WO2018157292A1 - 组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器 - Google Patents

组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器 Download PDF

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WO2018157292A1
WO2018157292A1 PCT/CN2017/075233 CN2017075233W WO2018157292A1 WO 2018157292 A1 WO2018157292 A1 WO 2018157292A1 CN 2017075233 W CN2017075233 W CN 2017075233W WO 2018157292 A1 WO2018157292 A1 WO 2018157292A1
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weight
polyol
parts
polyether
polyurethane foam
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PCT/CN2017/075233
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English (en)
French (fr)
Inventor
余远明
赵士虎
曲绍鹤
袁海霞
朱洪阳
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芜湖美的厨卫电器制造有限公司
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Priority to PCT/CN2017/075233 priority Critical patent/WO2018157292A1/zh
Publication of WO2018157292A1 publication Critical patent/WO2018157292A1/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
    • C08G18/28—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
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

Definitions

  • the invention relates to the field of water heaters, in particular to a combined polyether, a rigid polyurethane foam, a preparation method thereof and a water heater.
  • rigid polyurethane foam is usually coated on the outer surface of the inner tank to reduce the heat loss of the water in the inner tank to improve the energy saving capacity of the water heater.
  • the currently used rigid polyurethane foam is prepared by using a foaming agent including HCFC-141b (monofluorodichloroethane), and HCFC-141b (monofluorodichloroethane) has a destructive effect on the ozone layer. Meet environmental requirements.
  • the main object of the present invention is to propose a combined polyether intended to make the rigid polyurethane foam obtained from the combined polyether environmentally friendly.
  • the combined polyether proposed by the present invention comprises a polyol comprising a polyether polyol and/or a polyester polyol, and a foaming agent comprising hexafluorobutene.
  • the blowing agent further comprises pentane and/or hydrofluorocarbon.
  • the pentane comprises at least one of cyclopentane, isopentane and n-pentane.
  • the hydrofluorocarbon is one of pentafluoropropane, pentafluorobutane and tetrafluoroethane.
  • the polyether polyol comprises at least one of a polyether polyol A, a polyether polyol B, and a polyether polyol C, the polyester polyol being a polyester polyol D, wherein:
  • the polyether polyol A is prepared by polymerizing propylene oxide with sorbitol as a starting agent, having a viscosity of 8000 to 15000 mPa ⁇ s, a hydroxyl value of 360 to 500 mgKOH/g, and a functionality of 6;
  • the polyether polyol B is obtained by polymerizing propylene oxide with glycerin as a starting agent, having a viscosity of 250-600 mPa ⁇ s and a hydroxyl value of 150-350 mgKOH/g;
  • the polyether polyol C is prepared by polymerizing oxidized propylene with sucrose as a starting agent, having a viscosity of 5000 to 12000 mPa ⁇ s and a hydroxyl value of 360 to 440 mgKOH/g;
  • the polyester polyol D is a phthalic anhydride polyester having a viscosity of 1000 to 2000 mPa ⁇ s, a hydroxyl value of 200 to 350 mgKOH/g, and a functionality of 2.7.
  • the combined polyether further comprises water, a composite catalyst, a foam stabilizer and a flame retardant, wherein:
  • the composite catalyst comprises pentamethyldiethylenetriamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine and tetramethylhexamethylenediamine, dimethylcyclohexylamine, 1,2- At least one of dimethylimidazole and dimethylbenzylamine, (2-hydroxypropyl)trimethylformate, a quaternary ammonium salt, and a quaternary ammonium salt;
  • the foam stabilizer is a silicone oil of Si-C structure
  • the flame retardant includes tris(2-chloroethyl)phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, neopentyl glycol ethylene phosphate At least one of an ester, dimethyl methylphosphonate, resorcinol bis(diphenyl phosphate), diethyl ethyl phosphate, and dimethyl propyl phosphate.
  • the combined polyether comprises:
  • the polyether polyol A has a weight fraction of 40 to 60
  • the polyether polyol B has a weight fraction of 5 to 15
  • the polyether polyol C has a weight fraction of 20 to 30.
  • the polyester polyol D has a weight fraction of 5 to 15, and the flame retardant has a weight fraction of 5 to 10.
  • the invention also provides a preparation method of a rigid polyurethane foam, comprising the following steps:
  • the combined polyether comprises a polyol and a blowing agent, the polyol comprising a polyether polyol and/or a polyester polyol, the blowing agent comprising hexafluorobutene ;
  • the uniformly mixed composition is injected into the foaming cavity for foaming.
  • the organic isocyanate is a multi-stage polyphenyl polyisocyanate.
  • the weight ratio between the organic isocyanate and the combined polyether is from 0.9 to 1.3.
  • the foaming cavity has an external temperature range of 20 to 50 ° C and an internal temperature range of 20 to 50 ° C.
  • the temperature of the composition ranges from 15 to 25 ° C, and the operating pressure of the injection ranges from 12 to 14 MPa.
  • the present invention also proposes a rigid polyurethane foam prepared by the aforementioned method for producing a rigid polyurethane foam.
  • the present invention also provides a water heater comprising a liner and a rigid polyurethane foam prepared by the method for preparing the aforementioned rigid polyurethane foam and attached to the outer surface of the inner liner.
  • the foaming agent used in combining the polyether comprises hexafluorobutene, the hexafluorobutene has low thermal conductivity, zero ozone depletion potential and acceptable low global warming potential (less than 10.0) And the like, therefore, the rigid polyurethane foam obtained by the combined polyether can be environmentally friendly and has a low thermal conductivity, so that the water heater coated with the rigid polyurethane foam can meet environmental protection requirements and has low energy. Consumption.
  • FIG. 1 is a schematic flow chart of an embodiment of a method for preparing a rigid polyurethane foam of the present invention.
  • first”, “second”, etc. are used for descriptive purposes only, and are not to be construed as indicating or Implied its relative importance or implicitly indicates the number of technical features indicated.
  • features defining “first” or “second” may include at least one of the features, either explicitly or implicitly.
  • the technical solutions between the various embodiments may be combined with each other, but must be based on the realization of those skilled in the art, and when the combination of the technical solutions is contradictory or impossible to implement, it should be considered that the combination of the technical solutions does not exist. It is also within the scope of protection required by the present invention.
  • the invention proposes a combined polyether.
  • the combined polyether comprises a polyol and a blowing agent.
  • the polyol includes a polyether polyol and a polyester polyol
  • the foaming agent includes hexafluorobutene (abbreviated as FEA-1100).
  • FEA-1100 has the advantages of low thermal conductivity, zero ozone depletion potential, and acceptable low global warming potential (less than 10.0), so that the combined polyether including FEA-1100 can be obtained.
  • the polyurethane foam is environmentally friendly and has a low thermal conductivity, so that the water heater coated with the rigid polyurethane foam can meet environmental requirements and has low energy consumption.
  • the polyol in the combined polyether may further include only one of a polyether polyol and a polyester polyol.
  • the blowing agent may further include at least one of pentane and hydrofluorocarbon, thereby ensuring that the obtained rigid polyurethane foam is environmentally friendly and has a low thermal conductivity.
  • the pentane may include at least one of cyclopentane, isopentane, and n-pentane, and preferably includes cyclopentane
  • the hydrofluorocarbon may be pentafluoropropane (HFC-245fa), pentafluorobutane.
  • HFC-365mfc tetrafluoroethane
  • HFC-134a tetrafluoroethane
  • the polyether polyol comprises at least one of polyether polyol A, polyether polyol B and polyether polyol C, and the polyester polyol is polyester polyol D, wherein :
  • the polyether polyol A is prepared by polymerizing propylene oxide with sorbitol as a starting agent, having a viscosity of 8000 to 15000 mPa ⁇ s, a hydroxyl value of 360 to 500 mgKOH/g, and a functionality of 6.
  • the polyether polyol A can increase the strength of the prepared rigid polyurethane foam, make the cells in the prepared rigid polyurethane foam fine and uniform, and can reduce the thermal conductivity.
  • the polyether polyol B is obtained by polymerizing propylene oxide with glycerin as a starting agent, and has a viscosity of 250 to 600 mPa ⁇ s and a hydroxyl value of 150 to 350 mgKOH/g.
  • the polyether polyol B improves the fluidity of the combined polyether and improves the adhesion of the prepared rigid polyurethane foam.
  • Polyether polyol C is prepared by polymerizing oxidized propylene with sucrose as a starting agent, viscosity of 5000 ⁇ 12000mpa•s, and hydroxyl value of 360 ⁇ 440mgKOH/g.
  • the polyether polyol C has high functionality, has high activity in reaction with organic isocyanate, and has a fast curing speed after foaming.
  • the shortcoming of the prepared rigid polyurethane foam skin is easy to be crisp, and the bond strength and mechanical strength of the prepared rigid polyurethane foam are improved.
  • the polyester polyol D is a phthalic anhydride polyester having a viscosity of 1000 to 2000 mPa ⁇ s, a hydroxyl value of 200 to 350 mgKOH/g, and a functionality of 2.7.
  • the polyester polyol D contains a benzene ring, which can improve the strength of the prepared rigid polyurethane foam and reduce the thermal conductivity of the prepared rigid polyurethane foam; in addition, the polyester polyol D has small viscosity and good fluidity, which is favorable for the polyester polyol D. Improve the adhesion of the prepared rigid polyurethane foam.
  • the combined polyether further comprises water, a composite catalyst, a foam stabilizer and a flame retardant, wherein:
  • the composite catalyst includes pentamethyldiethylenetriamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine (PC-12), tetramethylhexamethylenediamine, dimethylcyclohexylamine (PC) -8), at least one of 1,2-dimethylimidazole and dimethylbenzylamine, (2-hydroxypropyl)trimethylformate (TMR-2), a quaternary ammonium salt, and a quaternary ammonium salt
  • TMR-2 (2-hydroxypropyl)trimethylformate
  • TMR-2 quaternary ammonium salt
  • a quaternary ammonium salt a quaternary ammonium salt
  • a composite catalyst can increase the flow rate of the foam while increasing the reaction speed, so as to facilitate rapid demolding.
  • the composite catalyst generally includes a foaming catalyst, a gel catalyst, and a polymerization catalyst.
  • the foam stabilizer is a silicone oil of Si-C structure, such as Moto's L-6863, L-6988, L-6952; EST's AK8812, AK8809, etc., and preferably L-6988, AK8809; such a foam stabilizer
  • the nucleation effect of the combined polyether at the time of foaming can be improved.
  • Flame retardants include tris(2-chloroethyl)phosphate (TCEP), tris(2-chloropropyl) phosphate (TCPP), tris(2,3-dichloropropyl) phosphate (TDCPP), new Pentylene glycol ethylene glycol phosphate, dimethyl methylphosphonate (DMMP), resorcinol bis(diphenyl phosphate) (RDP), diethyl diethyl phosphate (DEEP) and propyl phosphate At least one of methyl esters (DMPP); such flame retardants can reduce the flammability of the prepared rigid polyurethane foam.
  • TCEP tris(2-chloroethyl)phosphate
  • TCPP tris(2-chloropropyl) phosphate
  • TDCPP tris(2,3-dichloropropyl) phosphate
  • DMMP dimethyl methylphosphonate
  • RDP resorcinol bis(diphenyl phosphate)
  • the flame retardant is preferably neopentyl glycol ethylene glycol phosphate, dimethyl methylphosphonate (DMMP), resorcinol bis (diphenyl phosphate) (RDP), diethyl phosphate At least one of ester (DEEP) and dimethyl propyl phosphate (DMPP), such flame retardant is a halogen-free flame retardant.
  • the combined polyether preferably comprises: 30 to 60 parts by weight of polyether polyol A; 3 to 15 parts by weight of polyether polyol B; 15 to 40 parts by weight of polyether polyol C; 5 to 20 parts by weight of polyester polyol D; 0 to 15 parts by weight of pentane; 0 to 20 parts by weight of hydrofluorocarbon; 1 to 30 parts by weight of FEA-1100; 0.5 to 2.0 parts by weight of water; ⁇ 3.5 parts by weight of the composite catalyst; 1 to 5 parts by weight of the foam stabilizer; and 1 to 15 parts by weight of the flame retardant.
  • the rigid polyurethane foam coated on the outer liner is usually prepared by foaming at a higher temperature, and the ordinary foamed material is not suitable for foaming at a higher temperature.
  • the foamed material of the combined polyether under the formulation of the present embodiment can be applied to the foaming preparation at a higher temperature, and can meet the preparation requirements of the rigid polyurethane foam of the water heater.
  • the weight fraction of the polyether polyol A may further preferably be 40 to 60, so that the heat conductivity of the prepared rigid polyurethane foam is low.
  • the parts by weight of the polyether polyol B may further preferably be 5 to 15, so that the combined polyether has a high fluidity.
  • the part by weight of the polyether polyol C may be further preferably from 20 to 30, so that the bond strength and mechanical strength of the prepared rigid polyurethane foam are high.
  • the part by weight of the polyester polyol D may further preferably be 5 to 15. Since the functionality of the polyester polyol D is small, the amount of the polyester polyol D is not excessive, otherwise the release property of the prepared rigid polyurethane foam is affected.
  • the parts by weight of the flame retardant may further preferably be 5 to 10, so that the temperability of the prepared rigid polyurethane foam is low.
  • the invention also proposes a preparation method of a rigid polyurethane foam.
  • a method for preparing the rigid polyurethane foam comprises the following steps:
  • Step S10 mixing the organic isocyanate and the combined polyether uniformly;
  • step S20 the uniformly mixed composition is injected into the foaming cavity to be foamed.
  • the specific structure of the combined polyether refers to the above embodiment.
  • the combined polyether comprises a polyol and a foaming agent, wherein the polyol comprises a polyether polyol and/or a polyester polyol, and a foaming agent. Includes hexafluorobutene.
  • the rigid polyurethane foam prepared by the preparation method of the rigid polyurethane foam of the present invention can be made environmentally friendly and has a low thermal conductivity, so that the water heater coated with the rigid polyurethane foam can satisfy the requirements. Environmentally friendly and low energy consumption.
  • the composition for injecting the foaming cavity further comprises an organic isocyanate such as, but not limited to, PM2010 of Yantai Wanhua, the organic isocyanate can improve the fluidity of the foam and keep the foam high. Strength; Generally, the organic isocyanate is preferably a plurality of grades of polyphenyl polyisocyanate.
  • the weight ratio between the organic isocyanate and the combined polyether is preferably from 0.9 to 1.3 in order to balance the strength and brittleness of the obtained rigid polyurethane foam.
  • step S10 the method further includes the steps of:
  • premixing of the components in the combined polyether and the mixing of the organic isocyanate with the premixed polyether are advantageous for uniform mixing of the composition comprising the organic isocyanate and the combined polyether. Thereby, the overall performance consistency of the prepared rigid polyurethane foam is improved.
  • the foaming cavity generally refers to a cavity that is spaced between the outer surface of the inner tank and the inner surface of the water heater casing.
  • the outer temperature of the foaming cavity ranges from 20 to 50 ° C
  • the internal temperature ranges from 20 to 50 ° C.
  • the temperature range of the composition is preferably 15 to 25 ° C
  • the operating pressure range of the injection is preferably 12 to 14 MPa.
  • Raw material formula 40 parts by weight of polyether polyol A, 6 parts by weight of polyether polyol B, 30 parts by weight of polyether polyol C, 10 parts by weight of polyester polyol, and 8.5 parts by weight of composite flame retardant ( DEEP to DMPP weight ratio 1:1), 0.4 parts by weight of foaming catalyst (PC-12), 1.9 parts by weight of gel catalyst (PC-8), 0.5 parts by weight of polymerization catalyst (TMR-2), 2.0 weight Parts of a silicone-based foam stabilizer, 0.7 parts by weight of water, 5.5 parts by weight of HFC-245fa, 25 parts by weight of FEA-1100, and 126.69 parts by weight of Yantai Wanhua's PM2010 (organic isocyanate).
  • the preparation method comprises: pre-mixing the components other than the organic isocyanate in the raw material formula in a stirring pressure tank; after being pre-mixed uniformly, transferring the premix to the white working tank of the foaming machine through a pump, thereby
  • the organic isocyanate contained in the black working tank is molded by a high-pressure mixing head under a pressure of 12.5 MPa into a water heater tank mold having a vent hole at the top; the outer temperature of the foam cavity mold is 28 ° C, and the internal temperature is 32 ° C.
  • the material temperature in the high pressure foaming machine is 18 °C.
  • Raw material formula 40 parts by weight of polyether polyol A, 10 parts by weight of polyether polyol B, 25 parts by weight of polyether polyol C, 15 parts by weight of polyester polyol, and 4 parts of composite flame retardant (DEEP 1:1 by weight ratio to DMPP, 0.5 part 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 Silicone foam stabilizer, 1.5 parts by weight of water, 24 parts by weight of HCFC-141b, 130.20 parts by weight of Yantai Wanhua's PM2010 (organic isocyanate).
  • DEEP 1:1 by weight ratio to DMPP 0.5 part 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 Silicone foam stabilizer, 1.5 parts by weight of water, 24 parts by weight of HCFC-
  • the properties of the rigid polyurethane foams obtained in the examples and comparative examples were measured.
  • the test standard of foam core density is in accordance with GB/T6343-2009
  • the thermal conductivity test of foam is carried out according to the standard GB/T10295-2008
  • the energy efficiency test of solar water heater is in accordance with the standard GB. Conducted at 18708-2002.
  • Performance parameter Example Comparative example Foam core density kg / cubic meter 35.72 37.80 Thermal conductivity 22.5 ° C 18.70 18.60 Water heater energy consumption coefficient 0.670 0.660
  • the density of the foam core in the embodiment is lower than that in the comparative example, which can reduce the amount of foaming of the rigid polyurethane foam in the water heater, reduce the cost, and reduce the total weight of the whole product;
  • the thermal conductivity coefficient and the water heater energy consumption coefficient are not much different from those in the comparative example. Therefore, the technical solution of the present invention can effectively solve the environmental protection problem caused by the foaming agent HCFC-141b in the foaming material in the water heater industry.
  • the invention also provides a rigid polyurethane foam prepared by the above-mentioned preparation method of the rigid polyurethane foam, and the specific steps of the preparation method of the rigid polyurethane foam refer to the above embodiment, because the rigid polyurethane foam All the technical solutions of all the above embodiments are adopted, so that at least all the beneficial effects brought by the technical solutions of the above embodiments are not repeated herein.
  • the present invention also provides a water heater comprising a liner and a rigid polyurethane foam.
  • the specific structure of the rigid polyurethane foam refers to the above embodiment. Since the water heater adopts all the technical solutions of all the above embodiments, it has at least the above. All the beneficial effects brought about by the technical solutions of the embodiments are not described herein again.
  • the rigid polyurethane foam is attached to the outer surface of the inner liner by means of high pressure foaming.

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Abstract

一种组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器，其中，组合聚醚包括多元醇和发泡剂，所述多元醇包括聚醚多元醇和/或聚酯多元醇，所述发泡剂包括六氟丁烯。以该组合聚醚所得的硬质聚氨酯泡沫材料环境友好且导热系数较低。

Description

组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器
技术领域
本发明涉及热水器领域，特别涉及一种组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器。
背景技术
在热水器行业，通常在其内胆的外表面包覆硬质聚氨酯泡沫，来降低内胆内水的热量损失，以提高热水器的节能能力。然而，目前常用的硬质聚氨酯泡沫是采用包括HCFC-141b（一氟二氯乙烷）的发泡剂所制备的，而HCFC-141b（一氟二氯乙烷）对臭氧层具有破坏作用，无法满足环保要求。
发明内容
本发明的主要目的是提出一种组合聚醚，旨在使得以该组合聚醚所得的硬质聚氨酯泡沫材料环境友好。
为实现上述目的，本发明提出的组合聚醚包括多元醇和发泡剂，所述多元醇包括聚醚多元醇和/或聚酯多元醇，所述发泡剂包括六氟丁烯。
优选地，所述发泡剂还包括戊烷和/或氢氟烃。
优选地，所述戊烷包括环戊烷、异戊烷和正戊烷中的至少一种。
优选地，所述氢氟烃为五氟丙烷、五氟丁烷和四氟乙烷中的一种。
优选地，所述聚醚多元醇包括聚醚多元醇A、聚醚多元醇B和聚醚多元醇C的至少一种，所述聚酯多元醇为聚酯多元醇D，其中：
所述聚醚多元醇A是以山梨醇为起始剂，与氧化丙烯聚合而成，粘度为8000~15000mpa•s，羟值为360~500mgKOH/g，官能度为6；
所述聚醚多元醇B是以甘油为起始剂，与氧化丙烯聚合而成，粘度为250~600mpa•s，羟值为150~350mgKOH/g；
所述聚醚多元醇C是以蔗糖为起始剂，与氧化丙烯聚合而成，粘度为5000~12000mpa•s，羟值为360~440mgKOH/g；
所述聚酯多元醇D为苯酐聚酯，粘度1000~2000mpa•s，羟值200~350mgKOH/g，官能度为2.7。
优选地，所述组合聚醚还包括水、复合催化剂、泡沫稳定剂和阻燃剂，其中：
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、（2-羟基丙基）三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种；
所述泡沫稳定剂为Si-C结构的硅油；
所述阻燃剂包括三（2-氯乙基）磷酸酯、磷酸三（2-氯丙基）酯、磷酸三（2，3-二氯丙基）酯、新戊二醇乙二醇磷酸酯、甲基膦酸二甲酯、间苯二酚双（二苯基磷酸酯）、乙基磷酸二乙酯和丙基磷酸二甲酯中的至少一种。
优选地，所述组合聚醚包括：
30~60重量份的所述聚醚多元醇A；
3~15重量份的所述聚醚多元醇B；
15~40重量份的所述聚醚多元醇C；
5~20重量份的所述聚酯多元醇D；
0~15重量份的所述戊烷；
0~20重量份的所述氢氟烃；
1~30重量份的所述六氟丁烯；
0.5~2.0重量份的所述水；
1~3.5重量份的所述复合催化剂；
1~5重量份的所述泡沫稳定剂；以及
1~15重量份的所述阻燃剂。
优选地，所述聚醚多元醇A的重量份数为40~60，所述聚醚多元醇B的重量份数为5~15，所述聚醚多元醇C的重量份数为20~30，所述聚酯多元醇D的重量份数为5~15，所述阻燃剂的重量份数为5~10。
本发明还提出一种硬质聚氨酯泡沫的制备方法，包括以下步骤：
将有机异氰酸酯与组合聚醚混合均匀；其中，所述组合聚醚包括多元醇和发泡剂，所述多元醇包括聚醚多元醇和/或聚酯多元醇，所述发泡剂包括六氟丁烯；
将混合均匀后的组合物注入发泡空腔进行发泡。
优选地，所述有机异氰酸酯为多次甲级多苯基多异氰酸酯。
优选地，所述有机异氰酸酯与所述组合聚醚之间的重量比值为0.9~1.3。
优选地，在所述将混合均匀后的组合物注入发泡空腔进行发泡的步骤中，所述发泡空腔的外部温度范围为20~50℃，内部温度范围为20~50℃。
优选地，在所述将混合均匀后的组合物注入发泡空腔进行发泡的步骤中，所述组合物的温度范围为15~25℃，所述注入的操作压力范围为12~14Mpa。
本发明还提出一种硬质聚氨酯泡沫，所述硬质聚氨酯泡沫由前述硬质聚氨酯泡沫的制备方法所制备。
本发明还提出一种热水器，包括内胆以及硬质聚氨酯泡沫，所述硬质聚氨酯泡沫由前述硬质聚氨酯泡沫的制备方法所制备，并附着于所述内胆的外表面。
本发明的技术方案中，组合聚醚所采用的发泡剂包括六氟丁烯，该六氟丁烯具有低导热系数、零臭氧消耗潜势以及可接受的低全球变暖潜势（小于10.0）等优势，因此，可使得以该组合聚醚所得硬质聚氨酯泡沫材料环境友好且导热系数较低，从而可使得由该硬质聚氨酯泡沫材料包覆内胆的热水器能满足环保要求且具有低能耗。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图示出的结构获得其他的附图。
图1为本发明硬质聚氨酯泡沫的制备方法一实施例的流程示意图。
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明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发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明，若本发明实施例中有涉及“第一”、“第二”等的描述，则该“第一”、“第二”等的描述仅用于描述目的，而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
本发明提出一种组合聚醚。
在本发明一实施例中，该组合聚醚包括多元醇和发泡剂。其中，多元醇包括聚醚多元醇和聚酯多元醇，发泡剂包括六氟丁烯（简称FEA-1100）。本实施例中，FEA-1100具有低导热系数、零臭氧消耗潜势以及可接受的低全球变暖潜势（小于10.0）等优势，因此，可使得以包括FEA-1100的组合聚醚所得硬质聚氨酯泡沫材料环境友好且导热系数较低，从而可使得由该硬质聚氨酯泡沫材料包覆内胆的热水器能满足环保要求且具有低能耗。然本设计不限于此，于其他实施例中，该组合聚醚中的多元醇还可仅包括聚醚多元醇和聚酯多元醇中的其中之一。
在本实施例中，进一步地，所述发泡剂还可包括戊烷和氢氟烃中的至少一种，由此，可在保证所得的硬质聚氨酯泡沫材料环境友好且具有较低导热系数的同时，降低原料成本。具体地，戊烷可以包括环戊烷、异戊烷和正戊烷中的至少一种，并优选地包括环戊烷；氢氟烃则可以为五氟丙烷（HFC-245fa）、五氟丁烷（HFC-365mfc）和四氟乙烷（HFC-134a）中的一种，并优选为五氟丙烷。
在本实施例中，进一步地，所述聚醚多元醇包括聚醚多元醇A、聚醚多元醇B和聚醚多元醇C的至少一种，聚酯多元醇为聚酯多元醇D，其中：
聚醚多元醇A是以山梨醇为起始剂，与氧化丙烯聚合而成，粘度为8000~15000mpa•s，羟值为360~500mgKOH/g，官能度为6。该聚醚多元醇A可以提高所制备的硬质聚氨酯泡沫的强度，使得所制备的硬质聚氨酯泡沫中泡孔细腻均匀，并可以降低导热系数。
聚醚多元醇B是以甘油为起始剂，与氧化丙烯聚合而成，粘度为250~600mpa•s，羟值为150~350mgKOH/g。该聚醚多元醇B可提高组合聚醚的流动性，改善所制备硬质聚氨酯泡沫的粘结性。
聚醚多元醇C是以蔗糖为起始剂，与氧化丙烯聚合而成，粘度为5000~12000mpa•s，羟值为360~440mgKOH/g。在通过该组合聚醚制备硬质聚氨酯泡沫的过程中，通常还需加入有机异氰酸酯；该聚醚多元醇C官能度高，与有机异氰酸酯反应具有较高的活性，发泡后固化速度快，可改善所制备的硬质聚氨酯泡沫表皮易酥脆的缺点，提高所制备硬质聚氨酯泡沫的粘结强度和力学强度。
聚酯多元醇D为苯酐聚酯，粘度1000~2000mpa•s，羟值200~350mgKOH/g，官能度2.7。该聚酯多元醇D含有苯环，可提高所制备硬质聚氨酯泡沫的强度，并降低所制备硬质聚氨酯泡沫的导热系数；另外，该聚酯多元醇D粘度小，流动性好，有利于改善所制备硬质聚氨酯泡沫的粘接性。
在本实施例中，进一步地，该组合聚醚还包括水、复合催化剂、泡沫稳定剂和阻燃剂，其中：
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（PC-12）和四甲基己二胺、二甲基环已胺（PC-8）、1，2-二甲基咪唑和二甲基苄胺、（2-羟基丙基）三甲基甲酸铵（TMR-2）、乙季铵盐和辛季铵盐中的至少一种；此类复合催化剂可在提高反应速度的同时，提高泡沫的流动性，以便于快速脱模。需要说明的是，复合催化剂通常包括发泡催化剂、凝胶催化剂和聚合催化剂。
泡沫稳定剂为Si-C结构的硅油，如迈图的L-6863，L-6988，L-6952；美思德的AK8812，AK8809等，并优选为L-6988，AK8809；此类泡沫稳定剂可提高组合聚醚在发泡时的成核效果。
阻燃剂包括三（2-氯乙基）磷酸酯（TCEP）、磷酸三（2-氯丙基）酯（TCPP）、磷酸三（2,3-二氯丙基）酯（TDCPP）、新戊二醇乙二醇磷酸酯、甲基膦酸二甲酯（DMMP）、间苯二酚双（二苯基磷酸酯）（RDP）、乙基磷酸二乙酯（DEEP）和丙基磷酸二甲酯（DMPP）中的至少一种；此类阻燃剂可降低所制备的硬质聚氨酯泡沫的可燃性。并且，该阻燃剂优选为新戊二醇乙二醇磷酸酯、甲基膦酸二甲酯（DMMP）、间苯二酚双（二苯基磷酸酯）（RDP）、乙基磷酸二乙酯（DEEP）和丙基磷酸二甲酯（DMPP）中的至少一种，此类阻燃剂为无卤阻燃剂。
在本实施例中，该组合聚醚中优选包括：30~60重量份的聚醚多元醇A；3~15重量份的聚醚多元醇B；15~40重量份的聚醚多元醇C；5~20重量份的聚酯多元醇D；0~15重量份的戊烷；0~20重量份的氢氟烃；1~30重量份的FEA-1100；0.5~2.0重量份的水；1~3.5重量份的复合催化剂；1~5重量份的泡沫稳定剂；以及1~15重量份的阻燃剂。考虑到热水器的制备工艺条件，包覆在其内胆外的硬质聚氨酯泡沫通常要在较高温度下进行发泡制备，而普通的发泡材料并不适合在较高温度下进行发泡。然而，采用本实施例配方下的组合聚醚的发泡材料，可适用于较高温度下的发泡制备，能满足热水器的硬质聚氨酯泡沫的制备要求。
需要说明的是，在本实施例中，聚醚多元醇A的重量份数可进一步优选为40~60，以使得所制备硬质聚氨酯泡沫的导热系数较低。聚醚多元醇B的重量份数可进一步优选为5~15，以使得该组合聚醚具有较高流动性。聚醚多元醇C的重量份数可进一步优选为20~30，以使得所制备硬质聚氨酯泡沫的粘结强度和力学强度较高。聚酯多元醇D的重量份数可进一步优选为5~15，由于聚酯多元醇D的官能度小，用量不宜过多，否则影响所制备硬质聚氨酯泡沫的脱模性能。阻燃剂的重量份数可进一步优选为5~10，以使得所制备硬质聚氨酯泡沫的可燃性较低。
本发明还提出一种硬质聚氨酯泡沫的制备方法。
参照图1，在本发明一实施例中，该硬质聚氨酯泡沫的制备方法包括以下步骤：
步骤S10、将有机异氰酸酯与组合聚醚混合均匀；
步骤S20、将混合均匀后的组合物注入发泡空腔进行发泡。
本实施例中，该组合聚醚的具体结构参照上述实施例，至少地，该组合聚醚包括多元醇和发泡剂，其中，多元醇包括聚醚多元醇和/或聚酯多元醇，发泡剂包括六氟丁烯。如此，可使得采用本发明硬质聚氨酯泡沫的制备方法所制备得到的硬质聚氨酯泡沫材料，环境友好且导热系数较低，从而可使得由该硬质聚氨酯泡沫材料包覆内胆的热水器能满足环保要求且具有低能耗。另外，本实施例中，用以注入发泡空腔的组合物中还包括有机异氰酸酯，例如但不限于为烟台万华的PM2010，该有机异氰酸酯可提高泡沫的流动性，并保持泡沫较高的强度；通常地，该有机异氰酸酯优选采用多次甲级多苯基多异氰酸酯。
可以理解，若有机异氰酸酯的重量占比过低，会使得制备所得的硬质聚氨酯泡沫强度小，尺寸稳定性差；若有机异氰酸酯的重量占比过高，会使得制备所得的硬质聚氨酯泡沫脆且粘接性差。本实施例中，有机异氰酸酯与组合聚醚之间的重量比值优选为0.9~1.3，以兼顾制备所得硬质聚氨酯泡沫的强度和脆度。
在本实施例中，通常地，在步骤S10之前，还包括步骤：
S30、将所述组合聚醚中的各组分进行预混合。
可以理解，先将组合聚醚中的各组分进行预混合，再将有机异氰酸酯与预混合后的组合聚醚进行混合，有利于包含该有机异氰酸酯和该组合聚醚的组合物的均匀混合，从而提高制备所得的硬质聚氨酯泡沫的整体性能一致性。
需要说明的是，对于热水器，其发泡空腔通常是指内胆外表面与热水器外壳内表面之间所间隔出的空腔。优选地，在步骤S20中，所述发泡空腔的外部温度范围为20~50℃，内部温度范围为20~50℃。另外，在步骤S20中，所述组合物的温度范围优选为15~25℃，所述注入的操作压力范围优选为12~14Mpa。
下面参考具体实施例，对本发明进行描述，需要说明的是，以下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
原料配方：40重量份的聚醚多元醇A、6重量份的聚醚多元醇B、30重量份的聚醚多元醇C、10重量份的聚酯多元醇、8.5重量份复合阻燃剂（DEEP与DMPP重量比1：1）、0.4重量份的发泡催化剂（PC-12）、1.9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、0.7重量份的水、5.5重量份的HFC-245fa、25重量份的FEA-1100、126.69重量份的烟台万华的PM2010（有机异氰酸酯）。
制备方法：将上述原料配方中除有机异氰酸酯以外的组分在搅拌压力罐中进行预混合均匀；待预混合均匀后，将预混物通过泵转移到发泡机的白料工作罐，从而与装在黑料工作罐中的有机异氰酸酯通过高压混合头在12.5MPa的压力下注入顶部具有排气孔的热水器水箱模具中成型；发泡空腔模具的外部温度为28℃，内部温度为32℃，高压发泡机中的料温为18℃。
对比例
原料配方：40重量份的聚醚多元醇A、10重量份的聚醚多元醇B、25重量份的聚醚多元醇C、15重量份的聚酯多元醇、复合阻燃剂4份（DEEP与DMPP重量比1：1）、0.5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重量份的硅类泡沫稳定剂、1.5重量份的水、24重量份的HCFC-141b、130.20重量份的烟台万华的PM2010（有机异氰酸酯）。
制备方法：同实施例。
对实施例和对比例所制得的硬质聚氨酯泡沫进行性能测定。其中，泡沫芯密度的测试标准按照GB/T6343-2009进行，泡沫导热系数测试按照标准GB/T10295-2008进行，太阳能热水器能效测试按照标准GB 18708-2002进行。
通过性能测定所获得的各项参数具体如下表：
性能参数 实施例 对比例
泡沫芯密度 千克/立方米 35.72 37.80
导热系数22.5℃ 18.70 18.60
热水器能耗系数 0.670 0.660
由上表可以看出，实施例中的泡沫芯密度较对比例中的低，可减小热水器中硬质聚氨酯泡沫的注泡量，降低成本的同时，降低产品整体的总重量；另外，实施例中的导热系数和热水器能耗系数与对比例中的相差不大，因此，本发明的技术方案可以有效解决热水器行业中的发泡材料采用发泡剂HCFC-141b所带来的环保问题。
本发明还提出一种硬质聚氨酯泡沫，该硬质聚氨酯泡沫由上述硬质聚氨酯泡沫的制备方法所制备，该硬质聚氨酯泡沫的制备方法的具体步骤参照上述实施例，由于本硬质聚氨酯泡沫采用了上述所有实施例的全部技术方案，因此至少具有上述实施例的技术方案所带来的所有有益效果，在此不再一一赘述。
本发明还提出一种热水器，该热水器包括内胆以及硬质聚氨酯泡沫，该硬质聚氨酯泡沫的具体构成参照上述实施例，由于本热水器采用了上述所有实施例的全部技术方案，因此至少具有上述实施例的技术方案所带来的所有有益效果，在此不再一一赘述。其中，硬质聚氨酯泡沫通过高压发泡的方式，附着于所述内胆的外表面。
以上所述仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的发明构思下，利用本发明说明书及附图内容所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。

Claims (19)

  1. 一种组合聚醚，其特征在于，包括多元醇和发泡剂，所述多元醇包括聚醚多元醇和/或聚酯多元醇，所述发泡剂包括六氟丁烯。
  2. 如权利要求1所述的组合聚醚，其特征在于，所述发泡剂还包括戊烷和/或氢氟烃。
  3. 如权利要求2所述的组合聚醚，其特征在于，所述戊烷包括环戊烷、异戊烷和正戊烷中的至少一种。
  4. 如权利要求2所述的组合聚醚，其特征在于，所述氢氟烃为五氟丙烷、五氟丁烷和四氟乙烷中的一种。
  5. 如权利要求2所述的组合聚醚，其特征在于，所述聚醚多元醇包括聚醚多元醇A、聚醚多元醇B和聚醚多元醇C的至少一种，所述聚酯多元醇为聚酯多元醇D，其中：
    所述聚醚多元醇A是以山梨醇为起始剂，与氧化丙烯聚合而成，粘度为8000~15000mpa•s，羟值为360~500mgKOH/g，官能度为6；
    所述聚醚多元醇B是以甘油为起始剂，与氧化丙烯聚合而成，粘度为250~600mpa•s，羟值为150~350mgKOH/g；
    所述聚醚多元醇C是以蔗糖为起始剂，与氧化丙烯聚合而成，粘度为5000~12000mpa•s，羟值为360~440mgKOH/g；
    所述聚酯多元醇D为苯酐聚酯，粘度1000~2000mpa•s，羟值200~350mgKOH/g，官能度为2.7。
  6. 如权利要求5所述的组合聚醚，其特征在于，还包括水、复合催化剂、泡沫稳定剂和阻燃剂，其中：
    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、（2-羟基丙基）三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种；
    所述泡沫稳定剂为Si-C结构的硅油；
    所述阻燃剂包括三（2-氯乙基）磷酸酯、磷酸三（2-氯丙基）酯、磷酸三（2，3-二氯丙基）酯、新戊二醇乙二醇磷酸酯、甲基膦酸二甲酯、间苯二酚双（二苯基磷酸酯）、乙基磷酸二乙酯和丙基磷酸二甲酯中的至少一种。
  7. 如权利要求6所述的组合聚醚，其特征在于，所述组合聚醚包括：
    30~60重量份的所述聚醚多元醇A；
    3~15重量份的所述聚醚多元醇B；
    15~40重量份的所述聚醚多元醇C；
    5~20重量份的所述聚酯多元醇D；
    0~15重量份的所述戊烷；
    0~20重量份的所述氢氟烃；
    1~30重量份的所述六氟丁烯；
    0.5~2.0重量份的所述水；
    1~3.5重量份的所述复合催化剂；
    1~5重量份的所述泡沫稳定剂；以及
    1~15重量份的所述阻燃剂。
  8. 如权利要求7所述的组合聚醚，其特征在于，所述聚醚多元醇A的重量份数为40~60，所述聚醚多元醇B的重量份数为5~15，所述聚醚多元醇C的重量份数为20~30，所述聚酯多元醇D的重量份数为5~15，所述阻燃剂的重量份数为5~10。
  9. 一种硬质聚氨酯泡沫的制备方法，其特征在于，包括以下步骤：
    将有机异氰酸酯与组合聚醚混合均匀；所述组合聚醚包括多元醇和发泡剂，所述多元醇包括聚醚多元醇和/或聚酯多元醇，所述发泡剂包括六氟丁烯
    将混合均匀后的组合物注入发泡空腔进行发泡。
  10. 如权利要求9所述的硬质聚氨酯泡沫的制备方法，其特征在于，所述发泡剂还包括戊烷和/或氢氟烃。
  11. 如权利要求10所述的硬质聚氨酯泡沫的制备方法，其特征在于，所述聚醚多元醇包括聚醚多元醇A、聚醚多元醇B和聚醚多元醇C的至少一种，所述聚酯多元醇为聚酯多元醇D，其中：
    所述聚醚多元醇A是以山梨醇为起始剂，与氧化丙烯聚合而成，粘度为8000~15000mpa•s，羟值为360~500mgKOH/g，官能度为6；
    所述聚醚多元醇B是以甘油为起始剂，与氧化丙烯聚合而成，粘度为250~600mpa•s，羟值为150~350mgKOH/g；
    所述聚醚多元醇C是以蔗糖为起始剂，与氧化丙烯聚合而成，粘度为5000~12000mpa•s，羟值为360~440mgKOH/g；
    所述聚酯多元醇D为苯酐聚酯，粘度1000~2000mpa•s，羟值200~350mgKOH/g，官能度为2.7。
  12. 如权利要求11所述的硬质聚氨酯泡沫的制备方法，其特征在于，还包括水、复合催化剂、泡沫稳定剂和阻燃剂，其中：
    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、（2-羟基丙基）三甲基甲酸铵、乙季铵盐和辛季铵盐中的至少一种；
    所述泡沫稳定剂为Si-C结构的硅油；
    所述阻燃剂包括三（2-氯乙基）磷酸酯、磷酸三（2-氯丙基）酯、磷酸三（2，3-二氯丙基）酯、新戊二醇乙二醇磷酸酯、甲基膦酸二甲酯、间苯二酚双（二苯基磷酸酯）、乙基磷酸二乙酯和丙基磷酸二甲酯中的至少一种。
  13. 如权利要求12所述的硬质聚氨酯泡沫的制备方法，其特征在于，所述组合聚醚包括：
    30~60重量份的所述聚醚多元醇A；
    3~15重量份的所述聚醚多元醇B；
    15~40重量份的所述聚醚多元醇C；
    5~20重量份的所述聚酯多元醇D；
    0~15重量份的所述戊烷；
    0~20重量份的所述氢氟烃；
    1~30重量份的所述六氟丁烯；
    0.5~2.0重量份的所述水；
    1~3.5重量份的所述复合催化剂；
    1~5重量份的所述泡沫稳定剂；以及
    1~15重量份的所述阻燃剂。
  14. 如权利要求9所述的硬质聚氨酯泡沫的制备方法，其特征在于，所述有机异氰酸酯为多次甲级多苯基多异氰酸酯。
  15. 如权利要求9所述的硬质聚氨酯泡沫的制备方法，其特征在于，所述有机异氰酸酯与所述组合聚醚之间的重量比值为0.9~1.3。
  16. 如权利要求9所述的硬质聚氨酯泡沫的制备方法，其特征在于，在所述将混合均匀后的组合物注入发泡空腔进行发泡的步骤中，所述发泡空腔的外部温度范围为20~50℃，内部温度范围为20~50℃。
  17. 如权利要求16所述的硬质聚氨酯泡沫的制备方法，其特征在于，在所述将混合均匀后的组合物注入发泡空腔进行发泡的步骤中，所述组合物的温度范围为15~25℃，所述注入的操作压力范围为12~14Mpa。
  18. 一种硬质聚氨酯泡沫，其特征在于，所述硬质聚氨酯泡沫由如权利要求9所述的硬质聚氨酯泡沫的制备方法所制备。
  19. 一种热水器，其特征在于，包括内胆、以及如权利要求18所述的硬质聚氨酯泡沫，所述硬质聚氨酯泡沫附着于所述内胆的外表面。
PCT/CN2017/075233 2017-02-28 2017-02-28 组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器 WO2018157292A1 (zh)

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