CN101948563B - Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof - Google Patents
Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof Download PDFInfo
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- CN101948563B CN101948563B CN2010102639007A CN201010263900A CN101948563B CN 101948563 B CN101948563 B CN 101948563B CN 2010102639007 A CN2010102639007 A CN 2010102639007A CN 201010263900 A CN201010263900 A CN 201010263900A CN 101948563 B CN101948563 B CN 101948563B
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P80/00—Climate change mitigation technologies for sector-wide applications
- Y02P80/20—Climate change mitigation technologies for sector-wide applications using renewable energy
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Abstract
The invention provides pentane type composite polyether, which comprises the following components: polyether polyol 8210H, polyether polyol SA460, foam stabilizer, polyurethane synthesis catalyst, pentane foaming agent and water. In the pentane type composite polyether, pentane is used as the foaming agent; the pentane foaming agent has the advantages of low GWP value and zero ODP value and completely conforms to the environmental protection requirements for replacing HCFC-141B in the industry of a solar water heater, while the cost is low. The composite polyether overcomes the shortcoming of low compatibility between pentane and polyether and has high compatibility with pentane, high flow property and good foaming effect; and the viscosity of the composite polyether is suitable for the production technology of the solar water heater. The composite polymer has obvious advantages on application in the industry of solar water heater. The rigid polyurethane foam prepared by the action between the composite polymer and isocyanate has high heat conductivity and size stability.
Description
Technical field
The present invention relates to hard polyurethane foam foaming field, relate in particular to a kind of pentane type combined polyether, the invention still further relates to a kind of compsn that contains this pentane type combined polyether, and the hard polyurethane foam and the application thereof that make by this pentane type combined polyether.
Background technology
Along with the widespread use of hard polyurethane foams, it also more and more receives people's attention to the negative impact of environment.The refrigerator ice cabinet industry of China has been transferred to the cyclopentane type combined polyether from HCFC-141B type combined polyether basically.But, be main still with the HCFC-141B combined polyether in the sun power industry.Yet HCFC-141B still can damage atmospheric ozone layer as a kind of transitional product.Under the catalysis of low-carbon economy, " green " hard polyurethane foam cry with latent value (GWP) value of low global greenhouse effect and the latent value (ODP) of zero ozone depletion is increasingly high.
According to statistics, in order to substitute the HCFC-141B whipping agent, domestic have only several producers of a line brand after 2007, to attempt having carried out foaming experiments such as HFC-245fa Quan Shui, and carried out the short run popularization.
The big urethane company in east is through the adjustment to the polyethers system; With HFC-245fa, HFC-365mfc is the insulation requirement that the polyurethane foam of whipping agent all can reach the solar water heater product; Compressive strength is greater than 150kpa, thermal conductivity 17-19mW/mK, but such whipping agent higher cost has restricted its development; And its GWP value is much higher than pentane (HC) whipping agent, is the whipping agent of relative environmental protection in the greenhouse gases.
Take all factors into consideration from environmental protection, foaming properties each side, prove that through lot of test the HC whipping agent can solve hydrogen fluorohydrocarbon (HFC) and full water foamed shortcoming.Tool using value is three kinds of pentamethylene, Skellysolve A and iso-pentane in the HC foaming, is referred to as pentane class whipping agent, and it is owing at room temperature be all liquid state, and it is zero that ODP value is, and the GWP value is very low, and is nontoxic, minimum and come into one's own to environmental influence.
At present; Also do not adopt the reason of HC whipping agent to be because the HC whipping agent belongs to inflammable volatile organic compounds in the solar water heater industry; Can explode under finite concentration and condition with air,, need existing metering, storage and foaming machine are carried out bigger improvement and increase the safe handling facility for guaranteeing safety; And operative technique needs strict control, thereby equipment cost is high than HCFC, HFC foamed system.But having given the HC whipping agent, present domestic refrigerator industry proves that well safety-problems is solved comprehensively.And the once improvement input through to equipment can be used the cheap HC whipping agent that is easy to get, and has obtained better controlled for production cost.But because the technology of sun power industry and to urethane flowing property, foaming density etc. require inconsistent; Pentane type combined polyether in the refrigerator field is not suitable for the sun power industry, therefore needs badly and seeks a kind of pentane type combined polyether that can be applicable to the solar water heater field.
Summary of the invention
Technical problem to be solved by this invention is in order to have overcome existing combined polyether and the pentane foaming agent consistency is poor; And existing pentane type combined polyether is not suitable for the shortcoming in solar water heater field; A kind of pentane type combined polyether, a kind of compsn that is used to prepare hard polyurethane foam are provided, a kind of hard polyurethane foam and application thereof.Pentane type combined polyether of the present invention as whipping agent, has zero odp value, low GWP value, environmental protection and low cost and other advantages with pentane.Combined polyether of the present invention can satisfy the requirement of solar water heater field to hard polyurethane foam performance of heat protective material and ME well, can make all very excellent hard polyurethane foam of various aspects of performance such as dimensional stability, thermal conductivity, compressive strength.
The invention provides a kind of pentane type combined polyether, it comprises following compositions: polyether glycol 8210H, polyether glycol SA460, suds-stabilizing agent, urethane synthetic catalyst, pentane foaming agent and water.
Wherein, What the mass fraction of each composition was preferable in the pentane type combined polyether of the present invention is: polyether glycol 8210H 6-8 part; Polyether glycol SA4602-4 part; Suds-stabilizing agent 0.2-0.3 part, urethane synthetic catalyst 0.2-0.35 part, pentane foaming agent 1-1.3 part and water 0.05-0.1 part; What wherein, described urethane synthetic catalyst was preferable is 0.22-0.3 part.
In the present invention's one preferred implementation; Described pentane type combined polyether is grouped into by the one-tenth of following mass fraction: polyether glycol 8210H 6-8 part; Polyether glycol SA4602-4 part; Suds-stabilizing agent 0.2-0.3 part, urethane synthetic catalyst 0.2-0.35 part, pentane foaming agent 1.0-1.3 part and water 0.05-0.1 part; What wherein, described urethane synthetic catalyst was preferable is 0.22-0.3 part.
Wherein, described polyether glycol 8210H is the polyether glycol of the special screening for pentane type combined polyether.Said polyether glycol 8210H is the commercially available prod, and its viscosity is 3000-4000mpa.s (25 ℃), and functionality is 4.3, and number-average molecular weight is 560, and hydroxyl value is 400-450mgKOH/g, and moisture is less than 0.1wt%.
Wherein, described polyether glycol SA460 is the commercially available prod, and its viscosity is 12000-15000mpa.s (25 ℃), and functionality is 6, and number-average molecular weight is 730, and hydroxyl value is 440-480mgKOH/g, and moisture is less than 0.1wt%.
Wherein, described suds-stabilizing agent is the conventional all kinds of suds-stabilizing agents that use in hard polyurethane foam field, and preferable is the silicone suds-stabilizing agent, and that better is the B8462 of goldschmidt chemical corporation and/or the L6900 of U.S. Mitugao New Material Group company etc.
Wherein, described urethane synthetic catalyst is the catalyzer that is used for the hard polyurethane foam foaming, can be amines catalyst and/or organo-metallic class catalyzer, and more satisfactory is to unite to use amines catalyst and organo-metallic class catalyzer.Wherein, what described amines catalyst was preferable is tertiary amine catalyst, and that better is N, N, N`, N``, N```-five methyl diethylentriamine and/or triethylenediamine.Described organo-metallic class catalyzer is preferable is in isocaprylic acid potassium, Potassium ethanoate and the potassium oleate one or more.Urethane synthetic catalyst of the present invention comprises triethylenediamine and isocaprylic acid potassium in the time of best, and what wherein the mass ratio of triethylenediamine and isocaprylic acid potassium was preferable is 1: 1-2.5: 1.
Wherein, pentane foaming agent of the present invention can be selected in this area various pentane foaming agents commonly used for use, and like in pentamethylene, Skellysolve A and the iso-pentane one or more, preferable is the mixture or the pentamethylene of pentamethylene and iso-pentane.In said mixture, the mixing quality of pentamethylene and iso-pentane than preferable be 6: 4～8: 2.
What wherein, described water was preferable is deionized water.
In the preferable instance of the present invention one, pentane type combined polyether of the present invention comprises the composition of following mass fraction: polyether glycol 8210H 6-8 part, polyether glycol SA4602-4 part; Silicone suds-stabilizing agent B8462 or L69000.2-0.3 part, N, N; N`, N``, N```-five methyl diethylentriamine 0.02-0.03 part; Triethylenediamine 0.1-0.2 part, isocaprylic acid potassium, Potassium ethanoate or potassium oleate 0.08-0.12 part, pentamethylene 0.7-0.13 part; Iso-pentane 0-0.3 part, and deionized water 0.05-0.10 part.
In another preferred implementation of the present invention, pentane type combined polyether of the present invention is grouped into by the one-tenth of following mass fraction: polyether glycol 8210H 6-8 part, polyether glycol SA4602-4 part; Silicone suds-stabilizing agent B8462 or L69000.2-0.3 part, N, N; N`, N``, N```-five methyl diethylentriamine 0.02-0.03 part; Triethylenediamine 0.1-0.2 part, isocaprylic acid potassium, Potassium ethanoate or potassium oleate 0.08-0.12 part, pentamethylene 0.7-0.13 part; Iso-pentane 0-0.3 part, and deionized water 0.05-0.10 part.
Preferably, as required, also can contain other conventional additives of this area in the pentane type combined polyether of the present invention, as long as it does not influence the technique effect of pentane type combined polyether of the present invention basically.
The preparation method of pentane type combined polyether of the present invention is: with above-mentioned each composition by mass fraction having the uniform mixing in the still of puddling of security device, promptly obtain pentane type combined polyether.Described mixing is preferably carried out in stainless steel is puddled still, and what mixing time was preferable is 2-5 hour.
Pentane type combined polyether of the present invention is mainly used in the polyurethane insulation coating of solar water heater, and than present industry present situation, it possesses tangible environment-friendly advantage, excellent flowability ability, excellent size stability and excellent thermal conductivity.Pentane type combined polyether of the present invention directly places itself and isocyanic ester between shell and the inner bag of solar water heater and foams in use, can obtain hard polyurethane foam, thereby play the effect of filling and being incubated.
Therefore; The present invention also provides a kind of compsn that is used to prepare polyurethane foam; It comprises pentane type combined polyether of the present invention and isocyanic ester, and the mass ratio of wherein said pentane type combined polyether and isocyanic ester is 1: 1-1: 1.3, and preferable is 1: 1-1: 1.2.What described isocyanic ester was preferable is polymeric MDI (having another name called polyphenyl polymethylene polyisocyanates or thick MDI); Polymeric MDI among the present invention adopts the 44V20 of Bayer (BAYER) company, 5005 of the M20S of BASF AG or U.S.'s Hensel graceful (huntsman) urethane ltd.If the consideration cost factor, what the mass ratio of pentane type combined polyether of the present invention and isocyanic ester was preferable is 1: 1-1: 1.2.If do not consider cost factor, preferable is more than 1: 1.2, can improve the foamy quality well.Compsn of the present invention before use; Wherein pentane type combined polyether and isocyanic ester do not contact all the time; Therefore form that can suit is sold and is preserved said composition, during use pentane type combined polyether and isocyanic ester is mixed according to the above ratio, foams.
The present invention also provides a kind of hard polyurethane foam, and it is made by following method: is 1 with described pentane type combined polyether and isocyanic ester in mass ratio: 1-1: 1.3 ratio is mixed post-foaming, gets final product.What described isocyanic ester was preferable is polymeric MDI (having another name called polyphenyl polymethylene polyisocyanates or thick MDI), and the polymeric MDI among the present invention adopts the 44V20 of Bayer (BAYER) company, the M20S of BASF AG or the U.S..
What wherein, described blowing temperature was preferable is 20-25 ℃.Preferably adopt the high pressure machine to foam.
The present invention also provides the application of a kind of described hard polyurethane foam as the polyurethane insulation coating of solar water heater.
Among the present invention, above-mentioned optimum condition can be on the basis that meets this area general knowledge arbitrary combination, promptly obtain the preferable instance of the present invention.
The raw material that the present invention uses and reagent is all commercially available gets.
Positive progressive effect of the present invention is:
1, as whipping agent, pentane foaming agent has the advantage of low GWP value and zero odp value to pentane type combined polyether of the present invention with pentane, meet the environmental requirement that substitutes HCFC-141B in the solar water heater industry fully, and cost is low.
2, pentane type combined polyether of the present invention has overcome the shortcoming of pentane and polyethers consistency difference, from polyether glycol, filter out with excellent properties with the excellent product of pentane consistency as main body polyethers of the present invention.The combined polyether that obtains thus has that not only the consistency with pentane is good, and good flowing properties have excellent foaming effect, and the viscosity of combined polyether is applicable to the production technique of solar water heater.Application in the solar water heater industry has remarkable advantages.
3, the hard polyurethane foam that obtains after pentane type combined polyether of the present invention and the isocyanic ester effect has excellent thermal conductivity, dimensional stability.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
The polyether glycol 8210H that uses among the following embodiment, SA460 are Shanghai Dongda Polyurethane Co., Ltd's product.Polyether glycol NT403 purchases the big chemical industry Ltd in blue star east in Shandong.
Silicone suds-stabilizing agent B8462 purchases in goldschmidt chemical corporation, and L6900 purchases the Mitugao New Material Group company in the U.S..
The whipping agent pentamethylene is purchased in the Beijing Dongfang Yakeli Chemical Science Co., Ltd.
Isocyanic ester is a polymeric MDI, purchases in Bayer A.G, and model is 44V20.
Embodiment 1
One, the prescription of ring/iso-pentane type combined polyether:
7 parts of polyether glycol 8210H, polyether glycol SA4603 part, silicone suds-stabilizing agent B84620.2 part; N, N, N`; N``, 0.02 part of N```-five methyl diethylentriamine, 0.20 part of triethylenediamine; 0.08 part in isocaprylic acid potassium, 0.7 part of pentamethylene, 0.10 part of 0.3 part of iso-pentane and deionized water.
Two, the preparation method of ring/iso-pentane type combined polyether: the prescription according to ring/iso-pentane type combined polyether stirs above-mentioned each composition speed with 500 rev/mins under room temperature 2 hours, and blowing promptly gets.
Three, the preparation of hard polyurethane foam lagging material: will encircle/iso-pentane combined polyether and isocyanic ester in 20 ℃ react to such an extent that foam density be 35kg/m by mass ratio at 1: 1.15
3Sun power use the hard polyurethane foam lagging material, the physical and chemical performance of this hard polyurethane foam is seen table 1.
Four, the preparation of contrast 1 hard polyurethane foam lagging material:
1, HCFC-141B combined polyether preparation method: with 41109 parts of polyether glycols, polyether glycol NT4031 part, silicone suds-stabilizing agent B84620.2 part; N, N, N`; N``, 0.02 part of N```-five methyl diethylentriamine, 0.1 part of triethylenediamine; 0.1 part in isocaprylic acid potassium, 0.10 part of 1.5 parts of HCFC-141B and the deionized water speed with 500 rev/mins under room temperature stirred 2 hours, and blowing promptly gets the HCFC-141B combined polyether.
2, the preparation of contrast 1 hard polyurethane foam lagging material: 1: 1.15 in 20 ℃ react to such an extent that foam density be 35.2kg/m by mass ratio HCFC-141B combined polyether and isocyanic ester
3Sun power use the hard polyurethane foam lagging material, this physical and chemical performance that contrasts 1 hard polyurethane foam is seen table 1.
Table 1
Embodiment 2
One, the prescription of cyclopentane type combined polyether:
8 parts of polyether glycol 8210H, polyether glycol SA4602 part, silicone suds-stabilizing agent L69000.3 part, N; N; N`, N``, 0.05 part of 0.03 part of N```-five methyl diethylentriamine, 0.15 part of triethylenediamine, 0.12 part of Potassium ethanoate, 1.0 parts of pentamethylene and deionized water.
Two, the preparation method of cyclopentane type combined polyether: the prescription according to the cyclopentane type combined polyether stirs above-mentioned each composition speed with 500 rev/mins under room temperature 2 hours, and blowing promptly gets.
Three, the preparation of hard polyurethane foam lagging material: 1: 1.0 in 25 ℃ react to such an extent that foam density be 37kg/m by mass ratio pentamethylene combined polyether and isocyanic ester
3Sun power use the hard polyurethane foam lagging material, the physical and chemical performance of this hard polyurethane foam is seen table 2.
Four, the preparation of contrast 2 hard polyurethane foam lagging materials:
1, HCFC-141B combined polyether preparation method: with 41109 parts of polyether glycols, polyether glycol NT4031 part, silicone suds-stabilizing agent L69000.3 part; N, N, N`; N``, 0.03 part of N```-five methyl diethylentriamine, 0.15 part of triethylenediamine; 0.12 part of Potassium ethanoate, 0.05 part of 1.8 parts of HCFC-141B and the deionized water speed with 500 rev/mins under room temperature stirred 2 hours, and blowing promptly gets the HCFC-141B combined polyether.
2, the preparation of contrast 2 hard polyurethane foam lagging materials: 1: 1.0 react to such an extent that foam density be 37.2kg/m by mass ratio HCFC-141B combined polyether and isocyanic ester
3Sun power use the hard polyurethane foam lagging material, this physical and chemical performance that contrasts 2 hard polyurethane foams is seen table 2.
Table 2
Embodiment 3
One, the prescription of cyclopentane type combined polyether:
6 parts of polyether glycol 8210H, polyether glycol SA4604 part, silicone suds-stabilizing agent L69000.2 part, N; N; N`, N``, 0.08 part of 0.02 part of N```-five methyl diethylentriamine, 0.1 part of triethylenediamine, 0.1 part of potassium oleate, 1.3 parts of pentamethylene and deionized water.
Two, the preparation method of cyclopentane type combined polyether: the prescription according to the cyclopentane type combined polyether stirs above-mentioned each composition speed with 500 rev/mins under room temperature 2 hours, and blowing promptly gets.
Three, the preparation of hard polyurethane foam lagging material: with above-mentioned cyclopentane type combined polyether and isocyanic ester mass ratio is to react to such an extent that foam density be 38kg/m at 1: 1.30
3Sun power use the hard polyurethane foam lagging material.
Four, the preparation of contrast 3 hard polyurethane foam lagging materials:
1, HCFC-141B combined polyether preparation method: with 41109 parts of polyether glycols, polyether glycol NT4031 part, silicone suds-stabilizing agent L69000.2; N, N, N`; N``, 0.02 part of N```-five methyl diethylentriamine, 0.10 part of triethylenediamine; 0.10 part of potassium oleate, 0.08 part of 2.0 parts of HCFC-141B and the deionized water speed with 500 rev/mins under room temperature stirred 2 hours, and blowing promptly gets the HCFC-141B combined polyether.
2, the preparation of contrast 3 hard polyurethane foam lagging materials: 1: 1.30 react to such an extent that foam density be 38kg/m by mass ratio HCFC-141B combined polyether and isocyanic ester
3Sun power use the hard polyurethane foam lagging material, this physical and chemical performance that contrasts 3 hard polyurethane foams is seen table 3.
Table 3
Claims (20)
1. pentane type combined polyether; It is characterized in that: said pentane type combined polyether comprises the composition of following mass fraction: polyether glycol 8210H 6-8 part; Polyether glycol SA460 2-4 part; Suds-stabilizing agent 0.2-0.3 part, urethane synthetic catalyst 0.2-0.35 part, pentane foaming agent 1-1.3 part and water 0.05-0.1 part.
2. pentane type combined polyether as claimed in claim 1; It is characterized in that: said pentane type combined polyether is grouped into by the one-tenth of following mass fraction: polyether glycol 8210H 6-8 part; Polyether glycol SA460 2-4 part; Suds-stabilizing agent 0.2-0.3 part, urethane synthetic catalyst 0.20-0.35 part, pentane foaming agent 1.0-1.3 part and water 0.05-0.10 part.
3. according to claim 1 or claim 2 pentane type combined polyether, it is characterized in that: described urethane synthetic catalyst is the 0.22-0.3 mass parts.
4. according to claim 1 or claim 2 pentane type combined polyether, it is characterized in that: described suds-stabilizing agent is the silicone suds-stabilizing agent.
5. pentane type combined polyether as claimed in claim 4 is characterized in that: described silicone suds-stabilizing agent is silicone suds-stabilizing agent B8462 and/or L6900.
6. according to claim 1 or claim 2 pentane type combined polyether, it is characterized in that: described urethane synthetic catalyst is amines catalyst and/or organo-metallic class catalyzer.
7. pentane type combined polyether as claimed in claim 6 is characterized in that: described amines catalyst is a tertiary amine catalyst; Described organo-metallic class catalyzer is one or more in isocaprylic acid potassium, Potassium ethanoate and the potassium oleate.
8. pentane type combined polyether as claimed in claim 7 is characterized in that: described tertiary amine catalyst is N, N, N`, N`, N``-five methyl diethylentriamine and/or triethylenediamine.
9. pentane type combined polyether as claimed in claim 6 is characterized in that: described urethane synthetic catalyst comprises triethylenediamine and isocaprylic acid potassium.
10. pentane type combined polyether as claimed in claim 9 is characterized in that: the mass ratio of triethylenediamine and isocaprylic acid potassium is 1: 1-2.5: 1.
11. pentane type combined polyether according to claim 1 or claim 2 is characterized in that: described pentane foaming agent is one or more in pentamethylene, Skellysolve A and the iso-pentane.
12. pentane type combined polyether as claimed in claim 11 is characterized in that: described pentane foaming agent is the mixture or the pentamethylene of pentamethylene and iso-pentane.
13. pentane type combined polyether as claimed in claim 12 is characterized in that: in said mixture, the mixing quality of pentamethylene and iso-pentane ratio is 6: 4-8: 2.
14. a compsn that is used to prepare polyurethane foam is characterized in that: it comprises like each described pentane type combined polyether and isocyanic ester in the claim 1～13.
15. compsn as claimed in claim 14 is characterized in that: the mass ratio of said pentane type combined polyether and isocyanic ester is 1: 1-1: 1.3.
16. compsn as claimed in claim 15 is characterized in that: the mass ratio of said pentane type combined polyether and isocyanic ester is 1: 1-1: 1.2.
17. like each described compsn in the claim 14～16, it is characterized in that: described isocyanic ester is a polymeric MDI.
18. a hard polyurethane foam is characterized in that: it is made by following method: is 1 with each described pentane type combined polyether and isocyanic ester in the claim 1～13 in mass ratio: 1-1: 1.3 ratio is mixed post-foaming, gets final product.
19. hard polyurethane foam as claimed in claim 18 is characterized in that: the temperature of described foaming is 20-25 ℃; Foaming is carried out in the high pressure machine; Described isocyanic ester is a polymeric MDI.
20. like the application of claim 18 or 19 described hard polyurethane foams as the polyurethane insulation coating of solar water heater.
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| CN2010102639007A CN101948563B (en) | 2010-08-24 | 2010-08-24 | Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof |
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| CN103570902B (en) * | 2012-07-18 | 2016-02-24 | 上海东大聚氨酯有限公司 | High density polyurethane and feedstock composition, combined polyether, preparation method and purposes |
| CN104387559B (en) * | 2014-11-27 | 2017-06-09 | 山东一诺威新材料有限公司 | Acoustical absorption heat preserving spraying combined polyether of half perforate and preparation method thereof |
| CN107266700A (en) * | 2017-07-18 | 2017-10-20 | 成都新柯力化工科技有限公司 | A kind of stability pentane system environment-friendly foaming agent for polyurethane foam |
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| CN101787203B (en) * | 2010-03-24 | 2011-12-07 | 山东东大聚合物股份有限公司 | Composite material adopting pentafluorobutane as foaming agent for solar water heater and preparation method thereof |
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