CN103709372A - Medical freezer type polyurethane thermal insulation material and preparation method thereof - Google Patents
Medical freezer type polyurethane thermal insulation material and preparation method thereof Download PDFInfo
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- CN103709372A CN103709372A CN201310718048.1A CN201310718048A CN103709372A CN 103709372 A CN103709372 A CN 103709372A CN 201310718048 A CN201310718048 A CN 201310718048A CN 103709372 A CN103709372 A CN 103709372A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to the technical field of polyurethane foaming plastic, and in particular relates to a low-conductivity low-energy consumption medical freezer type polyurethane thermal insulation material and a preparation method thereof. The thermal insulation material consists of the following ingredients in parts by weight: 40-50 parts of polyether polyol A, 15-25 parts of polyether polyol B, 20-30 parts of polyether polyol C, 10-15 parts of polyether polyol D, 2.0-4.0 parts of foam stabilizer, 2.0-4.0 parts of water, 1.2-4.5 parts of catalyst and 25-35 parts of foaming agent. Compared with the prior art, rigid polyurethane foaming plastic prepared by using the combined polyether produced in the invention has lower heat conductivity coefficient, the value of system k is ranged from 18.0 mW/m.k to 18.5 mW/m.k, the energy consumption can be remarkably reduced and the thermal insulation performance of the foaming system can be effectively improved; simultaneously, the foam density has higher compression strength and better low temperature resistance in comparison with that of a pure cyclopentane system, the whole foam density can be reduced by 10%-15%, and the foam performance is better than that of the pure cyclopentane system.
Description
Technical field
The invention belongs to urethane foam technical field, be specifically related to a kind of low medical refrigerator type polyurethane of less energy-consumption lagging material and preparation method thereof of leading.
Background technology
Polyurethane foam is the leader in current all heat-insulating heat-preserving materials, is widely used in many adiabatic heat-insulations fields such as refrigerator ice cabinet, solar water heater, pipeline building heat preservation, cold storage plate, communications and transportation, aviation be military.In recent years, rise day by day along with life science and biological gene technology, the demand of the medical Freezer Products of low temperature is ascendant trend year by year, the medical refrigerator demand of low temperature of especially-86 ℃ is maximum, in medical treatment, scientific research, in biotechnology field, be widely used in the preparation of low temperature environment and the low-temperature storage of material, because the medical refrigerator cabinet of low temperature internal-external temperature difference is larger, so common inhomogeneous quality and safety that has a strong impact on preservation object of the temperature distribution in cabinet, simultaneously because polyurethane foam is for a long time under lower temperature conditions, low temperature dimensional stability to polyurethane foam, compressive strength and thermal conductivity all have higher requirement, and common ring pentane type composite polyether emphasis is considered whipping agent security, foam density dimensional stability and the heat retaining property higher and foam of preparation are poor simultaneously, foam compression intensity and low temperature resistant dimensional stability prepared by HCFC-141B are poor, the relatively large thickness of foam layer that causes of foam shrinkage strain amount in time of working under long-term cold condition will reduce gradually, the performances such as the thermal conductivity of foam and ultimate compression strength all will decrease, urethane foam insulation heat-proof quality reduces obviously, greatly affect heat insulation effect and increased energy consumption, cause the wasting of resources.
Summary of the invention
The object of the present invention is to provide a kind of low medical refrigerator type polyurethane of less energy-consumption lagging material of leading, this lagging material effectively reduces thermal conductivity and the refrigerator complete machine energy consumption of polyurethane foam, and there is excellent low temperature resistant dimensional stability and higher compressive strength, environmental friendliness, can meet under long-term cold condition and use; The present invention provides its preparation method simultaneously.
Medical refrigerator type polyurethane lagging material of the present invention, consists of A component and B component, and the weight ratio of A component and B component is 1:1.0-1.2, wherein:
A component is, in parts by weight:
Wherein, polyether glycol A, polyether glycol B, polyether glycol C and tetra-kinds of raw material gross weight umbers of polyether glycol D are 100 parts;
Described polyether glycol A is 5-6 functionality, the polyether glycol that hydroxyl value is 460 ± 20mgKOH/g;
Described polyether glycol B is 4-5 functionality, the polyether glycol that hydroxyl value is 375 ± 20mgKOH/g;
Described polyether glycol C is 4 functionality, the polyether glycol that hydroxyl value is 400 ± 20mgKOH/g;
Described polyether glycol D is 3 functionality, the polyether glycol that hydroxyl value is 330 ± 10mgKOH/g;
B component is:
Polymerization diphenylmethanediisocyanate, preferably PM200 (Yantai Wanhua Polyurethane Co., Ltd) or M20S (BASF AG).
Wherein,
The described preferred SA460 of polyether glycol A or NJ6207, SA460 manufacturer is Shandong Lanxing Dongda Chemical Co.,Ltd, NJ6207 manufacturer is Jurong Ningwu New Materials Development Co., Ltd.; The preferred SA380 of polyether glycol B or NJ6209, SA380 manufacturer is Shandong Lanxing Dongda Chemical Co.,Ltd, NJ6209 manufacturer is Jurong Ningwu New Materials Development Co., Ltd.; The preferred YD-401P of polyether glycol C, manufacturer is Yadong, Hebei Chemical Group company limited; The preferred NJ305 of polyether glycol D, manufacturer is Jurong Ningwu New Materials Development Co., Ltd..
Described suds-stabilizing agent is the low silicone oil L-6863 that leads, and manufacturer is U.S. MomentivePerformanceMaterials.
Described chemical foaming agent is water.
Described catalyzer is N, N-dimethylcyclohexylamine (Y-12), N, N-diformazan basic ring benzylamine (Y-27), 1,3,5-tri-(dimethylamino-propyl)-hexahydrotriazine (PC-41) or TMR-2(US Air gas chemical company) in one or more.
Described pneumatogen is HFC-245FA, the Honeywell Inc. that manufacturer is the U.S..
The preparation method of described medical refrigerator type polyurethane lagging material, step is as follows:
First load weighted polyether glycol A, polyether glycol B, polyether glycol C and polyether glycol D are added in reactor and stirred, then add load weighted suds-stabilizing agent, catalyzer, chemical foaming agent, pneumatogen, stir at normal temperatures 1.0-1.5 hour, obtain A component;
During use, A component is mixed and reacted according to weight ratio 1:1.0-1.2 with B component, prepare medical refrigerator type polyurethane lagging material.
The present invention uses the novel low blowing agent H FC-245FA that leads as pneumatogen, coordination by various polyethers systems, catalyst system is arranged in pairs or groups, add low silicone oil L-6863 and the low synergy of leading polyethers YD-401P led, effectively reduce the thermal conductivity of polyurethane foam and improved compressive strength and the low temperature resistant dimensional stability of foam.
Compared with prior art, the present invention has following beneficial effect:
Hard polyurethane foam lagging material prepared by the present invention, the thermal conductivity of foam can be in 18.0～18.5mW/mK scope, effectively reduce in the medical refrigerator life-time service of low temperature process energy consumption problem, saved the energy, foam density is compared with pure pentamethylene system simultaneously, ultimate compression strength is higher, low temperature resistant dimensional stability is better, can reduce foam global density 10-15%, the foam system self that the present invention generates in addition has higher strength and toughness, higher with the cohesive strength of refrigerator box body, there will not be shelling lamination problem, the dimensional stability of foam and good fluidity, can meet the service requirements under long-term cold condition, preparation method of the present invention is simple and easy to operate, production process three-waste free pollution, safety and environmental protection.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The described low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading consists of A component and B component, and the weight ratio of A component and B component is 1:1.1, wherein:
A component is, in parts by weight:
During preparation, each raw material is put in reactor and stirred, obtain A component, A component is reacted with isocyanic ester (PM200), obtain the low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading.Specific targets are as follows:
Moulding core density 32.4kg/m
3
Thermal conductivity 0.0184W/mK
Compressive strength 185.4kpa
Dimensional stability
-30℃，24h： 0.10%
100℃，24h： 0.16%
Rate of closed hole 95.1%
Embodiment 2
The described low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading consists of A component and B component, and the weight ratio of A component and B component is 1:1.0, wherein:
A component is, in parts by weight:
During preparation, each raw material is put in reactor and stirred, obtain A component, A component is reacted with isocyanic ester (M20S), obtain the low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading.Specific targets are as follows:
Moulding core density 34.1kg/m
3
Thermal conductivity 0.0182W/mK
Compressive strength 201.6kpa
Dimensional stability
-30℃，24h： 0.06%
100℃，24h： 0.11%
Rate of closed hole 96.2%
Embodiment 3
The described low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading consists of A component and B component, and the weight ratio of A component and B component is 1:1.1, wherein:
A component is, in parts by weight:
During preparation, each raw material is put in reactor and stirred, obtain A component, A component is reacted with isocyanic ester (M20S), obtain the low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading.Specific targets are as follows:
Moulding core density 33.6kg/m
3
Thermal conductivity 0.0180W/mK
Compressive strength 197.3kpa
Dimensional stability
-30℃，24h： 0.10%
100℃，24h： 0.15%
Rate of closed hole 95.7%
Embodiment 4
The described low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading consists of A component and B component, and the weight ratio of A component and B component is 1:1.2, wherein:
A component is, in parts by weight:
During preparation, each raw material is put in reactor and stirred, obtain A component, A component is reacted with isocyanic ester (PM200), obtain the low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading.Specific targets are as follows:
Moulding core density 33.2kg/m
3
Thermal conductivity 0.0183W/mK
Compressive strength 195.8kpa
Dimensional stability
-30℃，24h： 0.11%
100℃，24h： 0.17%
Rate of closed hole 95.3%
Embodiment 5
The described low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading consists of A component and B component, and the weight ratio of A component and B component is 1:1.1, wherein:
A component is, in parts by weight:
During preparation, each raw material is put in reactor and stirred, obtain A component, A component is reacted with isocyanic ester (PM200), obtain the low medical refrigerator type polyurethane of the less energy-consumption lagging material of leading.Specific targets are as follows:
Moulding core density 33.9kg/m
3
Thermal conductivity 0.0182W/mK
Compressive strength 198.4kpa
Dimensional stability
-30℃，24h： 0.10%
100℃，24h： 0.15%
Rate of closed hole 96.0%.
Claims (6)
1. a medical refrigerator type polyurethane lagging material, is characterized in that consisting of A component and B component, and the weight ratio of A component and B component is 1:1.0-1.2, wherein:
A component is, in parts by weight:
Polyether glycol A, polyether glycol B, polyether glycol C and tetra-kinds of raw material gross weight umbers of polyether glycol D are 100 parts;
Described polyether glycol A is 5-6 functionality, the polyether glycol that hydroxyl value is 460 ± 20mgKOH/g;
Described polyether glycol B is 4-5 functionality, the polyether glycol that hydroxyl value is 375 ± 20mgKOH/g;
Described polyether glycol C is 4 functionality, the polyether glycol that hydroxyl value is 400 ± 20mgKOH/g;
Described polyether glycol D is 3 functionality, the polyether glycol that hydroxyl value is 330 ± 10mgKOH/g;
B component is:
Polymerization diphenylmethanediisocyanate.
2. medical refrigerator type polyurethane lagging material according to claim 1, is characterized in that: described suds-stabilizing agent is the low silicone oil L-6863 that leads.
3. medical refrigerator type polyurethane lagging material according to claim 1, is characterized in that: described chemical foaming agent is water.
4. medical refrigerator type polyurethane lagging material according to claim 1, it is characterized in that: described catalyzer is N N-dimethylcyclohexylamine, N, N-diformazan basic ring benzylamine, 1, one or more in 3,5-tri-(dimethylamino-propyl)-hexahydrotriazine or TMR-2.
5. medical refrigerator type polyurethane lagging material according to claim 1, is characterized in that: described pneumatogen is HFC-245FA.
6. a preparation method for the arbitrary described medical refrigerator type polyurethane lagging material of claim 1-5, is characterized in that, step is as follows:
First load weighted polyether glycol A, polyether glycol B, polyether glycol C and polyether glycol D are added in reactor and stirred, then add load weighted suds-stabilizing agent, catalyzer, chemical foaming agent, pneumatogen, stir at normal temperatures 1.0-1.5 hour, obtain A component;
During use, A component is mixed and reacted according to weight ratio 1:1.0-1.2 with B component, prepare medical refrigerator type polyurethane lagging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310718048.1A CN103709372B (en) | 2013-12-23 | 2013-12-23 | Medical freezer type polyurethane thermal insulation material and preparation method thereof |
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| CN201310718048.1A CN103709372B (en) | 2013-12-23 | 2013-12-23 | Medical freezer type polyurethane thermal insulation material and preparation method thereof |
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| CN103709372B CN103709372B (en) | 2016-01-27 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448222A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Low-conductivity polyurethane thermal insulation material for ultrathin refrigerator freezers and preparation method thereof |
| CN105085970A (en) * | 2015-08-11 | 2015-11-25 | 江苏利宏科技发展有限公司 | HFC-245eb type combined polyether for refrigerator polyurethane plastic and preparation method thereof |
| CN105313256A (en) * | 2014-07-13 | 2016-02-10 | 齐克先 | Thermal insulation pipe foaming process and polyurethane material |
| CN106220825A (en) * | 2016-08-01 | 2016-12-14 | 山东诺威新材料有限公司 | Refrigerator car polyurethane bulk bubble insulation material and preparation method thereof |
| CN106750094A (en) * | 2016-12-02 | 2017-05-31 | 上海东大聚氨酯有限公司 | A kind of environment protection pipe polyurethane raw material composition and its application method |
| CN107118320A (en) * | 2017-06-28 | 2017-09-01 | 山东诺威新材料有限公司 | Food/pharmaceutical incubator polyurethane heat insulation material and preparation method thereof |
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| CN102167899A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Polyurethane rigid foam combined polyether for electric water heater |
| CN102977314A (en) * | 2012-12-10 | 2013-03-20 | 山东东大一诺威新材料有限公司 | Environment-friendly composite polyether for ultralow-temperature freezer, preparation method and application |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5561172A (en) * | 1992-02-14 | 1996-10-01 | Daikin Industries, Ltd. | Method of producing rigid polyurethane foams |
| CN102167897A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Rigid polyurethane foam special for laminboard |
| CN102167899A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Polyurethane rigid foam combined polyether for electric water heater |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105313256A (en) * | 2014-07-13 | 2016-02-10 | 齐克先 | Thermal insulation pipe foaming process and polyurethane material |
| CN104448222A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Low-conductivity polyurethane thermal insulation material for ultrathin refrigerator freezers and preparation method thereof |
| CN104448222B (en) * | 2014-11-27 | 2017-01-04 | 山东一诺威新材料有限公司 | Ultra-thin refrigerator low conductivity type polyurethane heat insulation material and preparation method thereof |
| CN105085970A (en) * | 2015-08-11 | 2015-11-25 | 江苏利宏科技发展有限公司 | HFC-245eb type combined polyether for refrigerator polyurethane plastic and preparation method thereof |
| CN106220825A (en) * | 2016-08-01 | 2016-12-14 | 山东诺威新材料有限公司 | Refrigerator car polyurethane bulk bubble insulation material and preparation method thereof |
| CN106750094A (en) * | 2016-12-02 | 2017-05-31 | 上海东大聚氨酯有限公司 | A kind of environment protection pipe polyurethane raw material composition and its application method |
| CN106750094B (en) * | 2016-12-02 | 2019-05-03 | 上海东大聚氨酯有限公司 | A kind of environment protection pipe polyurethane raw material composition and its application method |
| CN107118320A (en) * | 2017-06-28 | 2017-09-01 | 山东诺威新材料有限公司 | Food/pharmaceutical incubator polyurethane heat insulation material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103709372B (en) | 2016-01-27 |
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