CN102079803A - Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition - Google Patents
Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition Download PDFInfo
- Publication number
- CN102079803A CN102079803A CN200910199487XA CN200910199487A CN102079803A CN 102079803 A CN102079803 A CN 102079803A CN 200910199487X A CN200910199487X A CN 200910199487XA CN 200910199487 A CN200910199487 A CN 200910199487A CN 102079803 A CN102079803 A CN 102079803A
- Authority
- CN
- China
- Prior art keywords
- combined polyether
- type combined
- polyether
- water
- water type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a full-water-type combined polyether and an application method thereof. The full-water-type combined polyether comprises polyether polyol SA380, polyether polyol 310, a foam stabilizer, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine and water. The invention also discloses a composition for preparing polyurethane rigid foam. The full-water-type combined polyether disclosed by the invention overcomes the defect that Freon foaming agents used in the existing combined polyether can produce irreversible pollution in the environment, and the defects of foam deformation, higher brittleness and the like when water is used as the foaming agent. The invention provides a full-water-type combined polyether which uses water as the foaming agent; and the prepared combined polyether has the advantages of favorable thermal conductivity, excellent dimensional stability, excellent flowability, excellent demoldability and high compression strength, is especially suitable to be used as a heat insulating material in the field of solar water heaters, and has obvious environmental-protection advantage and social benefit.
Description
Technical field
The present invention relates to hard polyurethane foam foaming field, relate in particular to a kind of complete water type combined polyether and using method thereof.The invention still further relates to a kind of hard polyurethane foam composition that contains described complete water type combined polyether.
Background technology
Hard polyurethane foam is widely used in industries such as insulation, refrigeration, building with its excellent performance, but along with the extensive expansion of its application, its negative impact to environment has been beaten alarm bell to people.The whipping agent that the polyurethane foam industry adopts mainly contains: HCFC (Hydrochlorofluorocarbons), HFC (hydrogen fluorohydrocarbon), HC (alkane), liquid CO
2Or water.Whipping agent such as HCFC, HFC is all freonll-11 class (CFCs) whipping agent, the use in fluorine Lyons can consume the destruction of atmospheric ozone layer material to atmospheric ozone layer, causing uviolizing to strengthen and threaten the existence of the mankind and other tellurians, is one of serious environmental problem the most that the present mankind face.Since 2006, the action of protection ozonosphere entered the critical period of honouring an agreement.Substitute plan according to " Montreal Agreement amendment " and national CFC, we are faced with year reduction 50% of main Ozone Depleting Substances to 2005, are cut to the challenge of zero this target to reduction 85% in 2007, by 2010.
In the CFC alternative Process, extensively adopting ODP value is zero whipping agent such as pentamethylene (or ring/iso-pentane) and transition alternate blowing agent H CFC-141B, and China's solar water heater foams employing at present is HCFC-141B and HFC-245fa or partly uses HFC-365fm.These several pneumatogens all can produce Greenhouse effect to environment.
Be in environmental protection and consider, hope can be researched and developed a kind of combined polyether that can the water foaming, replaces freonll-11 class whipping agent thus.Yet, the less whipping agent that uses water as in hard polyurethane foam, major cause is: when 1. water foams, can produce CO during owing to foaming in foam
2, normal temperature forms negative pressure down easily.Therefore need make foam solid phase intensity greater than formed negative pressure, avoid causing foam deformation.The most conventional method is that foam density is brought up to 30%, and the very big increase that this just causes cost is difficult to promote.Another mode recently improves foamy body by the quality that improves combined polyether and isocyanic ester, as mass ratio is brought up to 1: 1.5, causes cost to raise equally.2. water foams formed polyurethane foam because water has participated in having formed this crumbly mass of urea with the reaction of isocyanic ester, causes the shell of foam and solar water heater and inner bag not bonding.Rare complete water type combined polyether that is used for the solar water heater lagging material in the existing market.The performance index of commercially available complete water type combined polyether are:
Summary of the invention
Technical problem to be solved by this invention is to have overcome when water is as whipping agent in the above-mentioned prior art, the foamy body of polyurethane foam and cohesiveness reduce, and combined polyether and isocyanic ester proportioning height, the defective that causes cost to raise provides a kind of complete water type combined polyether, this combined polyether with water as whipping agent, can take into account environmental requirement, can solve the problem of hard polyurethane foam intensity and cohesiveness undercarriage again, and reduce the proportioning of combined polyether and isocyanic ester, cost is low.Complete water type combined polyether of the present invention is applicable to the preparation polyurethane heat insulation material, especially is suitable for the sun power polyurethane insulation coating.
For can water as whipping agent, must avoid in foaming process, forming this crumbly mass of urea, and foamy deformation, the present invention is directed to a kind of polyether glycol for this reason, filtered out the combined polyether that can cooperate this polyether glycol use and can reach the foaming effect of excellence with excellent properties.
Therefore, the invention provides a kind of complete water type combined polyether, it comprises following each composition: polyether glycol SA380, polyether glycol 310, suds-stabilizing agent, N, N-dimethylcyclohexylamine, N, N-dimethyl benzylamine and water.
Wherein, what the mass fraction of each composition of complete water type combined polyether of the present invention was preferable is: polyether glycol SA380 5-7 part, polyether glycol 310 3-5 parts, suds-stabilizing agent 0.2-0.3 part, N, N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
Complete water type combined polyether of the present invention is a kind of colourless to lurid transparent liquid, and its physical performance index sees Table 1.
Table 1
Wherein, described polyether glycol SA380 is the commercially available prod, and its viscosity is 2000-3000mpa.s (25 ℃), and functionality is 6.0, and hydroxyl value is 250-350mgKOH/g, and moisture is less than 0.1%.
Wherein, described polyether glycol 310 is the conventional reagent in this area, and functionality is 3, and hydroxyl value is 100-200mgKOH/g, and moisture is less than 0.1%.
Wherein, described suds-stabilizing agent is the conventional all kinds of suds-stabilizing agents that use in hard polyurethane foam field, and preferable is siliceous class A foam A stablizer, and that better is the B8462 of goldschmidt chemical corporation and/or the L6900 of the U.S. 1 Mitugao New Material Group company 1 etc.
Wherein, N, N-dimethylcyclohexylamine and N, the N-dimethyl benzylamine is as the catalyzer of polyurethane reaction, these two kinds of catalyzer use together can be eliminated water and isocyanate reaction formation urea key and further form allophanate, and the fragility that reduces polyurethane foam also improves its cohesiveness.
What wherein, described water was preferable is deionized water.
Preferably, also can contain other conventional additives of this area in the complete water type combined polyether of the present invention as required, as long as it does not influence the technique effect of combined polyether of the present invention substantially.
In the preferable example of the present invention one, complete water type combined polyether of the present invention is grouped into by the one-tenth of following each mass fraction: polyether glycol SA380 5-7 part, polyether glycol 310 3-5 parts, suds-stabilizing agent 0.2-0.3 part, N, N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
Complete water type combined polyether of the present invention is mainly used in the polyurethane insulation coating of solar water heater, and than present present situation, this invention possesses tangible environment-friendly advantage and social benefit, and the shell of solar water heater is had good cohesive force.
The preparation method of complete water type combined polyether of the present invention is: each composition is pressed the mass fraction uniform mixing, promptly obtain the complete water type combined polyether.What described mixing was preferable carries out in stainless steel is puddled still, and what mixing time was preferable is 2-5 hour.
The using method of complete water type combined polyether of the present invention can be carried out with reference to the conventional using method of this area combined polyether.The present invention also provides a kind of using method of described complete water type combined polyether especially, and it comprises the steps: complete water type combined polyether of the present invention and isocyanic ester (thick MDI) are pressed mass ratio 1: 1.0-1: 1.4 mixed afterreaction.Like this can be in lower scope with cost control.Under the prerequisite of not considering cost factor, the mass ratio of combined polyether of the present invention and isocyanic ester also can be higher than l: 1.4, as with prior art in identical 1: 1.5.
The present invention also provides a kind of composition that is used to prepare polyurethane foam, and it comprises complete water type combined polyether of the present invention and isocyanic ester, and wherein the mass ratio of combined polyether and isocyanic ester is 1: 1-1: 1.4.
Among the present invention, above-mentioned each optimum condition, can be on the basis that meets this area general knowledge arbitrary combination, promptly get the preferred embodiments of the invention.
The reagent that the present invention uses and raw material is all commercially available gets.
Positive progressive effect of the present invention is:
1, in the complete water type combined polyether of the present invention with water as whipping agent, possessed good thermal conductivity, excellent size stability, flowability and demolding performace, compressive strength height with the polyurethane foam that obtains after the isocyanic ester effect.
2, complete water type combined polyether of the present invention is with its good adhesive property, and the thermal insulation layer field at solar water heater has tangible environment-friendly advantage and social benefit.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
The polyether glycol SA380 that uses among the following embodiment purchases in the B8462 of Shanghai Dongda Polyurethane Co., Ltd and purchases in goldschmidt chemical corporation.L6900 purchases the Mitugao New Material Group company in the U.S..
Embodiment 1
The prescription of complete water type combined polyether:
6 parts of polyether glycol SA380,310 4 parts of polyether glycols, silicone suds-stabilizing agent B84620.2 part, N, 0.2 part of N-dimethylcyclohexylamine, N, 0.1 part of N-dimethyl benzylamine, 0.4 part in water.
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.2 can get foam density 35kg/m
3The sun power polyurethane foam heat insulation material.
Embodiment 2
Complete water type combined polyether prescription:
5 parts of polyether glycol SA380,310 5 parts of polyether glycols, silicone suds-stabilizing agent B84620.25 part, N, 0.25 part of N-dimethylcyclohexylamine, N, 0.2 part of N-dimethyl benzylamine, 0.3 part in water.
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.0 can get foam density 38kg/m
3The sun power polyurethane foam heat insulation material.
Embodiment 3
The prescription of complete water type combined polyether:
7 parts of polyether glycol SA380,310 3 parts of polyether glycols, silicone suds-stabilizing agent L69000.3 part, N, 0.3 part of N-dimethylcyclohexylamine, N, 0.2 part of N-dimethyl benzylamine, 0.45 part in water,
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.2 can get foam density 37kg/m
3The sun power polyurethane foam heat insulation material.
The application of complete water type combined polyether of effect embodiment 1 sun power
The combined polyether of embodiment 1 is added the POL feed liquid storage tank of foaming machine, polyisocyanates is added the ISO feed liquid storage tank of foaming machine; Adjust the temperature of charge of foaming machine, adjust flow and material ratio, calculate the foaming shot (4 kilograms) of 20 vacuum pipe solars, cast, after foaming finished, the l0min demoulding was transferred to curing chamber (30-50 ℃), slaking 12h with sun power.Room temperature was placed after 3 days, and delivery is moulded bubble and detected its foaming properties, sees Table 2.
Table 2
By table 2 as seen, indexs such as the intensity of the polyurethane foam heat insulation material that makes with complete water type combined polyether of the present invention, cohesiveness, rate of closed hole, dimensional stability all have significantly than existing combined polyether and improve.
Claims (7)
1. a complete water type combined polyether is characterized in that it comprises following each composition: polyether glycol SA380, polyether glycol 310, suds-stabilizing agent, N, N-dimethylcyclohexylamine, N, N-dimethyl benzylamine and water.
2. complete water type combined polyether as claimed in claim 1, it is characterized in that: the mass fraction of described each composition of complete water type combined polyether is: polyether glycol SA3805-7 part, polyether glycol 3103-5 part, suds-stabilizing agent 0.2-0.3 part, N, N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
3. complete water type combined polyether as claimed in claim 1 or 2 is characterized in that: described suds-stabilizing agent is siliceous class A foam A stablizer.
4. complete water type combined polyether as claimed in claim 3 is characterized in that: described siliceous class A foam A stablizer is B8462 and/or L6900.
5. complete water type combined polyether as claimed in claim 1 or 2, it is characterized in that: described complete water type combined polyether is grouped into by the one-tenth of following each mass fraction: polyether glycol SA380 5-7 part, polyether glycol 310 3-5 parts, suds-stabilizing agent 0.2-0.3 part, N, N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
6. the using method of a complete water type combined polyether is characterized in that: it comprises the steps: each described complete water type combined polyether and isocyanic ester in the claim 1～5 by mass ratio 1: 1.0-1: after 1.4 the mixed promptly.
7. composition that is used to prepare polyurethane foam, it is characterized in that: it comprises each described complete water type combined polyether and isocyanic ester in the claim 1～5, and wherein the mass ratio of combined polyether and isocyanic ester is 1: 1-1: 1.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910199487XA CN102079803B (en) | 2009-11-27 | 2009-11-27 | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910199487XA CN102079803B (en) | 2009-11-27 | 2009-11-27 | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102079803A true CN102079803A (en) | 2011-06-01 |
| CN102079803B CN102079803B (en) | 2012-08-22 |
Family
ID=44086020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910199487XA Expired - Fee Related CN102079803B (en) | 2009-11-27 | 2009-11-27 | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102079803B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604024A (en) * | 2012-02-02 | 2012-07-25 | 上海东大聚氨酯有限公司 | Fluorine-free flame retardant polyurethane combined polyether and using method thereof |
| CN102942671A (en) * | 2012-12-03 | 2013-02-27 | 山东东大一诺威新材料有限公司 | External thermal-insulation environment-friendly composite polyether for delivering high-temperature media and preparation method thereof |
| CN103213236A (en) * | 2013-04-08 | 2013-07-24 | 南京恒能新材料有限公司 | Manufacturing process of polyurethane heat-insulating plate |
| CN103319677A (en) * | 2013-07-15 | 2013-09-25 | 广西吉顺能源科技有公司 | Polyether polyol foam thermal-insulation material for water tank of solar water heater |
| CN103665295A (en) * | 2012-09-21 | 2014-03-26 | 上海东大聚氨酯有限公司 | Combined polyether, raw material composition and polyurethane foam as well as preparation method and application of combined polyether, raw material composition and polyurethane foam |
| CN103772636A (en) * | 2013-12-25 | 2014-05-07 | 广西超星太阳能科技有限公司 | Polyurethane rigid foam composition |
| CN103897142A (en) * | 2013-11-13 | 2014-07-02 | 中国寰球工程公司 | Casting type foaming-in-site deep-cooling heat insulating material for valve |
| CN106366276A (en) * | 2016-08-26 | 2017-02-01 | 江苏中圣管道工程技术有限公司 | High-density rigid polyurethane foam material prefabricated heat insulating pipeline and prefabricating method |
| CN107814899A (en) * | 2017-11-13 | 2018-03-20 | 清远市蓝林新材料有限公司 | Combined polyether glycol insulation material for solar water container and preparation method thereof |
| CN109021206A (en) * | 2018-05-22 | 2018-12-18 | 南京红宝丽聚氨酯有限公司 | Low-density polyurethane continuous slab preparation method in a kind of full water |
| CN109776748A (en) * | 2019-01-22 | 2019-05-21 | 天津爱德加科技有限公司 | A kind of full hydraulic matter polyurethane foam composition polyethers of high temperature resistant, hard polyurethane foams and preparation method thereof |
| CN111560108A (en) * | 2020-05-15 | 2020-08-21 | 上海抚佳精细化工有限公司 | Full-water polyurethane rigid foam and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494244C (en) * | 2006-12-28 | 2009-06-03 | 四川师范大学 | Hard polyurethane foam plastic specially adapted for pipe insulation layer |
| US9550854B2 (en) * | 2007-10-12 | 2017-01-24 | Honeywell International Inc. | Amine catalysts for polyurethane foams |
| CN100564418C (en) * | 2007-10-24 | 2009-12-02 | 济南大学 | A kind of monocomponent polyurethane adhesive and preparation method thereof and application |
| PT2090621E (en) * | 2008-02-18 | 2010-04-15 | Preform Gmbh | Sound absorbing foam system |
-
2009
- 2009-11-27 CN CN200910199487XA patent/CN102079803B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604024B (en) * | 2012-02-02 | 2013-11-13 | 上海东大聚氨酯有限公司 | Fluorine-free flame retardant polyurethane combined polyether and using method thereof |
| CN102604024A (en) * | 2012-02-02 | 2012-07-25 | 上海东大聚氨酯有限公司 | Fluorine-free flame retardant polyurethane combined polyether and using method thereof |
| CN103665295B (en) * | 2012-09-21 | 2016-04-20 | 上海东大聚氨酯有限公司 | Combined polyether, feedstock composition, polyurethane foam and its production and use |
| CN103665295A (en) * | 2012-09-21 | 2014-03-26 | 上海东大聚氨酯有限公司 | Combined polyether, raw material composition and polyurethane foam as well as preparation method and application of combined polyether, raw material composition and polyurethane foam |
| CN102942671B (en) * | 2012-12-03 | 2014-11-05 | 山东一诺威新材料有限公司 | External thermal-insulation environment-friendly composite polyether for delivering high-temperature media and preparation method thereof |
| CN102942671A (en) * | 2012-12-03 | 2013-02-27 | 山东东大一诺威新材料有限公司 | External thermal-insulation environment-friendly composite polyether for delivering high-temperature media and preparation method thereof |
| CN103213236A (en) * | 2013-04-08 | 2013-07-24 | 南京恒能新材料有限公司 | Manufacturing process of polyurethane heat-insulating plate |
| CN103319677A (en) * | 2013-07-15 | 2013-09-25 | 广西吉顺能源科技有公司 | Polyether polyol foam thermal-insulation material for water tank of solar water heater |
| CN103319677B (en) * | 2013-07-15 | 2016-02-03 | 广西吉顺能源科技有限公司 | Solar water heater water tank polyether glycol cellular insulant |
| CN103897142A (en) * | 2013-11-13 | 2014-07-02 | 中国寰球工程公司 | Casting type foaming-in-site deep-cooling heat insulating material for valve |
| CN103897142B (en) * | 2013-11-13 | 2017-04-12 | 中国寰球工程有限公司 | Casting type foaming-in-site deep-cooling heat insulating material for valve |
| CN103772636A (en) * | 2013-12-25 | 2014-05-07 | 广西超星太阳能科技有限公司 | Polyurethane rigid foam composition |
| CN106366276A (en) * | 2016-08-26 | 2017-02-01 | 江苏中圣管道工程技术有限公司 | High-density rigid polyurethane foam material prefabricated heat insulating pipeline and prefabricating method |
| CN107814899A (en) * | 2017-11-13 | 2018-03-20 | 清远市蓝林新材料有限公司 | Combined polyether glycol insulation material for solar water container and preparation method thereof |
| CN109021206A (en) * | 2018-05-22 | 2018-12-18 | 南京红宝丽聚氨酯有限公司 | Low-density polyurethane continuous slab preparation method in a kind of full water |
| CN109776748A (en) * | 2019-01-22 | 2019-05-21 | 天津爱德加科技有限公司 | A kind of full hydraulic matter polyurethane foam composition polyethers of high temperature resistant, hard polyurethane foams and preparation method thereof |
| CN111560108A (en) * | 2020-05-15 | 2020-08-21 | 上海抚佳精细化工有限公司 | Full-water polyurethane rigid foam and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102079803B (en) | 2012-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102079803B (en) | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition | |
| CN102229697B (en) | Solar polyurethane thermal insulation material | |
| CN102030977B (en) | Conjugate polyether, polyurethane raw material composition, polyurethane foams and applications thereof | |
| CN103665296B (en) | Low temperature is low leads polyurethane foam, feedstock composition, combined polyether and preparation method | |
| CN111647191B (en) | Low-conductivity foaming agent composition, polyurethane rigid foam and preparation method thereof | |
| CN106750093A (en) | A kind of refrigerator for the polyurethane foam system of refrigerator and based on it | |
| CN102766247A (en) | Rigid polyurethane/polyvinyl chloride composite foam plastic and preparation method thereof | |
| CN103319678A (en) | Polyurethane rigid foam thermal-insulation material for water tank of solar water heater | |
| CN101161699B (en) | Polyether polyvalent alcohol for preparing no-freon polyurethane hard foam plastic and preparation method thereof | |
| CN102977314A (en) | Environment-friendly composite polyether for ultralow-temperature freezer, preparation method and application | |
| JP3700499B2 (en) | refrigerator | |
| CN100509903C (en) | Hard polyurethane foam plastic | |
| CN101016364A (en) | Hard polyurethane foam plastic prepared by third-generation foaming agent | |
| CN101948563B (en) | Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof | |
| CN113754850A (en) | Polyurethane foam and preparation method and application thereof | |
| WO2024016743A1 (en) | Rigid polyurethane foam, preparation method therefor, and thermal insulation material, refrigerator or freezer comprising rigid polyurethane foam | |
| CN112175158A (en) | Refrigerator, hard polyurethane foam and preparation method of hard polyurethane foam | |
| CN101544778A (en) | Vesicant composite for producing rigid polyurethane foam and application thereof | |
| CN113637136B (en) | Mixed foaming agent combined polyether and polyurethane hard foam | |
| CN114133512B (en) | All-water foaming polyurethane raw material composition for polyurethane security door and preparation method thereof | |
| CN106832212B (en) | Storage-type electric water heater polyurethane rigid foam material and preparation method thereof | |
| CN102532453A (en) | Normal pentane foamed rigid polyurethane foam combined polyether for refrigerator | |
| CN106220825A (en) | Refrigerator car polyurethane bulk bubble insulation material and preparation method thereof | |
| KR100850995B1 (en) | A composition for preparing rigid polyurethane foam and rigid polyurethane foam made therefrom | |
| CN103739808A (en) | Polyurethane thermal-insulation material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120822 Termination date: 20191127 |