所述异氰酸酯为多次甲基多苯基多异氰酸酯。由此，可以进一步提高聚氨酯泡沫的粘接性能。
在本发明的第二个方面，本发明提出了一种聚氨酯泡沫。根据本发明的实施例，该聚氨酯泡沫是由上述所述的聚氨酯组合物制成的。由此，通过使用上述的聚氨酯组合物，可以使的所得聚氨酯泡沫具有密度低、粘接性能好和生产成本低的特点。
另外，根据本发明上述实施例的聚氨酯泡沫还可以具有如下附加的技术特征：
在本发明的一些实施例中，所述聚氨酯泡沫的密度小于28.5kg/m3。
在本发明的一些实施例中，所述聚氨酯泡沫的导热系数小于17.5mW/m·k。
在本发明的一些实施例中，所述聚氨酯泡沫的压缩强度大于150kpa。
在本发明的一些实施例中，所述聚氨酯泡沫的粘结强度大于280kpa。
在本发明的第三个方面，本发明提出了一种冰箱。根据本发明的实施例，该冰箱包括上述所述的聚氨酯泡沫。由此，通过使用上述的聚氨酯泡沫，使得该冰箱具有保温效果好且能耗低的特点。
在本发明的第四个方面，本发明提出了一种制备上述所述聚氨酯泡沫的方法。根据本发明的实施例，该方法包括：
提供预混物，所述预混物包含山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水和复合催化剂；以及
将所述预混物与异氰酸酯注入至模具中进行熟化处理，以便获得所述聚氨酯泡沫。
根据本发明实施例的制备聚氨酯泡沫的方法可以制备得到上述具有密度低、粘接性能好和生产成本低的聚氨酯泡沫，并且通过采用低气相导热系数、低GWP、零ODP发泡剂，不仅可以满足节能要求，而且对环境友好，绿色环保。
另外，根据本发明上述实施例的制备聚氨酯泡沫的方法还可以具有如下附加的技术特征：
在本发明的一些实施例中，所述模具中设置有具有预定形状的冰箱内胆。
在本发明的一些实施例中，所述模具为冰箱模腔。
在本发明的一些实施例中，所述模具的温度为38～45℃。
在本发明的一些实施例中，所述预设压力为130～150bar。
在本发明的一些实施例中，所述预定时间为178～181s。
根据本发明的再一个实施例，本发明的提出了一种聚氨酯组合物。
根据本发明的又一个实施例，本发明提出了一种聚氨酯泡沫及其制备方法。
本发明的又一个实施例，本发明提出了一种冰箱，该冰箱内胆上设置有利用上述聚氨酯泡沫的制备方法制备的聚氨酯泡沫。
为实现上述目的，根据本发明的第一方面的实施例，提出了一种聚氨酯组合物，该聚氨酯组合物由下列原料按照重量份配比制成：山梨醇聚醚多元醇25～60重量份、复合聚醚多元醇15～40重量份、二苯基甲烷二胺聚醚多元醇3～30重量份、甘油聚醚多元醇3～15重量份、芳香族聚酯多元醇3～20重量份、复合交联剂0～5重量份、发泡剂1～55重量份、泡沫稳定剂1.0～5.0重量份、水0.5～2.0重量份、复合催化剂1.0～3.5重量份、异氰酸酯120～160 重量份；其中，所述异氰酸酯的指数为0.95～1.10。
根据本发明的一个实施例，所述山梨醇聚醚多元醇由山梨醇和氧化丙烯聚合而成，所述山梨醇为起始剂，其中，所述山梨醇聚醚多元醇25～50重量份，所述山梨醇聚醚多元醇的羟值为380～470mgKOH/g，所述山梨醇聚醚多元醇的粘度为8000～15000mpa·s，所述山梨醇聚醚多元醇的官能度为6；所述复合聚醚多元醇由蔗糖、三乙醇胺和所述氧化丙烯聚合而成，所述蔗糖和所述三乙醇胺为起始剂，其中，所述复合聚醚多元醇15～30重量份，所述蔗糖与所述三乙醇胺的重量比为1～4：1，所述复合聚醚多元醇的官能度4～6，所述复合聚醚多元醇的羟值360～420mgKOH/g，所述复合聚醚多元醇的粘度为5000～12000mpa·s；所述二苯基甲烷二胺聚醚多元醇由二苯基甲烷二胺、所述氧化丙烯和氧化乙烯聚合而成，所述二苯基甲烷二胺为起始剂，其中，所述二苯基甲烷二胺聚醚多元醇5～25重量份，所述氧化丙烯与所述氧化乙烯重量比为1～4：1，所述二苯基甲烷二胺聚醚多元醇的羟值380～440mgKOH/g，所述二苯基甲烷二胺聚醚多元醇的粘度15000～25000mpa·s；所述甘油聚醚多元醇由甘油与所述氧化丙烯聚合而成，所述甘油为起始剂，其中，所述甘油聚醚多元醇3～10重量份，所述甘油聚醚多元醇的羟值160～300mgKOH/g，所述甘油聚醚多元醇的粘度200～600mpa·s；所述芳香族聚酯多元醇为苯酐聚酯，其中，所述芳香族聚酯多元醇5～15重量份，所述芳香族聚酯多元醇的羟值200～350mgKOH/g，所述芳香族聚酯多元醇的粘度1000～2000mpa·s，所述芳香族聚酯多元醇的官能度2.7；所述发泡剂由反式-1-氯-3,3,3-三氟丙烯组成或由所述反式-1-氯-3,3,3-三氟丙烯以及环戊烷和/或五氟丙烷混合组成，其中，所述反式-1-氯-3,3,3-三氟丙烯1～55重量份，所述环戊烷0～15重量份，所述五氟丙烷0～20重量份；所述复合催化剂由五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺和四甲基己二胺、二甲基环已胺、1,2-二甲基咪唑和二甲基苄胺、三甲基甲酸铵、乙季铵盐和辛季铵盐的一种或多种组成；所述泡沫稳定剂为Si-C结构的硅油；所述复合交联剂由乙二醇、丙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、三乙醇胺、乙二胺、二苯基甲烷二胺的多种组成；所述水1.2～1.9重量份；所述有机异氰酸酯为多次甲级多苯基多异氰酸酯。
根据本发明的实施例提供的聚氨酯组合物，粘度小，反应速度平缓，流动性及粘接性良好；其中，山梨醇聚醚多元醇以山梨醇为起始剂，不但可以提高泡沫的强度，且制备出的泡沫泡孔细腻，而且能够降低泡沫的导热系数；复合聚醚多元醇兼具高官能度聚醚和胺基聚醚的特点，制备的泡沫具有较高的强度，与有机异氰酸酯反应具有较高的活性，且发泡后固化速度快，有效的改善泡沫表皮易酥脆的缺点，以及提高了粘接强度；而二苯基甲烷二胺聚醚多元醇是由二苯基甲烷二胺为起始剂，与氧化丙烯和氧化乙烯聚合而成，其中，该二苯基甲烷二胺为胺基聚醚，分子中含有2个苯环，这样大大提高了聚氨酯本身的强度，且与聚醚多元醇一起使用，可以提高泡沫的强度和脱模性，同时可以改善粘接性能；而在 该聚氨酯组合物中加入甘油聚醚多元醇，是因为甘油聚醚多元醇具有良好的流动性，这样有利于提高粘接性，但是用量不能太多，太多时会影响泡沫的强度，优选地，该甘油聚醚多元醇为3～10重量份；其中，该聚氨酯组合物中的芳香族聚酯多元醇中含有苯环，可以提高泡沫的强度、降低泡沫的导热系数，粘度小，流动性好，有利于改善泡沫的粘接性，但由于官能度小，用量不宜过多，优选地，芳香族聚酯多元醇的用量优选为5～15重量份；其中，该聚氨酯组合物的复合交联剂既能满足泡沫性能要求，又可以提高泡沫的粘结强度。在本发明的优选实施例中，优选为2或3官能度与4官能度交联剂的混合物，并且该复合交联剂的用量为0～5重量份。在具体实施案例中，复合交联剂优选甘油和乙二胺组成的混合物，其重量比为1：1，用量优选为2～4重量份；在该聚氨酯组合物中，水的比例也是非常重要的，过多的水或过少的水都会使泡沫表面酥脆，影响粘接强度，其中，若水过少，为保证泡沫流动性和泡沫的低密度，则物理发泡剂用量多，发泡时随着物理发泡剂的汽化将带走大量的反应热，影响熟化性能；若水过多时，水与异氰酸酯反应成产大量的脲基甲酸酯，导致泡沫表面酥脆，影响粘结强度。物理发泡剂和化学发泡剂及水需控制在适当的比例范围内，使组合聚醚粘度适中，且水与异氰酸酯反应产生的热量可以弥补物理发泡剂汽化带走的热量，达到提高泡沫粘接强度的效果。其中，水的用量优选为1.2～1.9重量份。
根据本发明的第二方面的实施例，提出了一种聚氨酯泡沫，其中，所述聚氨酯泡沫由上述所述的聚氨酯组合物制成。
根据本发明的一个实施例，所述聚氨酯泡沫的密度小于28.5kg/m3。
根据本发明的一个实施例，所述聚氨酯泡沫的导热系数小于17.5mW/m·k，所述聚氨酯泡沫的压缩强度大于150kpa，所述聚氨酯泡沫的粘结强度大于280kpa。
根据本发明的实施例提供的聚氨酯泡沫，有上述所述的聚氨酯组合物制备而成，该聚氨酯泡沫的密度小于28.5kg/m3，导热系数小于17.5mW/m·k，压缩强度大于150kpa，粘结强度大于280kpa，这样使得该聚氨酯泡沫具有较强的粘接性，并且在发泡后或高低温冲击后，泡沫与内胆不会脱离。
根据本发明的第三方面的实施例，提出了一种冰箱，包括上述任一实施例所述的聚氨酯泡沫。
根据本发明的实施例提供的冰箱，保温效果好，能耗低。此外，其它包含上述聚氨酯泡沫的制冷器件同样具有上述冰箱的有益效果。
根据本发明的第四方面的实施例，提出了一种聚氨酯泡沫的制造方法，包括：通过搅拌压力罐混合山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水、复合催化剂得到预混物；将所述预混物通过泵转移到发泡机的第一工作罐中，使其与所述发泡机的第二工 作罐中的异氰酸酯通过高压混合头在预设压力下注入到顶部具有排气孔的模具中；将所述模具中的所述预混物与所述异氰酸酯的混合物熟化预定时间，脱模后形成所述聚氨酯泡沫；其中，所述山梨醇聚醚多元醇25～60重量份、所述复合聚醚多元醇15～40重量份、所述二苯基甲烷二胺聚醚多元醇3～30重量份、所述甘油聚醚多元醇3～15重量份、所述芳香族聚酯多元醇3～20重量份、所述复合交联剂0～5重量份、所述发泡剂1～55重量份、所述泡沫稳定剂1.0～5.0重量份、所述水0.5～2.0重量份、所述复合催化剂1.0～3.5重量份、所述异氰酸酯120～160重量份，且所述异氰酸酯的指数为0.95～1.10。
根据本发明的一个实施例，所述模具的温度为38～45℃，所述预设压力在130～150bar的范围内，所述预定时间在178～181s的范围内。
根据本发明的一个实施例，在所述通过搅拌压力罐混合山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水、复合催化剂得到预混物之前，将冰箱的内胆材料裁成样块，贴覆在所述模具上。
根据本发明的实施例提供的制备方法，所用原材料为上述所述的聚氨酯组合物，而通过该方法制备出的聚氨酯泡沫，密度较小，小于28.5kg/m3，却具有较强的粘接性，且发泡后或高低温冲击后，泡沫与内胆不会脱离；此外，通过该方法制备出的聚氨酯泡沫导热系数较低，小于17.5mW/m·k，压缩强度高，最小压缩强度大于150Kpa。
值得说明的是，本发明提供的聚氨酯泡沫及其制备方法，采用低气相导热系数、低GWP、零ODP发泡剂，不仅满足了节能要求，而且对环境友好，绿色环保。
根据本发明的第五方面的实施例所述聚氨酯泡沫的制造方法，如图1所示，该方法包括：步骤102，通过搅拌压力罐混合山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水、复合催化剂得到预混物；步骤104，将所述预混物通过泵转移到发泡机的第一工作罐中，使其与所述发泡机的第二工作罐中的异氰酸酯通过高压混合头在预设压力下注入到顶部具有排气孔的模具中；步骤106，将所述模具中的所述预混物与所述异氰酸酯的混合物熟化预定时间，脱模后形成所述聚氨酯泡沫；其中，所述山梨醇聚醚多元醇25～60重量份、所述复合聚醚多元醇15～40重量份、所述二苯基甲烷二胺聚醚多元醇3～30重量份、所述甘油聚醚多元醇3～15重量份、所述芳香族聚酯多元醇3～20重量份、所述复合交联剂0～5重量份、所述发泡剂1～55重量份、所述泡沫稳定剂1.0～5.0重量份、所述水0.5～2.0重量份、所述复合催化剂1.0～3.5重量份、所述异氰酸酯120～160重量份，且所述异氰酸酯的指数为0.95～1.10。
根据本发明的实施例提供的聚氨酯泡沫的制备方法，所用原材料为上述所述的聚氨酯 组合物，该种制备方法与上述所述的制备方法区别仅在于发泡机中预混物与发泡异氰酸酯通过高压混合后，注入的模腔种类不一样，一个是注入到聚氨酯泡沫的模腔内，另一个是直接注入到冰箱的模腔内。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是根据本发明一个实施例的制备聚氨酯泡沫的方法流程示意图；
图2是根据本发明再一个实施例的制备聚氨酯泡沫的方法流程示意图。
发明详细描述
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
在本发明的第一个方面。本发明提出了一种聚氨酯组合物。根据本发明的实施例，该聚氨酯聚合物包括：25～60重量份的山梨醇聚醚多元醇；15～40重量份的复合聚醚多元醇；3～30重量份的二苯基甲烷二胺聚醚多元醇；3～15重量份的甘油聚醚多元醇；3～20重量份的芳香族聚酯多元醇；0～5重量份的复合交联剂；1～55重量份的发泡剂；1.0～5.0重量份的泡沫稳定剂；0.5～2.0重量份的水；1.0～3.5重量份的复合催化剂；以及120～160重量份的异氰酸酯，其中，所述异氰酸酯的指数为0.95～1.10。发明人发现，山梨醇聚醚多元醇不但可以提高泡沫的强度，而且制备得到的聚氨酯泡沫泡孔细腻，同时还能够降低聚氨酯泡沫的导热系数；复合聚醚多元醇兼具高官能度聚醚和胺基聚醚的特点，使得所得到的聚氨酯泡沫具有较高的强度，并且与异氰酸酯反应具有较高的活性，同时发泡后固化速度快，有效的改善了聚氨酯泡沫表皮易酥脆的缺点，从而显著提高其粘接性能；二苯基甲烷二胺聚醚多元醇可以显著提高聚氨酯泡沫的强度和脱模性，同时可以改善其粘接性能；甘油聚醚多元醇可以有效改善聚氨酯组合物的流动性，从而提高所得聚氨酯泡沫的粘接性能，而甘油聚醚多元醇用量过高会明显降低所得聚氨酯泡沫的强度；芳香族聚酯多元醇中由于含有苯环，可以显著提高聚氨酯泡沫的强度，并且降低其导热系数，同时芳香族聚酯多元醇粘度小，流动性好，从而有利于改善聚氨酯泡沫的粘接性能；复合交联剂既能满足聚氨酯泡沫性能要求，又可以提高其粘结性能；过多的水或过少的水都会使所得聚氨酯泡沫表面酥脆，从 而影响其粘接性能，若水过少，为保证泡沫流动性和泡沫的低密度，则物理发泡剂用量多，发泡时随着物理发泡剂的汽化将带走大量的反应热，从而影响熟化性能，而若水过多时，水与异氰酸酯反应产生大量的脲基甲酸酯，导致泡沫表面酥脆，影响粘结强度，因此，物理发泡剂和化学发泡剂及水需控制在适当的比例范围内，使组合聚醚粘度适中，且水与异氰酸酯反应产生的热量可以弥补物理发泡剂汽化带走的热量，达到提高泡沫粘接强度的效果。由此，选择本发明配方组成的聚氨酯组合物所得聚氨酯泡沫具有密度低且粘结性能良好的特点。
根据本发明的一个实施例，聚氨酯组合物包括：25～50重量份的山梨醇聚醚多元醇；15～30重量份的复合聚醚多元醇；5～25重量份的二苯基甲烷二胺聚醚多元醇；3～10重量份的甘油聚醚多元醇；5～15重量份的芳香族聚酯多元醇；2～4重量份的复合交联剂；1～55重量份的发泡剂；1.0～5.0重量份的泡沫稳定剂；1.2～1.9重量份的水；1.0～3.5重量份的复合催化剂；以及120～160重量份的异氰酸酯。由此，可以进一步降低所得聚氨酯泡沫的密度和生产成本，同时提高其粘结性能。
根据本发明的再一个实施例，山梨醇聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为380～470mgKOH/g，粘度为8000～15000mpa·s(25℃)，官能度为6的山梨醇聚醚多元醇。例如，可以选择以山梨醇为起始剂与氧化丙烯聚合而成的山梨醇聚醚多元醇。发明人发现，以山梨醇为起始剂得到的山梨醇聚醚不仅可以显著提高聚氨酯泡沫的强度，而且所得聚氨酯泡沫泡孔更为细腻，同时所得得到的聚氨酯泡沫导热系数更低。
根据本发明的又一个实施例，复合聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合聚醚多元醇可以由蔗糖、三乙醇胺和氧化丙烯聚合而成，其中，蔗糖与三乙醇胺的重量比为1～4：1，复合聚醚多元醇的官能度4～6，复合聚醚多元醇的羟值为360～420mgKOH/g，复合聚醚多元醇的粘度为5000～12000mpa·s(25℃)。发明人发现，该类型的复合聚醚多元醇可以使得所得到的聚氨酯泡沫具有更高的强度，并且与异氰酸酯反应具有较高的活性，同时发泡后固化速度快，有效的改善了聚氨酯泡沫表皮易酥脆的缺点，从而进一步提高其粘接性能。
根据本发明的又一个实施例，二苯基甲烷二胺聚醚多元醇的具体类型并不受特别限制，本领域技术人员根据实际需要进行选择，根据本发明的具体实施例，二苯基甲烷二胺聚醚多元醇可以由二苯基甲烷二胺、氧化丙烯和氧化乙烯聚合而成，其中，氧化丙烯与氧化乙烯重量比为1～4：1，二苯基甲烷二胺聚醚多元醇的羟值380～440mgKOH/g，二苯基甲烷二胺聚醚多元醇的粘度为15000～25000mpa·s(25℃)。发明人发现，二苯基甲烷二胺由于分子中含有2个苯环，从而可以显著提高所得聚氨酯泡沫的强度，并且和聚醚多元醇一起使用， 可以显著提高聚氨酯泡沫的强度和脱模性，同时进一步改善其粘接性能。
根据本发明的又一个实施例，甘油聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为160～300mgKOH/g，粘度为200～600mpa·s(25℃)的甘油聚醚多元醇。发明人发现，该类型的聚醚多元醇具有较高的流动性，从而进一步提高所得聚氨酯泡沫的粘接性能。
根据本发明的又一个实施例，芳香族聚酯多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为200～350mgKOH/g，粘度为1000～2000mpa·s，官能度为2.7的芳香族聚酯多元醇。发明人发现，该类型的芳香族聚酯多元醇可以显著提高聚氨酯泡沫的强度，并且可以显著降低所得聚氨酯泡沫的导热系数，同时粘度较小，流动性较高，从而可以进一步改善所得聚氨酯泡沫的粘接性能。根据本发明的具体示例，芳香族聚酯多元醇为苯酐聚酯。
根据本发明的又一个实施例，发泡剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，发泡剂可以包括反式-1-氯-3,3,3-三氟丙烯，其中，反式-1-氯-3,3,3-三氟丙烯的用量为1～55重量份。由此，可以进一步降低所得聚氨酯泡沫的密度。
根据本发明的又一个实施例，发泡剂可以进一步包括环戊烷和五氟丙烷中的至少一种，其中，环戊烷的用量为0～15重量份，五氟丙烷的用量为0～20重量份。由此，可以进一步降低所得聚氨酯泡沫的密度。
根据本发明的又一个实施例，复合催化剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合催化剂可以为选自五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺和四甲基己二胺、二甲基环已胺、1,2-二甲基咪唑和二甲基苄胺、三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种。发明人发现，该类型的复合催化剂可以显著提高聚氨酯组合物的熟化效率。
根据本发明的又一个实施例，泡沫稳定剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，泡沫稳定剂可以为硅油。发明人发现，使用硅油作为泡沫稳定剂可以明显促进聚氨酯发泡过程中聚氨酯泡沫的成型，并且所得聚氨酯泡沫泡孔细腻，从而有效防止泡沫的塌泡。
根据本发明的又一个实施例，复合交联剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合交联剂可以为选自乙二醇、丙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、三乙醇胺、乙二胺和二苯基甲烷二胺中的至少两种，优选甘油和乙二胺组成的混合物，根据本发明的具体示例，甘油和乙二胺的质量比可以为1:1。发明人发现，该类型的复合交联剂可以使得所得聚氨酯泡沫具有密度 低且粘结性能良好的特点。
根据本发明的又一个实施例，异氰酸酯的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，异氰酸酯可以为多次甲基多苯基多异氰酸酯。由此，该类异氰酸酯可以显著改善聚氨酯泡沫的粘接性能。
在本发明的第二个方面，本发明提出了一种聚氨酯泡沫。根据本发明的实施例，该聚氨酯泡沫是由上述描述的聚氨酯组合物制成的。由此，通过使用上述的聚氨酯组合物，可以使的所得聚氨酯泡沫具有密度低、粘接性能好和生产成本低的特点。需要说明的是，上述针对聚氨酯组合物所描述的优点和特征同样适用于该聚氨酯泡沫，此处不再赘述。
根据本发明的一个实施例，聚氨酯泡沫的密度小于28.5kg/m3。
根据本发明的再一个实施例，聚氨酯泡沫的导热系数小于17.5mW/m·k。
根据本发明的又一个实施例，聚氨酯泡沫的压缩强度大于150kpa。
根据本发明的又一个实施例，聚氨酯泡沫的粘结强度大于280kpa。
根据本发明实施例的聚氨酯泡沫，由于采用上述所述的聚氨酯组合物制备而成，使其密度小于28.5kg/m3，导热系数小于17.5mW/m·k，压缩强度大于150kpa，粘结强度大于280kpa，由此使得该聚氨酯泡沫具有较强的粘接性，并且在发泡后或高低温冲击后，泡沫与内胆不会脱离。
在本发明的第三个方面，本发明提出了一种冰箱。根据本发明的实施例，该冰箱包括上述所述的聚氨酯泡沫。由此，通过使用上述的聚氨酯泡沫，使得该冰箱具有保温效果好且能耗低的特点。需要说明的是，上述针对聚氨酯泡沫描述的特征和优点同样适用于该冰箱，此处不再赘述。
在本发明的第四个方面，本发明提出了一种制备聚氨酯泡沫的方法。根据本发明的实施例，该方法包括：提供预混物，所述预混物包含山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水和复合催化剂；以及将所述预混物与异氰酸酯注入至模具中进行熟化处理，以便获得所述聚氨酯泡沫。发明人发现，该方法可以制备得到上述具有密度低、粘接性能好和生产成本低的聚氨酯泡沫，并且通过采用低气相导热系数、低GWP、零ODP发泡剂，不仅可以满足节能要求，而且对环境友好，绿色环保。
下面参考图2对本发明实施例的制备聚氨酯泡沫的方法进行详细描述。根据本发明的实施例，该方法包括：
S100：提供预混物
根据本发明的实施例，预混物包含山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定 剂、水和复合催化剂。具体的，可以通过搅拌压力罐混合山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水和复合催化剂，从而可以得到的预混物。
根据本发明的一个实施例，预混物包含25～60重量份的山梨醇聚醚多元醇；15～40重量份的复合聚醚多元醇；3～30重量份的二苯基甲烷二胺聚醚多元醇；3～15重量份的甘油聚醚多元醇；3～20重量份的芳香族聚酯多元醇；0～5重量份的复合交联剂；1～55重量份的发泡剂；1.0～5.0重量份的泡沫稳定剂；0.5～2.0重量份的水和1.0～3.5重量份的复合催化剂。发明人发现，山梨醇聚醚多元醇不但可以提高泡沫的强度，而且制备得到的聚氨酯泡沫泡孔细腻，同时还能够降低聚氨酯泡沫的导热系数；复合聚醚多元醇兼具高官能度聚醚和胺基聚醚的特点，使得所得到的聚氨酯泡沫具有较高的强度，并且与异氰酸酯反应具有较高的活性，同时发泡后固化速度快，有效的改善了聚氨酯泡沫表皮易酥脆的缺点，从而显著提高其粘接性能；二苯基甲烷二胺聚醚多元醇可以显著提高聚氨酯泡沫的强度和脱模性，同时可以改善其粘接性能；甘油聚醚多元醇可以有效改善聚氨酯组合物的流动性，从而提高所得聚氨酯泡沫的粘接性能，而甘油聚醚多元醇用量过高会明显降低所得聚氨酯泡沫的强度；芳香族聚酯多元醇中由于含有苯环，可以显著提高聚氨酯泡沫的强度，并且降低其导热系数，同时芳香族聚酯多元醇粘度小，流动性好，从而有利于改善聚氨酯泡沫的粘接性能；复合交联剂既能满足聚氨酯泡沫性能要求，又可以提高其粘结性能；过多的水或过少的水都会使所得聚氨酯泡沫表面酥脆，从而影响其粘接性能，若水过少，为保证泡沫流动性和泡沫的低密度，则物理发泡剂用量多，发泡时随着物理发泡剂的汽化将带走大量的反应热，从而影响熟化性能，而若水过多时，水与异氰酸酯反应产生大量的脲基甲酸酯，导致泡沫表面酥脆，影响粘结强度，因此，物理发泡剂和化学发泡剂及水需控制在适当的比例范围内，使组合聚醚粘度适中，且水与异氰酸酯反应产生的热量可以弥补物理发泡剂汽化带走的热量，达到提高泡沫粘接强度的效果。由此，选择本发明配方组成的预混物所得聚氨酯泡沫具有密度低且粘结性能良好的特点。
根据本发明的一个实施例，预混物包括：25～50重量份的山梨醇聚醚多元醇；15～30重量份的复合聚醚多元醇；5～25重量份的二苯基甲烷二胺聚醚多元醇；3～10重量份的甘油聚醚多元醇；5～15重量份的芳香族聚酯多元醇；2～4重量份的复合交联剂；1～55重量份的发泡剂；1.0～5.0重量份的泡沫稳定剂；1.2～1.9重量份的水和1.0～3.5重量份的复合催化剂。由此，可以进一步提高所得聚氨酯泡沫的密度和生产成本，同时提高其粘结性能。
根据本发明的再一个实施例，山梨醇聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为380～470mgKOH/g，粘度为8000～15000mpa·s(25℃)，官能度为6的山梨醇聚醚多元醇。 例如，可以选择以山梨醇为起始剂与氧化丙烯聚合而成的山梨醇聚醚多元醇。发明人发现，以山梨醇为起始剂得到的山梨醇聚醚不仅可以显著提高聚氨酯泡沫的强度，而且所得聚氨酯泡沫泡孔更为细腻，同时所得得到的聚氨酯泡沫导热系数更低。
根据本发明的又一个实施例，复合聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合聚醚多元醇可以由蔗糖、三乙醇胺和氧化丙烯聚合而成，其中，蔗糖与三乙醇胺的重量比为1～4：1，复合聚醚多元醇的官能度4～6，复合聚醚多元醇的羟值为360～420mgKOH/g，复合聚醚多元醇的粘度为5000～12000mpa·s(25℃)。发明人发现，该类型的复合聚醚多元醇可以使得所得到的聚氨酯泡沫具有更高的强度，并且与异氰酸酯反应具有较高的活性，同时发泡后固化速度快，有效的改善了聚氨酯泡沫表皮易酥脆的缺点，从而进一步提高其粘接性能。
根据本发明的又一个实施例，二苯基甲烷二胺聚醚多元醇的具体类型并不受特别限制，本领域技术人员根据实际需要进行选择，根据本发明的具体实施例，二苯基甲烷二胺聚醚多元醇可以由二苯基甲烷二胺、氧化丙烯和氧化乙烯聚合而成，其中，氧化丙烯与氧化乙烯重量比为1～4：1，二苯基甲烷二胺聚醚多元醇的羟值380～440mgKOH/g，二苯基甲烷二胺聚醚多元醇的粘度为15000～25000mpa·s(25℃)。发明人发现，二苯基甲烷二胺由于分子中含有2个苯环，从而可以显著提高所得聚氨酯泡沫的强度，并且和聚醚多元醇一起使用，可以显著提高聚氨酯泡沫的强度和脱模性，同时进一步改善其粘接性能。
根据本发明的又一个实施例，甘油聚醚多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为160～300mgKOH/g，粘度为200～600mpa·s(25℃)的甘油聚醚多元醇。发明人发现，该类型的聚醚多元醇具有较高的流动性，从而进一步提高所得聚氨酯泡沫的粘接性能。
根据本发明的又一个实施例，芳香族聚酯多元醇的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，可以选择羟值为200～350mgKOH/g，粘度为1000～2000mpa·s，官能度为2.7的芳香族聚酯多元醇。发明人发现，该类型的芳香族聚酯多元醇可以显著提高聚氨酯泡沫的强度，并且可以显著降低所得聚氨酯泡沫的导热系数，同时粘度较小，流动性较高，从而可以进一步改善所得聚氨酯泡沫的粘接性能。根据本发明的具体示例，芳香族聚酯多元醇为苯酐聚酯。
根据本发明的又一个实施例，发泡剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，发泡剂可以包括反式-1-氯-3,3,3-三氟丙烯，其中，反式-1-氯-3,3,3-三氟丙烯的用量为1～55重量份。由此，可以进一步降低所得聚氨酯泡沫的密度。
根据本发明的又一个实施例，发泡剂可以进一步包括环戊烷和五氟丙烷中的至少一种， 其中，环戊烷的用量为0～15重量份，五氟丙烷的用量为0～20重量份。由此，可以进一步降低所得聚氨酯泡沫的密度。
根据本发明的又一个实施例，复合催化剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合催化剂可以为选自五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺和四甲基己二胺、二甲基环已胺、1,2-二甲基咪唑和二甲基苄胺、三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种。发明人发现，该类型的复合催化剂可以显著提高聚氨酯组合物的熟化效率。
根据本发明的又一个实施例，泡沫稳定剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，泡沫稳定剂可以为硅油。发明人发现，使用硅油作为泡沫稳定剂可以明显促进聚氨酯发泡过程中聚氨酯泡沫的成型，并且所得聚氨酯泡沫泡孔细腻，从而有效防止泡沫的塌泡。
根据本发明的又一个实施例，复合交联剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，复合交联剂可以为选自乙二醇、丙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、三乙醇胺、乙二胺和二苯基甲烷二胺中的至少两种，优选甘油和乙二胺组成的混合物，根据本发明的具体示例，甘油和乙二胺的质量比可以为1:1。发明人发现，该类型的复合交联剂可以使得所得聚氨酯泡沫具有密度低且粘结性能良好的特点。
S200：将预混物与异氰酸酯注入至模具中进行熟化处理
根据本发明的实施例，将预混物与异氰酸酯注入至模具中进行熟化处理，从而可以获得聚氨酯泡沫。具体的，将预混物通过泵转移到发泡机的第一工作罐中，将异氰酸酯注入到发泡机的第二工作罐中，然后通过高压混合头在预设压力下将预混物和异氰酸酯注入到顶部具有排气孔的模具中，然后将模具中的预混物和异氰酸酯熟化预定时间后脱模即可得到聚氨酯泡沫。
根据本发明的一个实施例，异氰酸酯的用量可以为120～160重量份，其中，异氰酸酯的指数为0.95～1.10。根据本发明的再一个实施例，异氰酸酯的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，异氰酸酯可以为多次甲基多苯基多异氰酸酯。由此，该类异氰酸酯可以显著改善聚氨酯泡沫的粘接性能。
根据本发明的一个实施例，模具可以为设置有预定形状的冰箱内胆的模具，具体的，将冰箱内胆材料裁成样块，然后将该样块贴覆在模具中，或模具可以为冰箱的模腔。
根据本发明的又一个实施例，模具的温度可以为38～45℃，优选40℃，预设压力为130～150bar，预定时间为178～181s。
根据本发明实施例的制备聚氨酯泡沫的方法所得到的聚氨酯泡沫密度较小(密度小于 28.5kg/m3)，但是具有较强的粘接性，并且发泡后或高低温冲击后，泡沫与内胆不会脱离，同时通过该方法制备得到的聚氨酯泡沫导热系数较低(导热系数小于17.5mW/m·k)，压缩强度高(最小压缩强度大于150Kpa)。
下面参考具体实施例，对本发明进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本发明。
实施例1
原料配方：40重量份的山梨醇聚醚多元醇、21.4重量份的复合聚醚多元醇、15重量份的二苯基甲烷二胺聚醚多元醇、5重量份的甘油聚醚多元醇、10重量份的芳香族聚酯多元醇、3重量份的复合交联剂(甘油和乙二胺重量比1：1)、0.5重量份的发泡催化剂(PC-12)、1.8重量份的凝胶催化剂(PC-8)、0.5重量份的聚合催化剂(TMR-2)、2.0重量份的硅油类泡沫稳定剂、1.6重量份的水、38重量份的反式-1-氯-3,3,3-三氟丙烯、133.9重量份的烟台万华的PM2010(异氰酸酯指数为0.97)。
制备方法1：将上述原料配方中除异氰酸酯以外的组分在搅拌压力罐中进行预混，预混结束后，将预混物通过泵转移到发泡机的白料工作罐，与装在黑料工作罐中的异氰酸酯通过高压混合头在140±10bar的压力下注入顶部具有排气孔的Ⅰ-Mould模具中(模具尺寸为1100×300×50mm)或H-Mould模具(模具尺寸为700×500×100mm)，模具温度为40℃，接着熟化180s，脱模后得到泡沫材料；
制备方法2：将冰箱内胆材料裁成100×40mm样块，均匀贴覆在Ⅰ-Mould模具上，采用制备方法1同样的方法将原料进行混合后，然后使用I-Mould模具(模具尺寸为700×500×100mm)进行成型，模具温度为40℃，熟化180s，脱模后得到泡沫材料。
实施例2
原料配方：40重量份的山梨醇聚醚多元醇、21.4重量份的复合聚醚多元醇、15重量份的二苯基甲烷二胺聚醚多元醇、5重量份的甘油聚醚多元醇、10重量份的芳香族聚酯多元醇、3重量份的复合交联剂(甘油和乙二胺重量比1：1)、0.6重量份的发泡催化剂(PC-12)、1.5重量份的凝胶催化剂(PC-8)、0.5重量份的聚合催化剂(TMR-2)、2.0重量份的硅油类泡沫稳定剂、1.8重量份的水、8重量份的反式-1-氯-3,3,3-三氟丙烯、12重量份的环戊烷、5重量份的五氟丙烷(HFC-245fa)，137.5重量份的烟台万华的PM2010(异氰酸酯指数为1.10)。
制备方法1：同实施例1；
制备方法2：同实施例1。
实施例3
原料组成：同实施例1；
制备方法：原料配方中除异氰酸酯以外的组分在搅拌压力罐中进行预混，预混结束后，将预混物通过泵转移到发泡机的白料工作罐，与装在黑料工作罐中的异氰酸酯通过高压混合头在140±10bar的压力下注入冰箱的模腔内。选择进行试验的制冷设备为对开门风冷冰箱，其具有泡沫材料厚度为90mm的冷冻室，泡沫材料厚度为65mm的冷藏室，泡沫材料厚度为65mm的变温室，内胆材料为HIPS/PE合金。
实施例4
原料组成：同实施例2；
制备方法：同实施例3。
对比例1
原料配方：20重量份的山梨醇聚醚多元醇、21.8重量份的复合聚醚多元醇、15重量份的二苯基甲烷二胺聚醚多元醇、20重量份的甘油聚醚多元醇、15重量份的芳香族聚酯多元醇、3重量份的乙二醇交联剂、0.5重量份的发泡催化剂(PC-12)、1.6重量份的凝胶催化剂(PC-8)、0.5重量份的聚合催化剂(TMR-2)、2.0重量份的硅类泡沫稳定剂、1.6重量份的水、38重量份的反式-1-氯-3,3,3-三氟丙烯、127.0重量份的烟台万华的PM2010(异氰酸酯指数为0.92)。
制备方法1：同实施例1；
制备方法2：同实施例1。
对比例2
原料配方：40重量份的山梨醇聚醚多元醇、21.9重量份的复合聚醚多元醇、20重量份的二苯基甲烷二胺聚醚多元醇、3重量份的聚醚多元醇D、5重量份的芳香族聚酯多元醇、3重量份的乙二胺交联剂、0.5重量份的发泡催化剂(PC-12)、1.6重量份的凝胶催化剂(PC-8)、0.5重量份的聚合催化剂(TMR-2)、2.0重量份的硅类泡沫稳定剂、2.5重量份的水、24重量份的反式-1-氯-3,3,3-三氟丙烯、142.6重量份的烟台万华的PM2010(异氰酸酯指数为1.15)。
制备方法1：同实施例1；
制备方法2：同实施例1。
对比例3
原料组成：同对比例2；
制备方法：同实施例3。
评价：
1、分别对实施例1-2和对比例1-2采用同制备方法1得到的泡沫材料、实施例3和对比例3所得到的冰箱内泡沫材料的导热系数、压缩强度、模塑芯密度和膨胀率进行评价，对实施例1-2和对比例1-2采用制备方法2得到的泡沫材料的粘接强度、实施例3-4和对比例3所得冰箱的高低温试验进行评价。
2、评价指标和测试方法：
导热系数的测试：根据ISO12939-01/DIN 52612，采用EKO HC-074-200导热仪在平均温度10℃(上板2℃，下板18℃)下测定。泡沫制备后24小时，从模塑部分的中心切割泡沫样品，并在切割后立即对这些样品进行测定，单位为mW/m·k。
压缩强度的测定：根据DIN53421-06-84，采用日本岛津AGS-J测定，单位Kpa。
模塑芯密度的测定：相同模具中发泡的泡沫除外表皮之外的密度，根据ASTM1622-88测定，单位kg/m3。
膨胀率的测定：用原始模具厚度除脱模后最大泡沫厚度与原始模具厚度之差计算膨胀率，单位％。如果泡沫脱模较早，则膨胀率较高。相似地，在相同的脱模时间内泡沫膨胀率小，则该泡沫制剂能较早脱模。
粘接强度的测定：根据GB/T26689-2011(附录)，采用日本岛津AGS-J万能试验机测试粘接力，粘接强度＝粘接力/试样断面面积，单位KPa。本发明粘接强度为15块样品的平均粘接强度。
高低温冲击测试：箱体发泡后，放置12h，高低温循环4个周期(高温+70℃，低温-40℃)，每个周期12小时，高温与低温稳定时间应≥2.5小时(一般为4小时)，升温时间在2小时以内，降温时间在5小时以内。
测试结果如表1和2所示：
表1 实施例1～2和对比例1～2泡沫材料性能对比
Figure PCTCN2015081692-appb-000001
由表1数据可知：实施例1～2中使用合适比例的多元醇组合物及助剂，制备的聚氨酯泡沫具有低密度和低导热系数，并具有较高的压缩强度，同时与基材之间的粘接强度较高。
对比例1中使用高比例的低官能度聚醚、低官能度的交联剂及较低的异氰酸酯指数，虽然具有较高的粘接强度，但泡沫导热系数较高、压缩强度较低，不符合生产工艺要求；对比例2使用高比例的化学发泡剂水、高官能度的交联剂及高的异氰酸酯指数，虽然具有较高压缩强度，但是泡沫的粘接强度明显较低。
表2 实施例3～4和对比例3冰箱性能对比
Figure PCTCN2015081692-appb-000002
由表2数据可知，与对比例3制备的冰箱相比，实施例3～4制备的冰箱的泡沫材料具有较低模塑芯密度、较低的导热系数，同时具有较高的粘接强度。
综上所述：本发明的聚氨酯组合物粘度小，反应速度平缓，流动性好，粘接性好；并且采用本发明聚氨酯组合物制备的聚氨酯泡沫，一方面，虽然密度较小(密度小于28.5kg/m3)，但是具有较强的粘接性，由此使得发泡后或高低温冲击后，泡沫与内胆不会脱离；另一方面，导热系数较低(小于17.5mW/m·k)，压缩强度高(最小压缩强度大于150Kpa)；同时采用本发明聚氨酯泡沫生产的制冷器件，例如冰箱，保温效果好，能耗低；此外，本发明通过采用低气相导热系数、低GWP、零ODP发泡剂，不仅可以满足节能要求，而且对环境友好，绿色环保。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和 组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (26)

  1. 一种聚氨酯组合物，其特征在于，包括：
    25～60重量份的山梨醇聚醚多元醇；
    15～40重量份的复合聚醚多元醇；
    3～30重量份的二苯基甲烷二胺聚醚多元醇；
    3～15重量份的甘油聚醚多元醇；
    3～20重量份的芳香族聚酯多元醇；
    0～5重量份的复合交联剂；
    1～55重量份的发泡剂；
    1.0～5.0重量份的泡沫稳定剂；
    0.5～2.0重量份的水；
    1.0～3.5重量份的复合催化剂；以及
    120～160重量份的异氰酸酯，
    其中，所述异氰酸酯的指数为0.95～1.10。
  2. 根据权利要求1所述的聚氨酯组合物，其特征在于，包括：
    25～50重量份的所述山梨醇聚醚多元醇；
    15～30重量份的所述复合聚醚多元醇；
    5～25重量份的所述二苯基甲烷二胺聚醚多元醇；
    3～10重量份的所述甘油聚醚多元醇；
    5～15重量份的所述芳香族聚酯多元醇；
    2～4重量份的所述复合交联剂；
    1～55重量份的所述发泡剂；
    1.0～5.0重量份的所述泡沫稳定剂；
    1.2～1.9重量份的所述水；
    1.0～3.5重量份的所述复合催化剂；以及
    120～160重量份的所述异氰酸酯。
  3. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述山梨醇聚醚多元醇的羟值为380～470mgKOH/g，所述山梨醇聚醚多元醇的粘度为8000～15000mpa·s，所述山梨醇聚醚多元醇的官能度为6。
  4. 根据权利要求2所述的聚氨酯化合物，其特征在于，所述复合聚醚多元醇由蔗糖、三乙醇胺和氧化丙烯聚合而成，其中，所述蔗糖与所述三乙醇胺的重量比为1～4：1，所述 复合聚醚多元醇的官能度4～6，所述复合聚醚多元醇的羟值为360～420mgKOH/g，所述复合聚醚多元醇的粘度为5000～12000mpa·s。
  5. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述二苯基甲烷二胺聚醚多元醇由二苯基甲烷二胺、氧化丙烯和氧化乙烯聚合而成，其中，所述氧化丙烯与所述氧化乙烯重量比为1～4：1，所述二苯基甲烷二胺聚醚多元醇的羟值380～440mgKOH/g，所述二苯基甲烷二胺聚醚多元醇的粘度为15000～25000mpa·s。
  6. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述甘油聚醚多元醇的羟值为160～300mgKOH/g，所述甘油聚醚多元醇的粘度为200～600mpa·s。
  7. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述芳香族聚酯多元醇的羟值为200～350mgKOH/g，所述芳香族聚酯多元醇的粘度为1000～2000mpa·s，所述芳香族聚酯多元醇的官能度为2.7。
  8. 根据权利要求7所述的聚氨酯组合物，其特征在于，所述芳香族聚酯多元醇为苯酐聚酯。
  9. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述发泡剂包括反式-1-氯-3,3,3-三氟丙烯，其中，所述反式-1-氯-3,3,3-三氟丙烯的用量为1～55重量份。
  10. 根据权利要求9所述的聚氨酯组合物，其特征在于，所述发泡剂进一步包括环戊烷和五氟丙烷中的至少一种，其中，所述环戊烷的用量为0～15重量份，所述五氟丙烷的用量为0～20重量份。
  11. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述复合催化剂为选自五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺和四甲基己二胺、二甲基环已胺、1,2-二甲基咪唑和二甲基苄胺、三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种。
  12. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述泡沫稳定剂为硅油。
  13. 根据权利要求2所述的聚氨酯组合物，其特征在于，所述复合交联剂为选自乙二醇、丙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、三乙醇胺、乙二胺和二苯基甲烷二胺中的至少两种。
  14. 根据权利要求2所述的聚氨酯聚合物，其特征在于，所述异氰酸酯为多次甲基多苯基多异氰酸酯。
  15. 一种聚氨酯泡沫，其特征在于，所述聚氨酯泡沫是由权利要求1～14中任一项所述的聚氨酯组合物制成的。
  16. 根据权利要求15所述的聚氨酯泡沫，其特征在于，所述聚氨酯泡沫的密度小于28.5kg/m3。
  17. 根据权利要求15所述的聚氨酯泡沫，其特征在于，所述聚氨酯泡沫的导热系数小 于17.5mW/m·k。
  18. 根据权利要求15所述的聚氨酯泡沫，其特征在于，所述聚氨酯泡沫的压缩强度大于150kpa。
  19. 根据权利要求15所述的聚氨酯泡沫，其特征在于，所述聚氨酯泡沫的粘结强度大于280kpa。
  20. 一种冰箱，其特征在于，包括权利要求15～19任一项所述的聚氨酯泡沫。
  21. 一种制备权利要求15～19任一项所述的聚氨酯泡沫的方法，其特征在于，包括：
    提供预混物，所述预混物包含山梨醇聚醚多元醇、复合聚醚多元醇、二苯基甲烷二胺聚醚多元醇、甘油聚醚多元醇、芳香族聚酯多元醇、复合交联剂、发泡剂、泡沫稳定剂、水和复合催化剂；以及
    将所述预混物与异氰酸酯注入至模具中进行熟化处理，以便获得所述聚氨酯泡沫。
  22. 根据权利要求21所述的方法，其特征在于，所述模具中设置有具有预定形状的冰箱内胆。
  23. 根据权利要求21所述的方法，其特征在于，所述模具为冰箱模腔。
  24. 根据权利要求21所述的方法，其特征在于，所述模具的温度为38～45℃。
  25. 根据权利要求21所述的方法，其特征在于，所述预设压力为130～150bar。
  26. 根据权利要求21所述的方法，其特征在于，所述预定时间为178～181s。
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CN119529227A (zh) * 2025-01-23 2025-02-28 山东美生热能科技有限公司 地热井油管用聚氨酯隔热保温材料及其制备方法

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