CN103382263B - Green-blowing agent produces method and the product of hard polyurethane foam - Google Patents
Green-blowing agent produces method and the product of hard polyurethane foam Download PDFInfo
- Publication number
- CN103382263B CN103382263B CN201310255953.8A CN201310255953A CN103382263B CN 103382263 B CN103382263 B CN 103382263B CN 201310255953 A CN201310255953 A CN 201310255953A CN 103382263 B CN103382263 B CN 103382263B
- Authority
- CN
- China
- Prior art keywords
- tetra
- polyurethane foam
- methyl ether
- hard polyurethane
- ethyl methyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of method that green-blowing agent produces hard polyurethane foam, reaction raw materials comprises polyisocyanates, polyvalent alcohol and whipping agent, and whipping agent is wherein 1,1,2,2-tetra-fluoro ethyl methyl ether,? 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, and only just mixes with other reactive component before the reaction, is the direct mixed foaming in scene.The present invention also provides the hard polyurethane foam material using aforesaid method to obtain simultaneously.The present invention is with 1,1,2,2-tetra-fluoro ethyl methyl ether is as whipping agent, and adopt on-the-spot directly mixed foaming technology (whipping agent is independently deposited, and only just mixes with other reactive component before the reaction) to prepare hard polyurethane foam lagging material, compared with existing technological process control, both can overcome the storage instability problem of Preblend, restriction can not have been produced to the use of catalyzer again; Hard polyurethane foam material excellent performance prepared by the method.
Description
Technical field
The invention belongs to hard polyurethane foam material technical field, be specifically related to a kind of containing 1,1,2,2-tetra-fluoro ethyl methyl ether (HFE-254pc) as the preparation method of the building materials insulation industry hard polyurethane foam of whipping agent and the product that obtained by the method.
Background technology
Polyurethane foam is with polyol and isocyanic ester for raw material, through the foam materials of addition polymerization, foaming under the effect of such as catalyzer, whipping agent.This material has excellent physical and mechanical properties, electric property, acoustical behavior and chemical resistance.Because its thermal conductivity is low, density is little, intensity is high, water-absorbent is little, adiabatic, insulation, sound insulation, chemical stability be good, be hit after response rate high, be therefore widely used in the fields such as oil, chemical industry, transport, building.
Current China mainly adopts HCFC-141b(dichloro one fluoroethane in hard polyurethane foam field) foam as transition whipping agent.But HCFC-141b also belongs to Ozone Depleting Substances (ODS), there is higher depletion latent energy value (ODP value) and global warming potential (GWP value), eliminated it in developed country and produced and application.China, as the contracting party of Montreal protocol, has formulated HCFCs and has accelerated to eliminate plan.
Existing market mainly contain pentane series and HFC series (HFC-245fa, HFC-365mfc etc.) as third generation substitutes for CFCs.But pentane class whipping agent obviously can affect the flame retardant properties of product, and brings potential safety hazard to production; The whipping agent Greenhouse effect of HFC series are large, and wherein the GWP value of HFC-245fa is the GWP value of 1020, HFC-365mfc is 782, also there is the defect of environmental protection aspect.Therefore must find a novel whipping agent, the Production requirement of hard polyurethane foam can be met, do not destroy ozone again, reduce Greenhouse effect simultaneously.
In the document " new generation of environment protection blowing agent H FE-254 " (building energy conservation, the 8th phase in 2008, p36-38), a novel environment-friendly foaming agent 1,1,2,2-tetra-fluoro ethyl methyl ether (HFE-254pc) of introduction of authors.This hydrogen fluorine ether (HFEs) class whipping agent and HFC similar, its ODP value is 0.But its GWP value is low, in an atmosphere short-lived, and environmental-protecting performance is excellent.But 1,1,2,2-tetra-fluoro ethyl methyl ether (HFE-254pc), owing to having-CF in molecule
2oCH
3structure, therefore, unstable chemcial property when it coexists with alkali in Preblend, is easily hydrolyzed due to the existence of moisture, the hypoacidity activity of catalyzer and the function of suds-stabilizing agent that are produced by hydrolysis, this brings bad impact to preparing hard polyaminoester hard foam.
In order to solve the problem, in patent CN101687973A, inventor provide and a kind ofly comprise the Preblend as whipping agent of HFE-254pc and water, this Preblend adopts N-substituted imidazole, N-replaces the N-substituted nitrogen-containing heterocyclic compounds such as morpholine as catalyzer to improve the stability of HFE-254pc in polyvalent alcohol in Preblend, but because N-substituted nitrogen-containing heterocyclic compound stink is unpleasant, not by the producer and consumers welcomed.
In patent application 201210069113.8, inventor provide the Preblend of a kind of hard polyurethane foams polyhydric alcohol composition, it adopts olefinic organic compounds (a-vinyl toluene), and at least one compound that N-substituted nitrogen-containing heterocyclic compound (N-substituted ring hexylamine) and triaizine compounds form is that catalyzer is to increase the stability of HFE-254pc in said composition Preblend.But a lot of widespread use at present and the tertiary amine catalyst of excellent performance cannot use in this foaming system in this case, as retardance catalyzer etc., have impact on technique and the product performance of production.
In patent CN101687973A, contriver also takes HFE-254pc/HFC-245fa (30/70 (weight ratio)) to mix, HFC-245fa is utilized to improve the flash-point of mixed foaming thing, but now foam body there occurs change, not using HFE-254pc as topmost whipping agent, and the discharge of greenhouse gases is still added to the use of HFC-245fa.
In patent CN1307230C, contriver suppresses the vapour pressure of HFC-245fa whipping agent with HFE-254pc, and can keep the physical property and heat-proof quality etc. of hard polyurethane foams, but HFE-254pc uses as the 3rd whipping agent, is not the topmost composition of whipping agent.
Summary of the invention
The first object of the present invention is to provide a kind of on-the-spot directly mixed foaming technology (can be continuous processing or interrupter method) and prepares the preparation method of hard polyurethane foam lagging material, to overcome the storage problem of HFE-254pc Preblend, and existing HFE-254pc Preblend produces the technical problem of restriction to the use of catalyzer.
The second object of the present invention is to provide a kind of hard polyurethane foam material using aforesaid method to prepare, and to overcome the storage problem of HFE-254pc Preblend, and existing HFE-254pc Preblend produces the technical problem of restriction to the use of catalyzer.
Technical scheme of the present invention is as follows:
A kind of green-blowing agent produces the method for hard polyurethane foam, reaction raw materials comprises polyisocyanates, polyvalent alcohol and whipping agent, and described whipping agent is 1,1,2,2-tetra-fluoro ethyl methyl ether, described 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, and only just mixes with other reactive component before the reaction, is the direct mixed foaming in scene.Preferably, with polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part.Wherein, blowing agent H FE-254pc can be commercially available any one, the product that the blowing agent H FE-254pc used in the embodiment of the present invention produces for Ju Hua group; And it is in the preferred embodiment, that heptafluoro-propane (HFC-227ea) is blended to eliminate flash-point with HFE-254pc; Wherein, HFC-227ea preferably addition be: the 1%-10% accounting for the blended whipping agent total mass obtained after described 1,1,2,2-tetra-fluoro ethyl methyl ether and described heptafluoro-propane HFC-227ea mix.
The direct mixed foaming technology in described scene is selected from interrupter method or continuous processing; Wherein,
Described interrupter method is: polyvalent alcohol and various auxiliary agent are mixed and made into Preblend, and whipping agent 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, and only just mix with described Preblend before foaming, the mixture obtained mixes rapidly with polyisocyanates, foams; The more specific scheme of of the method comprises the steps:
(1) polyvalent alcohol and various auxiliary agent are mixed and made into Preblend, this Preblend can standing storage;
(2), during foaming, Preblend and 1,1,2,2-tetra-fluoro ethyl methyl ether are mixed in a reservoir, make mixed solution, mixed solution pours into foaming machine A tank; Wherein, with polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part; Isocyanic ester pours into foaming machine B tank;
(3) mixed rapidly with isocyanic ester by above-mentioned mixed solution and foam, wherein, with polyvalent alcohol 100 parts by weight, the add-on of isocyanic ester is 20-400 weight part; Polyurethane foaming machine is high pressure foaming machine or low-pressure blowing machine, wherein uses during high pressure foaming machine and takes spray pattern to mix; Using during low-pressure blowing machine takes mechanical stirring to mix, rotating speed of agitator 800-10000 rev/min;
(4) molded, mould temperature 0-80 ° C;
(5) demoulding, obtains hard polyurethane foam material.
Described continuous processing is: 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, only before foaming with polyvalent alcohol, polyisocyanates, various auxiliary agent injects mixing equipment simultaneously and carries out continuous foamed.The more specific scheme of of the method comprises the steps:
(1) by polyvalent alcohol, various auxiliary agent, 1,1,2,2-tetra-fluoro ethyl methyl ether, isocyanic ester, is filled into independently raw material storage tank respectively;
(2) raw material in each storage tank is controlled to inject foaming machine hybrid chamber by mechanical pump by under meter, after high-speed mixing, inject mould; With polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part; The add-on of isocyanic ester is 20-400 weight part; Polyurethane foaming machine is high pressure foaming machine or low-pressure blowing machine; Wherein, using during high pressure foaming machine takes spray pattern to mix; Using during low-pressure blowing machine takes mechanical stirring to mix, rotating speed of agitator 800-10000 rev/min;
(3) molded, mould temperature 0-80 ° C;
(4) demoulding, obtains hard polyurethane foam material.
The polyvalent alcohol being applicable to manufacturing hard polyurethane foam of the present invention is without particular limitation, the conventional polyol for the manufacture of urethane can be selected, for material of construction hard polyurethane foams, the optional at least one in polyether glycol and polyester polyol of polyvalent alcohol; Preferably, described polyether glycol can be selected from the polyether polyol that the functionality formed for initiator with at least one of at least one in propylene glycol, ethylene glycol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, sorbyl alcohol and quadrol and tolylene diamine is 2-6, hydroxyl value is 18-800; Described polyester polyol is selected from least one and ethylene glycol, propylene glycol, glycerol, the TriMethylolPropane(TMP), 1 that backbone structure adopts hexanodioic acid and Tetra hydro Phthalic anhydride, 4-butyleneglycol, 1, the functionality that at least one polycondensation of 6 hexylene glycols, pentanediol is formed is 2-4, hydroxyl value is the polyester polyol of 50-500.
Polyisocyanates of the present invention can be the conventional polyisocyanates of this area for the manufacture of urethane.In an example of the present invention, the Non-limiting examples of described polyisocyanates has 4,4 '-'-diphenylmethane diisocyanate or diphenylmethanediisocyanate are correlated with modified product, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanates, poly methylene poly phenyl poly isocyanate or its relevant modified product.In a better example of the present invention, the NCO% content of described polyisocyanates is 18.0-36.0%.
Auxiliary agent of the present invention is optional prepares usual auxiliaries from polyurethane foam, such as catalyzer, fire retardant, UV light stabilizing agent etc.Those of ordinary skill in the art is according to concrete purposes and be not difficult to determine kind and the add-on in the reactive mixture thereof of concrete auxiliary agent in conjunction with its expertise, does not limit herein.
Wherein, the adoptable catalyzer of the present invention can be the conventional catalyst of this area for the manufacture of urethane.In a better example of the present invention, the not limiting example of described catalyzer has 1, 4-diazonium (2, 2, 2-cyclooctane), triethyl diamines (DABCO), N, N, N ', N ', N "-pentamethyl--diethyl triamine (PMDETA), N, N-dimethylcyclohexylamine (DMCHA), N, N-dimethyl benzylamine, N, N '-Tetramethyl Ethylene Diamine (TMEDA), Dimethylaminopropyl amine (DMAPA) AminZ, N, N-dimethylethanolamine (DMEA), 2, 4, 6-tri-(dimethylaminomethyl) phenol, N-ethylmorpholine (NEM), two N, N '-dimethyl amido ethyl ether, dibutyl tin dilaurate (DBTDL) etc.,
The adoptable fire retardant of the present invention can be the conventional flame retardants of this area for the manufacture of urethane.In a better example of the present invention, the Non-limiting examples of described fire retardant has melamine cyanurate, trimeric cyanamide, ammonium polyphosphate, tetrabromophenol A, IXOL 251, the dry glycol of tetrabromo-benzene etc.;
The invention provides a kind of hard polyurethane foam material, it adopts above-mentioned arbitrary method prepare and obtain.
Compared with prior art, beneficial effect of the present invention is as follows:
The first, hard polyurethane foam material of the present invention as whipping agent, can meet the requirement of polyurethane foam technique with 1,1,2,2-tetra-fluoro ethyl methyl ether (HFE-254pc), again can meet the requirement of environmental protection: zero odp value, low GWP value;
Second, the present invention is with 1,1,2,2-tetra-fluoro ethyl methyl ether (HFE-254pc) is as whipping agent, and (blowing agent H FE-254pc independently deposits to adopt on-the-spot directly mixed foaming technology, only just mix with other reactive component before the reaction) prepare hard polyurethane foam lagging material, compared with existing technological process control, both can overcome the storage instability problem of Preblend, restriction can not be produced to the use of catalyzer again;
3rd, the hard polyurethane foam material adopting the inventive method to prepare is compared with adopting the hard polyurethane foam material of traditional HFC-245fa whipping agent, and cream time is longer, is easier to control reaction aborning; Density is lower, and hard bubbling that unit whipping agent is produced is more; Foamy appearance is better; Mechanical property is better, better heat preservation; Excellent fireproof performance.
Certainly, implement arbitrary product of the present invention might not need to reach above-described all advantages simultaneously.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of those skilled in the art and adjustment, still belong to protection scope of the present invention in actual applications.
Embodiment 1
The present embodiment adopts interrupter method to prepare hard polyurethane foam material:
96 grams of HFE-254pc and 4 gram HFC-227ea are added container, after airtight rapidly, mixes, obtained mixed foaming agent, refrigerates stand-by;
Mixed by the catalyzer Dabco EG of the deionized water of the suds-stabilizing agent L-6860 of the polyether glycol ZS-4110 of 100 weight parts, 2 mass parts, 1 weight part, 0.5 weight part, stir, obtained combination A material, in the industrial production, combination A material also can standing storage;
Above-mentioned two steps in no particular order.103.5 grams of combination A material are mixed with 20 grams of mixed foaming agents, after stirring, 130 grams of isocyanic ester PM-200 is added mixture, in low-pressure blowing machine, takes mechanical stirring to mix, with 1500rpm rotating speed mix and blend 5 second under 25 ° of C.Pour mixture into transparent cup to be again molded, mould temperature 60 ° of C, observe foaming process, the afterwards demoulding, obtain hard polyurethane foam material.And performance test is carried out as following table 1 to the hard polyurethane foam material obtained.
Comparative example 1
This comparative example 1 is the comparative example of embodiment 1.
This comparative example 1 uses HFC-245fa as whipping agent, carries out same experiment with embodiment 1.The performance of the hard polyurethane foam material obtained is as following table 1.
[table 1]
Can be found out by the data of table 1, adopt the embodiment 1 of HFE-254pc/HFC-227ea whipping agent with adopt HFC-245fa as whipping agent comparative example 1 compared with, the cream time of hard polyurethane foam material is longer, is easier to control reaction aborning; Density is lower, and hard bubbling that unit whipping agent is produced is more; Foamy appearance is better.
Embodiment 2
The present embodiment adopts continuous processing to prepare hard polyurethane foam material:
96 grams of HFE-254pc and 4 gram HFC-227ea are added container, after airtight rapidly, mixes, obtained mixed foaming agent, refrigerates stand-by;
Polyvalent alcohol Desmophen 3607, L-6860, fire retardant TCPP, glycerine, catalyzer DBTDL, isocyanic ester MDI, mixed foaming agent (HFE-254pc/HFC-227ea) are filled into respective storage tank respectively.Adjust as following table 2 respectively by each outlet flow control, the flow of each raw material is controlled by under meter.
[table 2]
Start mechanical pump, the raw material in each storage tank is injected low-pressure blowing machine hybrid chamber, is uniformly mixed, rotating speed of agitator 10000 revs/min through high speed machine, mould molding is injected in ejection afterwards, and mould temperature 60 ° of C, afterwards demouldings, obtain hard polyurethane foam material.The detected result of the hard polyurethane foam material obtained is as following table 3.
[table 3]
As can be seen from Table 3, the hard polyurethane foam material abscess that the continuous processing of the present embodiment 2 is obtained evenly, finer and smoother, mechanical property is better, better heat preservation, and its excellent fireproof performance, can reach B1 level.
Each raw material cited by the present invention and method can realize the present invention, and the bound value of each raw material and technique, interval value can realize the present invention, do not enumerate embodiment at this.
Claims (6)
1. the method for a green-blowing agent production hard polyurethane foam, reaction raw materials comprises polyisocyanates, polyvalent alcohol, catalyzer and whipping agent, it is characterized in that, described catalyzer is selected from 1, 4-diazonium (2, 2, 2-cyclooctane), triethyl diamines, N, N, N ', N ', N "-pentamethyl--diethyl triamine, N, N-dimethylcyclohexylamine, N, N-dimethyl benzylamine, N, N '-Tetramethyl Ethylene Diamine, Dimethylaminopropyl amine, N, N-dimethylethanolamine, 2, 4, 6-tri-(dimethylaminomethyl) phenol, N-ethylmorpholine, two N, one in N '-dimethyl amido ethyl ether, described whipping agent is 1, 1, 2, 2-tetra-fluoro ethyl methyl ether, wherein, described 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, and only just mixes with other reactive component comprising described catalyzer before the reaction, is the direct mixed foaming in scene, the direct mixed foaming technology in described scene is selected from interrupter method or continuous processing, wherein,
Described interrupter method is: polyvalent alcohol and the various auxiliary agents comprising described catalyzer are mixed and made into Preblend, whipping agent 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, and only just mixes with described Preblend before foaming, the mixture obtained mixes rapidly with polyisocyanates, foams;
Described continuous processing is: 1,1,2,2-tetra-fluoro ethyl methyl ether is independently deposited, only before foaming with polyvalent alcohol, polyisocyanates, the various auxiliary agents comprising described catalyzer inject mixing equipment simultaneously and carry out continuous foamed.
2. green-blowing agent as claimed in claim 1 produces the method for hard polyurethane foam, and it is characterized in that, with polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part.
3. green-blowing agent as claimed in claim 1 produces the method for hard polyurethane foam, and it is characterized in that, described interrupter method comprises the steps:
(1) polyvalent alcohol and the various auxiliary agents comprising described catalyzer are mixed and made into Preblend;
(2), during foaming, Preblend and 1,1,2,2-tetra-fluoro ethyl methyl ether are mixed in a reservoir, make mixed solution, mixed solution pours into foaming machine A tank; Wherein, with polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part; Isocyanic ester pours into foaming machine B tank;
(3) mixed rapidly with isocyanic ester by above-mentioned mixed solution and foam, wherein, with polyvalent alcohol 100 parts by weight, the add-on of isocyanic ester is 20-400 weight part; Polyurethane foaming machine is high pressure foaming machine or low-pressure blowing machine, wherein uses during high pressure foaming machine and takes spray pattern to mix; Using during low-pressure blowing machine takes mechanical stirring to mix, rotating speed of agitator 800-10000 rev/min;
(4) molded, mould temperature 0-80 ° C;
(5) demoulding, obtains hard polyurethane foam material.
4. green-blowing agent as claimed in claim 1 produces the method for hard polyurethane foam, and it is characterized in that, described continuous processing comprises the steps:
(1) by polyvalent alcohol, comprise the various auxiliary agents of described catalyzer, 1,1,2,2-tetra-fluoro ethyl methyl ether, isocyanic ester, is filled into independently raw material storage tank respectively;
(2) raw material in each storage tank is controlled to inject foaming machine hybrid chamber by mechanical pump by under meter, after high-speed mixing, inject mould; With polyvalent alcohol 100 parts by weight, the add-on of 1,1,2,2-tetra-fluoro ethyl methyl ether is 2-100 weight part; The add-on of isocyanic ester is 20-400 weight part; Polyurethane foaming machine is high pressure foaming machine or low-pressure blowing machine; Wherein, using during high pressure foaming machine takes spray pattern to mix; Using during low-pressure blowing machine takes mechanical stirring to mix, rotating speed of agitator 800-10000 rev/min;
(3) molded, mould temperature 0-80 ° C;
(4) demoulding, obtains hard polyurethane foam material.
5. green-blowing agent as claimed in claim 1 produces the method for hard polyurethane foam, it is characterized in that, described whipping agent 1, also heptafluoro-propane HFC-227ea is added with in 1,2,2-tetra-fluoro ethyl methyl ether, described heptafluoro-propane HFC-227ea quality accounts for described 1, the 1%-10% of 1,2,2-tetra-fluoro ethyl methyl ether and described heptafluoro-propane HFC-227ea total mass.
6. green-blowing agent as described in claim 1 or 3 or 4 produces the method for hard polyurethane foam, it is characterized in that, described auxiliary agent also comprises following one or more: fire retardant, UV light stabilizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255953.8A CN103382263B (en) | 2013-06-25 | 2013-06-25 | Green-blowing agent produces method and the product of hard polyurethane foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255953.8A CN103382263B (en) | 2013-06-25 | 2013-06-25 | Green-blowing agent produces method and the product of hard polyurethane foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103382263A CN103382263A (en) | 2013-11-06 |
| CN103382263B true CN103382263B (en) | 2015-10-28 |
Family
ID=49490208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310255953.8A Expired - Fee Related CN103382263B (en) | 2013-06-25 | 2013-06-25 | Green-blowing agent produces method and the product of hard polyurethane foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103382263B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024766B (en) * | 2019-12-24 | 2021-12-07 | 比亚迪股份有限公司 | Polyurethane composition and polyurethane foam |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443134A (en) * | 2011-09-16 | 2012-05-09 | 广东万华容威聚氨酯有限公司 | Polyurethane rigid foam and preparation method thereof |
| CN102604022A (en) * | 2012-03-08 | 2012-07-25 | 巨化集团公司 | Hard polyurethane foam polyalcohol composite for refrigerating industry |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277458A (en) * | 2002-03-27 | 2003-10-02 | National Institute Of Advanced Industrial & Technology | Method for producing rigid foam |
| JP2009013247A (en) * | 2007-07-03 | 2009-01-22 | Central Glass Co Ltd | Stabilized premix for rigid polyurethane foam |
-
2013
- 2013-06-25 CN CN201310255953.8A patent/CN103382263B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443134A (en) * | 2011-09-16 | 2012-05-09 | 广东万华容威聚氨酯有限公司 | Polyurethane rigid foam and preparation method thereof |
| CN102604022A (en) * | 2012-03-08 | 2012-07-25 | 巨化集团公司 | Hard polyurethane foam polyalcohol composite for refrigerating industry |
Non-Patent Citations (2)
| Title |
|---|
| "新一代环保型发泡剂HFE-254";David Flanigan等;《建筑节能》;20081231(第8期);第36-38页 * |
| 陈鼎南编著.聚氨酯制品的制造原理.《聚氨酯制品生产工艺》.化学工业出版社,2008,第36-43页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103382263A (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6647343B2 (en) | Cis-1,1,1,4,4,4-hexafluoro-2-butene foam molding compositions and use of the compositions in the production of polyisocyanate-based foams | |
| CA3023927C (en) | Foam-forming compositions containing azeotrope-like mixtures containing cis-1,1,1,4,4,4-hexafluoro-2-butene and dimethoxymethane | |
| EP2129709B2 (en) | Process for preparing thermosetting foams | |
| KR100649377B1 (en) | Rigid foam compositions and methods employing alkyl alkanoates as a blowing agent | |
| JP2015071780A (en) | Compositions and use of cis-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in preparation of polyisocyanate-based foams | |
| JP2010534254A (en) | Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam molding compositions in the production of polyisocyanate-based foams | |
| CN104341573A (en) | Polyurethane foam plastic and preparation method thereof | |
| KR20160113128A (en) | Cryogenic insulation foam | |
| JP2018502960A (en) | Polyurethane foam composition, polyurethane foam, and use thereof | |
| EP2202262B1 (en) | Composition for rigid polyurethane foam and rigid polyurethane foam produced using the same | |
| BR112016016766B1 (en) | process and reaction system for preparing rigid polyisocyanurate foam, rigid polyisocyanurate foam, and polyfunctional isocyanate reactive composition | |
| CN110054752A (en) | A kind of low density rigid polyurethane foam and preparation method thereof | |
| CN106167540A (en) | Continuous way produces polyurethane plate high fire-retardance combined polyether and preparation method thereof | |
| AU1368999A (en) | Integral skin foams | |
| CN109422907B (en) | Blowing agents comprising polyamines and alkanolamine salts and use in polyurethane continuous panel foam materials | |
| CN103382263B (en) | Green-blowing agent produces method and the product of hard polyurethane foam | |
| CN109535688A (en) | A kind of polyurethane foam heat insulation material and preparation method thereof | |
| CN107955122A (en) | A kind of CO2Overcritical auxiliary blown rigid polyurethane foam and preparation method thereof | |
| CN110105537B (en) | Polyurethane rigid foam material and preparation method thereof | |
| CN105713401B (en) | It is a kind of full water foamed bitumen polyurethane hard foamed and preparation method thereof | |
| JP2001526728A (en) | Rigid polyurethane foam | |
| KR100982430B1 (en) | Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam | |
| HU207112B (en) | Foaming agent suitable for foaming plastics | |
| AU748858B2 (en) | Process for rigid polyurethane foams | |
| KR101306144B1 (en) | Water blowned polyurethane composition for earth-based lng tank and manufacturing method of it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HUAFON PUREN POLYURETHANE CO., LTD. TECHN Free format text: FORMER OWNER: SHANGHAI HUAFON PUREN POLYURETHANE CO., LTD. Effective date: 20140529 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20140529 Address after: 201203, 12, Lane 572, Lane 115, blue wave road, Zhangjiang hi tech park, Shanghai, Pudong New Area Applicant after: SHANGHAI HUAFON MATERIAL TECHNOLOGY Research Institute (L.P.) Applicant after: SHANGHAI HUAFON PUREN PU CO.,LTD. Applicant after: JUHUA Group TECHNOLOGY CENTER Address before: 201203, 12, Lane 572, Lane 115, blue wave road, Zhangjiang hi tech park, Shanghai, Pudong New Area Applicant before: SHANGHAI HUAFON MATERIAL TECHNOLOGY Research Institute (L.P.) Applicant before: SHANGHAI HUAFON PUREN PU CO.,LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |