CN101942106A - Foaming agent composition, foam composition, and manufacturing method of foam using the same - Google Patents
Foaming agent composition, foam composition, and manufacturing method of foam using the same Download PDFInfo
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- CN101942106A CN101942106A CN2009101742489A CN200910174248A CN101942106A CN 101942106 A CN101942106 A CN 101942106A CN 2009101742489 A CN2009101742489 A CN 2009101742489A CN 200910174248 A CN200910174248 A CN 200910174248A CN 101942106 A CN101942106 A CN 101942106A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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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
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a foaming agent composition, a foam composition and a method for manufacturing the same so as to be capable of provide low-cost foam with improved thermal conductivity compared with the prior art, thereby being capable of saving consumption and electricity obviously when the foam is used in refrigerators as insulated material. The foam composition contains cyclopentane, 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane.
Description
Technical field
The present invention relates to foaming agent composotion, foamed body composition and utilize it to make the method for foam, in more detail, the present invention relates to contain foaming agent composotion, the foamed body composition of three kinds of compositions and utilize its method of making foam, thus can be used in make cheap and with the existing improved foam of thermal conductivity of comparing.
Background technology
Though because of ozonosphere and Global warming continue carrying out the exploitation of new whipping agent, aspect energy efficiency, tempo is also very slow.
At present, use polyurethane material as the thermal insulation material of the thermal insulation material of buildings or refrigerator, though that polyurethane material helps is energy-conservation, the kind difference of the whipping agent of use shows than big-difference aspect energy efficiency during because of foaming.
The 1st generation products C FC-11 (trichlorofluoromethane) that uses with whipping agent as thermal insulation material is because the havoc ozonosphere, in developed country, ban use of, Korea S has also forbidden its use in refrigerator thermal insulation material field, present situation is, it is defined for the building field thermal insulation material, but can only use 2009.
In addition, as the 2nd generation product, as whipping agent, it bans use of in developed country to use HCFC-141b (dichloro one fluoroethane), though can use the year two thousand thirty in Korea S, can be strict more but estimate to its use restriction.In addition, realistic state is, because the product that uses this whipping agent to produce can not export to developed country, thereby the refrigerator manufacturing concern of Korea S do not re-use, and only uses in thermal insulation material for building field.
As the 2.5th generation product pentamethylene in the refrigerator manufacturing concern headed by the developed country, be used as the thermal insulation material whipping agent, but with use the 1st generation, the 2nd generation to compare during whipping agent to have the tendency that energy efficiency reduces.Essentially, this is caused by the whipping agent self characteristics.
In addition, as the 3rd generation whipping agent developed HFC-245fa (1,1,1,3, the 3-pentafluoropropane), HFC-365mfc (1,1,1,3, the 3-3-pentafluorobutane), and use in developed country, Korea S is also inquired into over against its use.And, in the part developed country, consider Global warming, in price, factor such as energy efficiency aspect, use, sometimes with these two kinds of whipping agents that become to assign to use foam of certain ratio mixing HFC-245fa and HFC-365mfc.Even use these whipping agents but mix, the effect of improving of thermal conductivity also only rests on faint degree, and because the price of these raw materials is higher, so the also corresponding rise of production unit cost when use or mixing are used both separately has disadvantageous shortcoming aspect cost.
Summary of the invention
The present invention proposes for the problem that solves above-mentioned prior art existence, its purpose is to provide foaming agent composotion that contains three kinds of compositions and the foamed body composition that contains this foaming agent composotion, thus can be used in make cheap and with the existing improved foam of thermal conductivity of comparing.
Other purposes of the present invention are to provide the method for utilizing above-mentioned foaming agent composotion to make foam.
The technical task of the invention described above is finished by the following method.
(1) a kind of foaming agent composotion, it contains pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-3-pentafluorobutane.
(2) as above-mentioned (1) described foaming agent composotion, it is characterized in that, in weight ratio, pentamethylene: 1,1,1,3, the 3-pentafluoropropane: 1,1,1,3, the 3-3-pentafluorobutane is 35～50: 33～25: 32～25.
(3) a kind of foamed body composition is characterized in that, this foamed body composition contains: above-mentioned (1) described foaming agent composotion; With at least a foamable polymkeric substance and/or a kind of foamable polymer precursor.
(4) a kind of manufacture method of foam, it is to utilize whipping agent that raw material is foamed to make the method for foam, it is characterized in that, this method comprises the steps: to add pentamethylene, 1,1 as whipping agent, 1,3,3-pentafluoropropane and 1,1,1,3, the 3-3-pentafluorobutane foams.
(5) as the manufacture method of above-mentioned (4) described foam, it is characterized in that, pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3, the 3-3-pentafluorobutane is with pentamethylene: 1,1,1,3,3-pentafluoropropane: 1,1,1,3, the 3-3-pentafluorobutane is 35～50: 33～25: 32～25 weight ratio is added.
(6) as the manufacture method of above-mentioned (4) described foam, it is characterized in that foaming raw material contains and is selected from by polymkeric substance MDI (diphenylmethanediisocyanate) (polymeric methylene diphenyldiisocyanate), at least a in the group that polyalcohol modified modification MDI and monomer M DI (monomericmethylene diphenyl diisocyanate) form.
As the manufacture method of above-mentioned (6) described foam, it is characterized in that (7) monomer M DI is carbodiimide (carbodiimide) modification MDI or uretonimine (uretonimine) modification MDI.
According to the present invention, can provide cheap and with the existing improved foam of thermal conductivity of comparing, thereby can significantly save consumption electric power in this foam is applied in product such as refrigerator as thermal insulation material the time.
Embodiment
Below, illustrate in greater detail content of the present invention.
The present invention includes and contain pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3, the foaming agent composotion of 3-3-pentafluorobutane and utilize the manufacture method of the foam of this foaming agent composotion.
Whipping agent of the present invention contains pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3, and the 3-3-pentafluorobutane is as essential composition, and preferably the ratio of mixture of each composition counts 35～50 with weight ratio: 33～25: 32～25.
The composition of these whipping agents is mixed when using three kinds of compositions with certain ratio, and resultant foam is compared with existing foam and has been significantly improved thermal conductivity.When breaking away from the content range of above-mentioned each composition, be difficult to the raising of expectation thermal conductivity, may cause that on the contrary the rerum natura of foam reduces, preferably in above-mentioned scope, use thus.
Foaming compositions of the present invention contains foaming agent composotion of the present invention and at least a foamable polymkeric substance and/or a kind of foamable polymer precursor.
The foamable polymkeric substance and the foamable polymer precursor that utilize among the present invention can use separately separately, also can both together use.At least a foamable polymer precursor of preferred use.
Contain in the foaming compositions of the present invention under the situation of foamable polymkeric substance and foamable polymer precursor, the content of foamable polymkeric substance and foamable polymer precursor than (foamable polymkeric substance/foamable polymer precursor) in weight ratio normally 50/50～0/100.
Above-mentioned foamable polymkeric substance for example can be enumerated styrene polymer class, vinyl chloride-base polymer class, ethene polymers class, and propene polymer class.These foamable polymkeric substance can use or make up two or more uses separately separately.
The styrene polymer class be the homopolymer of distyryl compound or distyryl compound and can with the multipolymer of the olefinic monomer of its copolymerization.As distyryl compound, can enumerate vinylbenzene, alpha-methyl styrene, cycloalkylation vinylbenzene, reach halogenated styrenes etc.As the cycloalkyl that contains in the cycloalkylation styrenic, can enumerate for example cyclopentyl and cyclohexyl, as the halogen atom that contains in the halogenated styrenes, can enumerate for example fluorine atom and chlorine atom.
As can with the concrete example of the olefinic monomer of distyryl compound copolymerization, can enumerate methyl methacrylate, vinyl cyanide, maleic anhydride, citraconic anhydride, itaconic anhydride, vinylformic acid, N-vinylcarbazole, divinyl, isoprene, Vinylstyrene etc.
The vinyl chloride-base polymer class is the homopolymer of vinylchlorid or the multipolymer of vinylchlorid and other vinyl monomers.As other vinyl monomer classes, can enumerate for example 2-butylene, vinylformic acid, propylene, divinyl etc.
The ethene polymers class is the homopolymer of ethene or the multipolymer of ethene and other vinyl monomers.The propene polymer class is the homopolymer of propylene or the multipolymer of propylene and other vinyl monomers.As the concrete example of other vinyl monomer classes, can enumerate 2-butylene, vinylformic acid, propylene, divinyl etc.
Foamable polymer precursor is meant the material that aggregates into polymkeric substance and foam simultaneously when making foam.
As the polymkeric substance that foamable polymer precursor forms by polymerization, can enumerate for example phenol based polymer, silicon based polymer, isocyanic ester based polymer.Preferred isocyanate based polymer wherein.Among the present invention, as foamable polymer precursor, utilization can constitute one or more monomer of these polymkeric substance.
The isocyanic ester based polymer can be by making at least a organic multiple isocyanate and having the compound that contains reactive hydrogen functional group more than two at least and react and obtain.
Above-mentioned have the compound that contains reactive hydrogen functional group if with above-mentioned organic multiple isocyanate reaction, then be not particularly limited.Having the compound that contains reactive hydrogen functional group can be that 1～3 normal amount is used with respect to 1 equivalent isocyanate group in the organic multiple isocyanate with active hydrogen usually.
Contain reactive hydrogen functional group and be meant functional group with active hydrogen.As this functional group, can enumerate for example hydroxyl, uncle or secondary amino group, carboxyl and sulfydryl etc.As containing reactive hydrogen functional group, hydroxyl suits usually.Have and also can have the identical or different reactive hydrogen functional group that contains in the compound that contains reactive hydrogen functional group.In addition, in having the compound that contains reactive hydrogen functional group, contain 1～3 usually and contain reactive hydrogen functional group.Contain reactive hydrogen functional group and may be used singly or in combination of two or more use.Especially preferably use compound with two above hydroxyls, its mixture or further contain the mixture of polyamines etc. with these compounds as principal constituent.
Among the present invention, can enumerate polyvalent alcohol as the compound that contains two above hydroxyls.
As available polyvalent alcohol among the present invention, can utilize the polyvalent alcohol that in polyurethane foam, uses usually.It is that polyvalent alcohol, polyester are the diethylidene based polymer of polyvalent alcohol, multivalence alcohol, hydroxyl etc. that this polyvalent alcohol has polyethers.
Concrete example as polyvalent alcohol, can enumerate for example ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, neopentyl glycol, 1,4-two (methylol) hexanaphthene, glycerine, the glycerine propoxylated glycerine, TriMethylolPropane(TMP), 1,2, the 6-hexanetriol, tetramethylolmethane, N.F,USP MANNITOL, Sorbitol Powder, Diethylene Glycol, triethylene glycol, TEG, senior polyoxyethylene glycol, dipropylene glycol, senior polypropylene glycol, dibutylene glycol, 4,4 '-dihydroxyl diphenyl propane, poly-(Diethylene Glycol) phthalic acid esterdiol, diethanolamine, trolamine, normal-butyl thanomin etc.
As polyethers is the example of polyvalent alcohol, can enumerate that initiators such as can utilizing multivalence alcohol, carbohydrate and aromatic amine comes addition cyclic ether, especially epoxy alkane such as propylene oxide and oxyethane and the polyethers that obtains is a polyvalent alcohol.In addition, also can use as polyvalent alcohol mainly is that the polyethers that is called as polymer polyatomic alcohol or graft polyol is the polyhydric alcohol composition that is dispersed with the particulate of vinyl polymer in the polyvalent alcohol.
As polyisocyanate compound, can use fragrant family isocyanic ester, fatty family isocyanic ester, alicyclic ring family isocyanic ester and their pre-polymerization build modification body etc.
Concrete example as fragrant family isocyanic ester, can enumerate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ditan-2,4-vulcabond, ditan-4,4-vulcabond, naphthalene-1,5-vulcabond, tritane-4,4 ', 4 "-triisocyanate etc.
As fatty family isocyanic ester, can enumerate ethylidene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and 1,12-ten dimethylene diisocyanates etc.
As alicyclic ring family isocyanic ester, can enumerate tetramethylene-1,3-vulcabond, hexanaphthene-1,3-vulcabond and hexanaphthene-1,4-vulcabond etc.
Modified polyisocyanate comprises pre-polymerization build modification body, the ester modified body of tricyanic acid and the urea modification body etc. of above-mentioned polyisocyanates.Can preferably enumerate polymethylene polyphenyl isocyanate (being generally called thick MDI) and polyphenylene polyphenylene isocyanic ester etc.
Particularly polymkeric substance MDI, be fit to the present invention through polyalcohol modified modification MDI, monomer M DI.
Above-mentionedly can followingly make: for example through polyalcohol modified modification MDI, 3～5% the methylenediphenyl diisocyanates (polymeric MDI) with sorbyl alcohol, adjacent ditolyl vulcabond, tetramethylolmethane or the sugared polyvalent alcohol of making as initiator (molecular weight 400～500) and 97～95% is mixed, 80～90 ℃ of holding temperatures, and stirred 2～5 hours.At this moment, the final NCO content of above-mentioned modification MDI is 29.0% to 31.0%.Monomer M DI is a solid at normal temperatures, and operation easily under the liquid state, thereby can use carbodiimide MDI (for example Cosmonate LL, LL, bright and beautiful lake Mitsui Chemicals) or uretonimine MDI.
With respect to the total amount of polyvalent alcohol, isocyanic ester (isocyanate index) is 80～130 under the situation of polyurethane foam usually, is 150～300 under the situation of isocyanurate-modified hard polyurethane foams.
In addition, contain foam control agent, catalyzer and other additives etc. in the foamed body composition of the present invention.
As foam control agent, can utilize the tensio-active agent of silicoorganic compound system usually, can enumerate SH-193, SH-195, SH-200 or the SRX-253 etc. of DOW CORNING east beautiful organosilicon company; F-230, F-305, F341, the F-348 of organosilicon company of SHIN-ETSU HANTOTAI; TFA-4200, the TFA-4202 etc. of the L-544 of Uni-Charm Co., Ltd., L-5310, L-5320, L-5420, L-5720 or organosilicon company of Toshiba.
With respect to above-mentioned foamable polymkeric substance of 100 weight parts and/or foamable polymer precursor, the usage quantity of foam control agent is 0.1～5 weight part normally, preferably 0.1～3 weight part.
Catalyzer is not particularly limited,, can utilizes amine series catalysts or organo-metallic series catalysts as long as utilize in the polyurethane foam field usually.As these examples, can enumerate Trimethylamine 99, triethylamine, N-methylmorpholine, N-ethylmorpholine, trimethylammonium aminoethylpiperazine, N, N-dimethylamino ether, five methyl diethylentriamine, N, amine series catalysts such as N-dimethylcyclohexylamine, tetramethyl-hexamethylene-diamine; Reach dibutyl tin laurate (dibutyltin dilaurate), lauric acid tin chloride, potassium octanoate, naphthoic acid cobalt, naphthoic acid nickel etc.
With respect to above-mentioned foamable polymkeric substance of 100 weight parts and/or foamable polymer precursor, the usage quantity of catalyzer is 0.1～5 weight part normally, preferably 0.1～3 weight part.
As other additives, also can mixed filler, stablizer, tinting material, fire retardant, dyestuff, pigment, hydrolysis-resisting agent, antiseptic-germicide etc.
The manufacture method that contains the foam of foaming agent composotion of the present invention can comprise the steps: in the presence of at least a foamable polymkeric substance and/or at least a foamable polymer precursor foaming agent composotion of the present invention to be vaporized.
In the manufacture method of foam of the present invention, can be before making foam with foamable polymkeric substance and/or foamable polymer precursor mixes with foaming agent composotion of the present invention and foaming agent composotion of the present invention is vaporized, the foaming agent composotion that also can use previously prepared foamed body composition of the present invention to make to contain in the foaming compositions is vaporized.
As the preferable production process of foam of the present invention, can enumerate following two kinds of methods.
The Production Example of (1) the 1st embodiment
In shaping mould (mold), inject foaming agent composotion of the present invention and foamable polymkeric substance and/or foamable polymer precursor, in shaping mould, make the foaming agent composotion vaporization form bubble.
At this moment,, can enumerate: after foaming agent composotion of the present invention and foamable polymkeric substance and/or foamable polymer precursor are injected into pattern, in process furnace, pass through the method that heats as the method that makes foaming agent composotion vaporization; After the foamed body composition that perhaps will contain foamable polymer precursor injects mould, the method for vaporizing by the polymerization reaction heat of foamable polymer precursor; Or the like.
As above can form foam, also can carry out the foam that moulding obtains having desired shape by utilizing known forming methods such as injection molding, high-pressure molding, low pressure molding as required.
The Production Example of (2) the 2nd embodiments
The manner is to use two kinds of foamable polymer precursors to make the method for foam.As employed foamable polymer precursor, preferred polyol and organic multiple isocyanate make their reactions become polymkeric substance.
For example, the mixture that will contain polyvalent alcohol, foam control agent, catalyzer and fluoridize the ring-type unsaturated hydrocarbons as composition (B), prepares initial composition with organic multiple isocyanate respectively as composition (A).Then, mixing element (A) and composition (B) also inject mould, foam, moulding.
Normally 15～60 ℃ of the mixing temperatures of initial composition are injected into open shaping mould or are injected under pressurization and seal in the shaping mould.The mixture of composition (A) and composition (B) adds by stirrer or agitating auger oar, perhaps utilizes the adverse current introductory technique to depress quick transmission adding.
The present invention makes the foaming agent composotion vaporization usually under 70～300 ℃, preferred 80～200 ℃ temperature.
Utilize the thermal conductivity excellence of the foam that the present invention obtains, be particularly suitable for being provided at material of construction and refrigerator purposes with thermal insulation material.Be applied to provide following effect under the situation of refrigerator especially:, also can significantly save consumption electric power even do not carry out the improvement of refrigerator manufacturing process.
Below, illustrate in greater detail content of the present invention with reference to embodiment.But should be noted that these embodiment just provide in order to help to understand the present invention, claim scope of the present invention is not subjected to the qualification of these embodiment.
[embodiment 1～3]
Use the ratio of mixture of following table 1 record in the present embodiment, utilize the square plate-shape metal mould that constitutes by aluminium, machined polyurethane foam under the state that lid, energy attemperation are arranged.The temperature of the upper and lower plates of metal pattern is roughly maintained 40 ℃, makes foam with long 700 millimeters, wide 210 millimeters, thick 50 millimeters size, inject polyurethane stock solution after, cover lid carried out the demoulding to polyurethane foam after 5 minutes.
[table 1] composition is than (unit: weight part)
[experimental example]
The foam made from above-mentioned comparative example and embodiment 1～3 is an object, assaying reaction and thermal conductivity, and the result is shown in following table 2.At this moment, during assaying reaction, with the temperature maintenance of composition at 23 ± 1 ℃, in mixing and blending machine, mixed for 5 seconds with the speed of about 4000rpm, put in the square chest of 200 * 200 * 200mm of uncovered, utilize stopwatch to measure, utilize the model-HC-074 of EKO company when measuring thermal conductivity.
[table 2]
Can confirm by The above results, compare, utilize the thermal conductivity of the foam that whipping agent of the present invention produces to significantly improve with the existing whipping agent that uses.Consider that it is very difficult in the reality thermal conductivity of refrigerator being improved 0.0010 to 0.0005 degree, therefore can be evaluated as The above results the achievement that has very much novelty.
As above made explanation, but should be understood to, be familiar with these those skilled in the art and can in the scope that does not break away from thought of the present invention and field, carry out various modifications and changes the present invention with reference to the preferred embodiments of the present invention.
Claims (7)
1. foaming agent composotion, it contains pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-3-pentafluorobutane.
2. foaming agent composotion as claimed in claim 1 is characterized in that, in weight ratio, and pentamethylene: 1,1,1,3, the 3-pentafluoropropane: 1,1,1,3, the 3-3-pentafluorobutane is 35～50: 33～25: 32～25.
3. a foamed body composition is characterized in that, this foamed body composition contains: the foaming agent composotion of claim 1; With at least a foamable polymkeric substance and/or a kind of foamable polymer precursor.
4. the manufacture method of a foam, it is to utilize whipping agent that raw material is foamed to make the method for foam, it is characterized in that, this method comprises the steps: to add pentamethylene, 1,1 as whipping agent, 1,3,3-pentafluoropropane and 1,1,1,3, the 3-3-pentafluorobutane foams.
5. the manufacture method of foam as claimed in claim 4 is characterized in that, with pentamethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,3, the 3-3-pentafluorobutane is with pentamethylene: 1,1,1,3,3-pentafluoropropane: 1,1,1,3, the 3-3-pentafluorobutane is 35～50: 33～25: 32～25 weight ratio is added.
6. the manufacture method of foam as claimed in claim 4, it is characterized in that foaming raw material contains and is selected from by polymkeric substance diphenylmethanediisocyanate (MDI), at least a in the group that polyalcohol modified modified diphenylmethane diisocyanate and monomer diphenylmethanediisocyanate are formed.
7. the manufacture method of foam as claimed in claim 6 is characterized in that, the monomer diphenylmethanediisocyanate is carbodiimide modified diphenylmethanediisocyanate or uretonimine-modified diphenylmethanediisocyanate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090061109A KR101132774B1 (en) | 2009-07-06 | 2009-07-06 | A blowing agent for insulating material, foam composition comprising the same, and preparation method of foam using the same |
| KR10-2009-0061109 | 2009-07-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101942106A true CN101942106A (en) | 2011-01-12 |
| CN101942106B CN101942106B (en) | 2014-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910174248.9A Expired - Fee Related CN101942106B (en) | 2009-07-06 | 2009-09-25 | Foaming agent composition, foam composition, and manufacturing method of foam using same |
Country Status (2)
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| KR (1) | KR101132774B1 (en) |
| CN (1) | CN101942106B (en) |
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| WO2012051761A1 (en) * | 2010-10-22 | 2012-04-26 | 南京宝新聚氨酯有限公司 | Quickly reactive composition for preparing hard polyurethane foam with low density |
| WO2013091128A1 (en) * | 2011-12-19 | 2013-06-27 | Honeywell International Inc | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
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| EP2500368A3 (en) | 2002-07-15 | 2012-11-28 | Tosoh Corporation | Catalyst and process for producing a rigid polyurethane foam |
| JP4396465B2 (en) | 2003-09-29 | 2010-01-13 | 東ソー株式会社 | Catalyst composition for producing rigid polyurethane foam and isocyanurate-modified rigid polyurethane foam, and raw material blending composition using the same |
| US20060258762A1 (en) * | 2005-05-13 | 2006-11-16 | Dobransky Michael A | Hydrocarbon or hydrofluorocarbon blown ASTM E-84 class I rigid polyurethane foams |
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2009
- 2009-07-06 KR KR1020090061109A patent/KR101132774B1/en active IP Right Grant
- 2009-09-25 CN CN200910174248.9A patent/CN101942106B/en not_active Expired - Fee Related
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| CN1529728A (en) * | 2001-03-21 | 2004-09-15 | ����Τ�����ʹ�˾ | Mixtures containing 1,1,1,3,3-pentafluoropropane and 1,1,3,3-pentafluorobutane |
| CN101550241A (en) * | 2009-05-19 | 2009-10-07 | 合肥美的荣事达电冰箱有限公司 | Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam |
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|---|---|---|---|---|
| WO2012051761A1 (en) * | 2010-10-22 | 2012-04-26 | 南京宝新聚氨酯有限公司 | Quickly reactive composition for preparing hard polyurethane foam with low density |
| WO2013091128A1 (en) * | 2011-12-19 | 2013-06-27 | Honeywell International Inc | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
| EP2794738A4 (en) * | 2011-12-19 | 2015-08-12 | Honeywell Int Inc | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
| CN107641214A (en) * | 2011-12-19 | 2018-01-30 | 霍尼韦尔国际公司 | Composition comprising 1,1,3,3,3 pentafluoropropanes and pentamethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110003703A (en) | 2011-01-13 |
| KR101132774B1 (en) | 2012-04-06 |
| CN101942106B (en) | 2014-03-12 |
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