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CN105085970A - HFC-245eb type combined polyether for refrigerator polyurethane plastic and preparation method thereof - Google Patents

HFC-245eb type combined polyether for refrigerator polyurethane plastic and preparation method thereof Download PDF

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Publication number
CN105085970A
CN105085970A CN201510490195.7A CN201510490195A CN105085970A CN 105085970 A CN105085970 A CN 105085970A CN 201510490195 A CN201510490195 A CN 201510490195A CN 105085970 A CN105085970 A CN 105085970A
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parts
hfc
polyether
polyether glycol
type combined
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傅东海
李志生
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Jiangsu Lihong Technology Development Co ltd
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Jiangsu Lihong Technology Development Co ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses HFC-245eb type combined polyether for refrigerator polyurethane plastic and a preparation method thereof, wherein the HFC-245eb type combined polyether for refrigerator polyurethane plastic comprises the following raw materials: 30-140 parts of polyether polyol, 0.7-6 parts of catalyst, 0-5 parts of foam stabilizer, 1-3 parts of water and 1-60 parts of foaming agent HFC-245eb 10. The HFC-245eb type combined polyether for the refrigerator polyurethane plastic has good heat insulation performance, mechanical strength and size stability by using HFC245eb as a foaming agent, is an ideal heat insulation material in the field of heat insulation of refrigerator and household appliances, is safe and environment-friendly, and meets the national requirements of energy conservation and emission reduction in the field of refrigerator and household appliances.

Description

A kind of HFC-245eb type combined polyether for refrigerator urethane plastic and preparation method thereof
Technical field
The present invention relates to a kind of HFC-245eb type combined polyether for refrigerator urethane plastic and preparation method thereof, belong to polyurethane foam and mould field.
Background technology
Rigid urethane foam is the heat insulating energy saving material of our times the best, and it is widely used in the fields such as refrigerator, building, communications and transportation, petrochemical complex, aviation be military and does heat preserving and insulating material and structure properties material.Whipping agent is most important a kind of auxiliary agent in PU porous plastics, and kind, the physical and mechanical properties, foam density, heat resistance etc. of quantity to PU of whipping agent have a direct impact.According to Montreal Protocol and follow-up amendment thereof, developing country uses the deadline of HCFC-141b to be the year two thousand thirty, Systems in Certain Developed Countries is required it is in 2010, requires to stop using hard bubbling in industry the end of the year in 2003 to the U.S., Japan and other countries.
Alternative whipping agent mainly HCFC-141b, pentamethylene or the iso-pentane that present domestic refrigerator field of household appliances adopts, but eliminate plan according to Chinese polyurethane foam industry HCFC-141b, eliminating of refrigerator ice cabinet, thermal container and small household appliances sub-industry HCFC-141b will be completed by 2015; And ring/iso-pentane foaming system is inflammable and explosive in process of production, very strict to processing requirement, its higher thermal conductivity also annoyings refrigerator household electrical appliances producer always simultaneously.
At present, although also there is the use of hydrocarbon blowing agents and full water class whipping agent, hydrocarbon blowing agents is because of inflammable and explosive, and insulated capacity is poor; And full water class foaming system exists that thermal conductivity is higher, dimensional stability is relatively poor, to shortcomings such as starting material requirement are higher, seldom apply at present in refrigerator field of household appliances.
Under the large policy environment background that country carries forward vigorously energy-saving and emission-reduction, refrigerator polyurethane rigid foam plastic finds more energy-conservation, safer, more environmental protection, the whipping agent of excellent thermal insulation performance seems especially important.
Summary of the invention
The invention provides a kind of HFC-245eb type combined polyether for refrigerator urethane plastic and preparation method thereof, whipping agent environmental protection used, safe, energy-conservation, reliable, excellent property, prepared rigid urethane foam has excellent heat-insulating property, physical strength and dimensional stability.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of HFC-245eb type combined polyether for refrigerator urethane plastic, its raw material comprises following component: polyether glycol 30 ~ 140 parts, catalyzer 0.7 ~ 6 part, suds-stabilizing agent 0 ~ 5 part, 1 ~ 3 part, water and blowing agent H FC-245eb10 ~ 60 part, described number is mass fraction.
Above-mentioned each raw material is put into container for stirring by above-mentioned mass parts even, namely obtain the HFC-245eb type combined polyether of refrigerator urethane plastic.The chemical name of above-mentioned blowing agent H FC-245eb is 1,1,2,3,3-pentafluoropropane.
Applicant finds after deliberation: HFC-245eb has lower boiling point and thermal conductivity, and compared with HCFC class, HFC-245eb is environmentally friendly, and the latent value ODP that damages the ozone layer is zero, and Greenhouse effect are dived, and GWP is lower for value, molecular weight 134.05g/mol, density 1.267g/m 3, boiling point 23 DEG C and non-flammable nontoxicity colourless gas; As compared to CFC-11 with HCFC-141b, HFC-245eb has lower boiling point and higher vapour pressure, some characteristic of foam can be improved, the performance especially under low temperature, make foam in certain temperature range, have larger mechanical property and more excellent heat-insulating property; Therefore, HFC-245eb has excellent physical property and environmental-protecting performance and carries out becoming refrigerator field of household appliances the staple product that ODS substitutes.
By the rigid urethane foam compact density obtained by the above-mentioned HFC-245eb type combined polyether for refrigerator urethane plastic at 30 ~ 48kg/m 3, having excellent heat-insulating property, dimensional stability and mechanical property, is the desirable lagging material of refrigerator household electrical appliance field of thermal insulation, safety, environmental protection, meets the energy-saving and emission-reduction requirement of country in refrigerator field of household appliances; And with low cost, security is high.
Preferably, for the HFC-245eb type combined polyether of refrigerator urethane plastic, its raw material comprises following component: polyether glycol 74 ~ 123 parts, catalyzer 1.6 ~ 2.9 parts, suds-stabilizing agent 2.5 ~ 3.5 parts, 2 ~ 2.2 parts, water and blowing agent H FC-245eb25 ~ 30 part, described number is mass fraction.
Existing various conventional polyether glycol all can solve the technical problem of the application, but in order to performances such as the heat retaining property, dimensional stability and the physical strengths that improve gained rigid urethane foam further, preferably, polyether glycol comprises: polyether glycol I 0 ~ 50 parts, polyether glycol II 0 ~ 70 parts, polyether glycol III 0 ~ 10 parts and polyester polyol IV 0 ~ 10 parts, described number is mass fraction; Wherein, the functionality of polyether glycol I is 4 ~ 6, and hydroxyl value is 390 ~ 550mgKOH/g, viscosity (25 DEG C) 4000 ~ 20000cp; The functionality of polyether glycol II is 4 ~ 6, and hydroxyl value is 350 ~ 480mgKOH/g, viscosity (25 DEG C) 2000 ~ 16000cp; The functionality of polyether glycol III is 2 ~ 4, and hydroxyl value is 110 ~ 450mgKOH/g, viscosity (25 DEG C) 100 ~ 800cp; The functionality 2 ~ 3 of polyester polyol IV, hydroxyl value 380 ~ 480mgKOH/g, viscosity (25 DEG C) 1500 ~ 8000cp.Further preferably, the functionality of polyether glycol I is 5; The functionality of polyether glycol II is 5.2; The functionality of polyether glycol III is 3; The functionality of polyester polyol IV is 2.2.
Polyether glycol is formed by initiator and Polymerization of Propylene Oxide; In order to improve the heat-insulating property of products obtained therefrom further, preferably, polyether glycol I initiator used is sorbyl alcohol; Polyether glycol II initiator used is sucrose or glycol ether, and is polymerized under the palmitic condition of interpolation; Polyether glycol III initiator used is glycerine; Polyester polyol IV initiator used is pure terephthalic acid, ethylene glycol or glycerine.
In order to further improve heat retaining property, the performance such as physical strength and dimensional stability of gained rigid urethane foam, further preferably, polyether glycol comprises: polyether glycol I 30 ~ 45 parts, polyether glycol II 40 ~ 60 parts, polyether glycol III 4 ~ 8 parts and polyester polyol IV 0 ~ 10 parts, described number is mass fraction.
The application can use existing conventional various catalyzer, but in order to ensure reaction efficiency further, and promote the synergistic effect between each component, preferably, catalyzer comprises: catalyzer I 0.5 ~ 2.5 parts, composite catalyst II 0.2 ~ 3 parts and catalyzer III 0 ~ 0.5 part, described number is mass fraction; Wherein, catalyzer I is N, N-dimethyl cyclohexyl amine, and composite catalyst II is at least one in quaternary ammonium salt compound, triethylene diamine or 1,3,5-bis-(dimethylamino-propyl) Hexahydrotriazine, and catalyzer III is pentamethyl-diethylenetriamine.
Above-mentioned quaternary ammonium salt compound is alkyl trimethyl quaternary ammonium salt, alkyldimethylbenzylammonium quaternary ammonium salt or alkyl dimethyl ethoxyl quaternary ammonium salt more preferably.Composite catalyst II is preferably triethylene diamine and 1,3,5-bis-(dimethylamino-propyl) Hexahydrotriazine mass ratio is 1:(1 ~ 2) mixture.
In order to further ensure reaction efficiency, make the synergistic effect between each component perform to the best, further preferably, catalyzer I 1.2 ~ 1.8 parts, composite catalyst II 0.4 ~ 0.8 part and catalyzer III 0 ~ 0.3 part, described number is mass fraction simultaneously.
In order to promote the synergistic effect between each component further, ensure quality product, preferably, suds-stabilizing agent is AK8830.Further preferably, in feed composition, the mass fraction of suds-stabilizing agent is 1.5 ~ 3.5 parts.
In order to cost-saving, the quality that ensures products obtained therefrom further simultaneously, preferably, in feed composition: the mass fraction of water is 2 ~ 2.2 parts, the mass fraction of blowing agent H FC-245eb is 25 ~ 30 parts.
The preparation method of the above-mentioned HFC-245eb type combined polyether for refrigerator urethane plastic, after polyether glycol, catalyzer, suds-stabilizing agent and water being mixed, then adds whipping agent and mixes, to obtain final product.
Above-mentioned mass fraction is the mass fraction under same benchmark.
The application's gained HFC-245eb type combined polyether and isocyanate reaction can be obtained polyurethane rigid foam plastic, and concrete technology is with reference to prior art.
The NM technology of the present invention is all with reference to prior art.
The present invention is used for the HFC-245eb type combined polyether of refrigerator urethane plastic, has good heat-insulating property, physical strength and dimensional stability by the refrigerator polyurethane rigid foam plastic using HFC245eb to obtain for whipping agent; The compact density of goods is at 30 ~ 48kg/m 3in scope, compressive strength is more than or equal to 150kPa, and thermal conductivity is less than 0.019w/ (m.k), Low-Temperature Size stability (-30 DEG C, 24h) be less than or equal to 0.1%, and high temperature dimensional stability (70 DEG C, relative humidity 95% ± 5%, 24h) be less than or equal to 0.8%, rate of closed hole is more than or equal to 95%, and water-intake rate is less than 2%, is the desirable lagging material of refrigerator household electrical appliance field of thermal insulation, safety, environmental protection, meet the energy-saving and emission-reduction requirement of country in refrigerator field of household appliances; The application preparation method is simple, has no special requirements to technological process.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment
Raw materials used as follows in each embodiment:
(name is called 600A to polyether glycol I, hydroxyl value 421mgKOH/g, functionality 5, viscosity (25 DEG C) 11500cp), (name is called 8238 to polyether glycol II, hydroxyl value 395mgKOH/g, functionality 5.2, viscosity (25 DEG C) 7350cp) be all that ShaoXing Hengfeng Polyurethane Industry Co., Ltd. produces; Polyether glycol III (being called VOANOLCP450, hydroxyl value 378mgKOH/g, functionality 3, viscosity (25 DEG C) 330cp) is DOW Chemical production; Polyester polyol IV (name is called 400A, hydroxyl value 425mgKOH/g, functionality 2.2, viscosity (25 DEG C) 2950cp) is the production of south, Zhangjiagang photoinitiator chemical company limited;
Catalyzer I is N, N-dimethyl cyclohexyl amine; Manufacturer is chemical plant, great river, Jiangdu; Composite catalyst II is triethylene diamine and 1,3,5-bis-(dimethylamino-propyl) Hexahydrotriazine mass ratio is 1:(1.5) mixture, manufacturer is chemical plant, great river, Jiangdu; Catalyzer III is pentamethyl-diethylenetriamine, and manufacturer is air Chemicals (Shanghai) Co., Ltd.;
Suds-stabilizing agent I is AK8830, and manufacturer is Nanjing Dymatic Shichuang Chemical Co., Ltd.;
Whipping agent is HFC-245eb, and chemical name is 1,1,2,3,3-pentafluoropropane, Jiangsu blue planet Environmental Protection Technology Co., Ltd of manufacturer.
Each embodiment is prepared all by the following method: by each raw material by table 1 to share drop into container for stirring evenly (by polyether glycol, catalyzer, after suds-stabilizing agent and water mix, again whipping agent added and mix), obtain using the combined polyether that HFC245eb is whipping agent, gained combined polyether and polyphenyl polymethylene polyisocyanates are by combined polyether again: isocyanic ester=1:(1.05 ~ 1.2) weight ratio carry out high-speed mixing reaction, wherein, temperature of reaction is 20-25 DEG C, stirring velocity is 3000r/min (stirring in initial time), initial time is 12 ± 5s, the fiber time is 80 ± 10s, the not sticky time is 120 ± 20s, make polyurethane rigid foam plastic.
The proportioning raw materials of each embodiment of table 1 and the performance table of products obtained therefrom
Note: 1. show Raw on and all calculate by quality share; 2. froth appearance core density is tested by standard GB/T/T26689-2011; Thermal conductivity is tested by standard GB/T/T10294-2008; Compressive strength is tested by standard GB/T/T8813-2008; Dimensional stability is tested by standard GB/T/T8811-2008; Rate of closed hole is tested by standard GB/T/T10799-2008; Water-intake rate is tested by standard GB/T/T8810-2005.

Claims (10)

1. the HFC-245eb type combined polyether for refrigerator urethane plastic, it is characterized in that: its raw material comprises following component: polyether glycol 30 ~ 140 parts, catalyzer 0.7 ~ 6 part, suds-stabilizing agent 0 ~ 5 part, 1 ~ 3 part, water and blowing agent H FC-245eb10 ~ 60 part, described number is mass fraction.
2. as claimed in claim 1 for the HFC-245eb type combined polyether of refrigerator urethane plastic, it is characterized in that: polyether glycol comprises: polyether glycol I 0 ~ 50 parts, polyether glycol II 0 ~ 70 parts, polyether glycol III 0 ~ 10 parts and polyester polyol IV 0 ~ 10 parts, described number is mass fraction; Wherein, the functionality of polyether glycol I is 4 ~ 6, and hydroxyl value is 390 ~ 550mgKOH/g, viscosity (25 DEG C) 4000 ~ 20000cp; The functionality of polyether glycol II is 4 ~ 6, and hydroxyl value is 350 ~ 480mgKOH/g, viscosity (25 DEG C) 2000 ~ 16000cp; The functionality of polyether glycol III is 2 ~ 4, and hydroxyl value is 110 ~ 450mgKOH/g, viscosity (25 DEG C) 100 ~ 800cp; The functionality 2 ~ 3 of polyester polyol IV, hydroxyl value 380 ~ 480mgKOH/g, viscosity (25 DEG C) 1500 ~ 8000cp.
3., as claimed in claim 2 for the HFC-245eb type combined polyether of refrigerator urethane plastic, it is characterized in that: polyether glycol is formed by initiator and Polymerization of Propylene Oxide; Wherein, polyether glycol I initiator used is sorbyl alcohol; Polyether glycol II initiator used is sucrose or glycol ether, and is polymerized under the palmitic condition of interpolation; Polyether glycol III initiator used is glycerine; Polyester polyol IV initiator used is pure terephthalic acid, ethylene glycol or glycerine.
4. as claimed in claim 2 for the HFC-245eb type combined polyether of refrigerator urethane plastic, it is characterized in that: polyether glycol comprises: polyether glycol I 30 ~ 45 parts, polyether glycol II 40 ~ 60 parts, polyether glycol III 4 ~ 8 parts and polyester polyol IV 0 ~ 10 parts, described number is mass fraction.
5. the HFC-245eb type combined polyether for refrigerator urethane plastic as described in claim 1-4 any one, it is characterized in that: catalyzer comprises: catalyzer I 0.5 ~ 2.5 parts, composite catalyst II 0.2 ~ 3 parts and catalyzer III 0 ~ 0.5 part, described number is mass fraction; Wherein, catalyzer I is N, N-dimethyl cyclohexyl amine, and composite catalyst II is at least one in quaternary ammonium salt compound, triethylene diamine or 1,3,5-bis-(dimethylamino-propyl) Hexahydrotriazine, and catalyzer III is pentamethyl-diethylenetriamine.
6. as claimed in claim 5 for the HFC-245eb type combined polyether of refrigerator urethane plastic, it is characterized in that: catalyzer comprises: catalyzer I 1.2 ~ 1.8 parts, composite catalyst II 0.4 ~ 0.8 part and catalyzer III 0 ~ 0.3 part, described number is mass fraction.
7. the HFC-245eb type combined polyether for refrigerator urethane plastic as described in claim 1-4 any one, is characterized in that: suds-stabilizing agent is AK8830.
8., as claimed in claim 7 for the HFC-245eb type combined polyether of refrigerator urethane plastic, it is characterized in that: in feed composition, the mass fraction of suds-stabilizing agent is 1.5 ~ 3.5 parts.
9. the HFC-245eb type combined polyether for refrigerator urethane plastic as described in claim 1-4 any one, is characterized in that: in feed composition, the mass fraction of water is 2 ~ 2.2 parts, the mass fraction of blowing agent H FC-245eb is 25 ~ 30 parts.
10. the preparation method of the HFC-245eb type combined polyether for refrigerator urethane plastic described in claim 1-9 any one, it is characterized in that: after polyether glycol, catalyzer, suds-stabilizing agent and water are mixed, again whipping agent added and mix, to obtain final product.
CN201510490195.7A 2015-08-11 2015-08-11 HFC-245eb type combined polyether for refrigerator polyurethane plastic and preparation method thereof Pending CN105085970A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276546A (en) * 2017-12-28 2018-07-13 青岛海尔股份有限公司 Polyurethane rigid foam plastic and preparation method thereof
WO2021196862A1 (en) * 2020-03-30 2021-10-07 青岛海尔电冰箱有限公司 Foamed material, heat-preservation box body, and preparation methods therefor

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CN1742033A (en) * 2003-01-22 2006-03-01 拜尔材料科学有限责任公司 Rigid polyurethane foams with improved properties
CN103709372A (en) * 2013-12-23 2014-04-09 山东一诺威新材料有限公司 Medical freezer type polyurethane thermal insulation material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1742033A (en) * 2003-01-22 2006-03-01 拜尔材料科学有限责任公司 Rigid polyurethane foams with improved properties
CN103709372A (en) * 2013-12-23 2014-04-09 山东一诺威新材料有限公司 Medical freezer type polyurethane thermal insulation material and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276546A (en) * 2017-12-28 2018-07-13 青岛海尔股份有限公司 Polyurethane rigid foam plastic and preparation method thereof
WO2021196862A1 (en) * 2020-03-30 2021-10-07 青岛海尔电冰箱有限公司 Foamed material, heat-preservation box body, and preparation methods therefor
US12325804B2 (en) 2020-03-30 2025-06-10 Qingdao Haier Refrigerator Co., Ltd. Foaming material, and thermal insulation cabinet and method for preparing same

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