CN100460436C - Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition - Google Patents
Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition Download PDFInfo
- Publication number
- CN100460436C CN100460436C CNB2004100048613A CN200410004861A CN100460436C CN 100460436 C CN100460436 C CN 100460436C CN B2004100048613 A CNB2004100048613 A CN B2004100048613A CN 200410004861 A CN200410004861 A CN 200410004861A CN 100460436 C CN100460436 C CN 100460436C
- Authority
- CN
- China
- Prior art keywords
- polyvalent alcohol
- composition
- water
- mass parts
- polyurethane foams
- 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 present invention relates to one kind of hard foamed polyurethane composition, which has water or water and HFC as foaming agent and has modified brittleness and excellent adhesion to surface material, and its production process. The present invention is realized through adding compound with adjacent unsaturated bond and carboxyl radical as modifier in 0.01-20 weight portions into organic polyisocyanate and/or polyhydric alcohol in 100 weight portions.
Description
Technical field
The present invention relates to hard polyurethane foams molding composition and manufacture method, relate in more detail the mixture that makes water or water and tynex class as whipping agent, fragility improved, with the hard polyurethane foams molding composition and the manufacture method of the binding property excellence of surfacing.
Background technology
In the past, as the method for making hard polyurethane foams, be well known that to use and contained the method for the tynex class (CFC class and the HCFC classes of CFC-11, HCFC-141b, HCFE-123, HCFC-22, CFC-12 etc.) of chlorine as whipping agent.But CFC class and HCFC class become one of reason that the environmental problem that damages the ozone layer is arranged, and are just wanting to reduce and discard them.Therefore, utilization is causing people's attention by the water foaming of the carbonic acid gas of the reaction generation of water and isocyanate group.In addition, so do not damage the ozone layer owing to chloride in the tynex class, use the foaming of hydrogen fluorine carbon (following note is made HFC) class just being subjected to people's attention.
For only making water is the hard polyurethane foams of whipping agent, has carried out all motions before this.For example, motion has: use the initiator of polyvalent alcohol to be tetramethylolmethane 40～70 weight parts, trolamine 10～50 weight parts, below glycerine 40 weight parts, the hydroxyl value that this mixture addition epoxide is formed is the method (reference example such as patent documentation 1) of the polyvalent alcohol of 300～450mgKOH/g, use has the method (reference example such as patent documentation 2) of the compound of aromatic series amino and/or imido grpup, the OH value that use obtains tolylene diamine addition EO and PO is 270～330 polyvalent alcohol 65～85 weight %, and with the OH value that methyl glucoside addition PO obtains the polyol blends of 400～460 polyvalent alcohol 15～35 weight %, and be used in combination with polyalkylene glycol silicon segmented copolymer with specific molecular structure method (reference example such as patent documentation 3) as surfactant, a large amount of terephthalate of also using, two alkaline fat acid esters, higher-boiling compounds such as ortho-phosphoric acid ester are as the method (reference example such as patent documentation 4) of viscosity depressant, contain tolylene diamine class short chain polyester polyvalent alcohol ethylenediamines short chain polyether polyols as polyhydroxy reactant with specified proportion, the glycerols long-chain polyether polyols, and the polyol blends of dipropylene glycol, and use by silicon concentration in molecular-weight average and the molecule as surfactant, and EO/PO is than the method (reference example such as patent documentation 5) of specific special silicon class surfactant, the method of the polyvalent alcohol that in the presence of catalyzer and solvent carbohydrate addition epoxide is obtained (reference example such as patent documentation 6) is used the method (reference example such as patent documentation 7) that contains more than the aromatic polyester polyol 5 weight % that obtain by terephthalic acid composition and high molecular weight polyols in polyhydroxy reactant as polyhydroxy reactant.
But, only make water as surfactant, use with propylene glycol as polyvalent alcohol, TriMethylolPropane(TMP), glycerine, quadrol, tolylene diamine, tetramethylolmethane, methyl glucoside, Sorbitol Powder, when sucrose etc. are the polyester polyol of initiator, perhaps only making water is surfactant, during polyester polyol that use obtains by polyvalent alcohol and polyvalent carboxylic acid condensate, compare with the foam that uses existing C FC-11 or HCFC-141b foaming, fragility strengthens, the problem that the binding property of result's generation and surfacing worsens. in addition, use the HFC time-like as surfactant, from the problem of greenhouse effects of the earth and the problem of price, use HFC few separately, and water is that the situation of whipping agent is many as the situation of whipping agent.Under this occasion, also with make water foaming same separately, produce the problem that foamy fragility strengthens, worsens with the binding property of surfacing.
Usually, making water is the occasion that whipping agent is made hard polyurethane foams, the carbonic acid gas that reaction by water and isocyanate group generates forms foam, but this reaction also generates urea groups simultaneously. urea groups cohesive force is strong, have strong foamy effect, particularly make the shortcoming of foam in the embrittlement of foam surface layer but but have on the contrary.If the upper layer embrittlement, the binding property of structured materials (surfacing) such as obstruction and iron plate, timber, paper significantly just.Increase the interpolation umber of water more, this tendency is strong more.Therefore, the water blown rigid polyurethane foam is existed because the problem that is difficult to make foamed low densityization that the umber increase of water brings.In addition, use in the foaming of HFC, owing to also using water foaming agent usually, so also exist and the same problem of the independent foaming of water.
As the fragility of improving foam surface and fusible method, the method (reference example such as patent documentation 8) of imidazoles catalyzer is for example used in motion.But, add the whole process that the imidazoles catalyzer quickens to form foam reactant, there is the restive shortcoming of forming the foam characteristic that produces by catalyzer.In addition, the also known method that the solvent of the reaction that use do not participate in organic multiple isocyanate and polyvalent alcohol is arranged. but when being to use solvent, it is all softening to have a foam, and intensity reduces, perhaps the shortcoming of volatilization or stripping solvent from foam.
[patent documentation 1] spy opens flat 5-186559 communique (the 2nd～3 page)
[patent documentation 2] spy opens flat 9-87352 communique (the 2nd～3 page)
[patent documentation 3] spy opens flat 5-97961 communique (the 2nd～4 page)
[patent documentation 4] spy opens flat 6-184340 communique (the 2nd～3 page)
[patent documentation 5] spy opens flat 10-45862 communique (the 2nd～3 page)
[patent documentation 6] spy opens flat 10-101762 communique (the 2nd～4 page)
[patent documentation 7] spy opens flat 10-231345 communique (page 2)
[patent documentation 8] spy opens flat 9-87351 communique (the 2nd～4 page)
The objective of the invention is to, provide a kind of make separately water be whipping agent occasion or and water and HFC class be the occasion of whipping agent, be used to make that fragility is improved, the composition that excellent fusible hard polyurethane foams arranged with surfacing with and manufacture method.
In order to address the above problem, the inventor is through the result of further investigation, find as the raw material that is used to make hard polyurethane foams, containing organic multiple isocyanate, polyvalent alcohol, as the water of whipping agent or as the water of whipping agent and the mixture of HFC class, catalyzer, in the raw material of surfactant, with respect to organic multiple isocyanate and/or polyvalent alcohol 100 mass parts, use is as compound 0.01～20 mass parts of the unsaturated link(age) with adjacency and the carboxyl of properties-correcting agent, the fragility of hard polyurethane foams is reduced, its binding property is improved, finished the present invention.Reducing brittle mechanism is to generate secondary amine owing to having the unsaturated link(age) of adjacency and the low molecular compound of carboxyl (A) with the primary amine groups reaction of giving birth to by water and polyisocyanate-based anti-production, further, the reason of itself and other polyisocyanates radical reaction.The occasion of common water foaming generates urea groups, and when using this low molecular compound (A) as properties-correcting agent, a hydrogen of urea groups produces by modifier molecules metathetical key.This displacement urea bond stops the excessive cohesion of urea bond, by this effect, reduces foamy fragility, and the result improves the binding property with surfacing.
That is to say the present invention such as following (1)～(3).
(1) a kind of hard polyurethane foams molding composition, it is characterized in that, by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant, as the water of whipping agent, also have in the composition that other auxiliary agents form as required, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
(2) a kind of hard polyurethane foams molding composition, it is characterized in that, by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant, as the water of whipping agent and hydrogen (chlorine) fluorine carbon, also have in the composition that other auxiliary agents form as required, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
(3) a kind of manufacture method of hard polyurethane foams is characterized in that, uses each described molding composition of (1)～(2).
Embodiment
The present invention will be described in more detail.
Among the present invention as the interpolation umber of the low molecular compound (A) of properties-correcting agent unsaturated link(age) that use, that have adjacency and carboxyl, with respect to polyvalent alcohol or organic multiple isocyanate 100 mass parts, preferred 0.01～20 mass parts, more preferably 0.1～15 mass parts. during less than 0.01 mass parts, reduce the brittle effect of water blown rigid polyurethane foamy and diminish, to such an extent as to can not find good binding property.In addition, if surpass 20 mass parts, the influence owing at the residual properties-correcting agent of foam inside may produce the problem that causes the dimensional stability deterioration reason.
As low molecular compound (A), can use toxilic acid, maleic acid ester, fumaric acid, fumarate, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, furoate clothing, the furoate clothing ester, propenal, Methylacrylaldehyde, Ba Dousuan, benzoquinones, isophorone etc., good from the Combination of preferred and polyvalent alcohol, and the viewpoint of the material that viscosity is low, so long as the material of number-average molecular weight less than 500, can use multiple material. wherein, the preferred carboxylicesters that uses, especially preferably use lower alcohol (carbon number is below the 8) ester of dibasic acid. further, wherein, from with the speed of response of primary amine, viscosity, Combination with organic isocyanate or polyvalent alcohol, foul smell, security, viewpoints such as price are most preferably used maleic acid ester.
As low molecular compound (A), not only can use the unsaturated link(age) with adjacency and the compound of carboxyl, also can use compound with hydroxyl isoreactivity hydrogen or isocyanate group.At this moment, this low molecular compound (A) not only participates in the formation reaction of urea groups, also forms crosslinking structure.
As the organic multiple isocyanate among the present invention, can use known various multi-functional aliphatics, alicyclic with aromatic isocyanate, for example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4-dicyclohexyl methyl vulcabond (H12MDI), toluenediisocyanate (TDI), rough toluenediisocyanate, the modification toluenediisocyanate, 4,4 '-diphenylmethanediisocyanate (4,4 '-MDI), polymeric MDI (is called rough diphenylmethanediisocyanate, former MDI etc. are designated hereinafter simply as p-MDI), modified diphenylmethane diisocyanate (carbodiimide modification, prepolymer modification etc.), Ortho Toluidine vulcabond (TODI), naphthyl vulcabond (NDI), xylylene vulcabond (XDI), lysinediisocyanate (LDI) etc.Among the present invention, preferred use 2,4 '-diphenylmethanediisocyanate (2,4 '-MDI), 2,2 '-diphenylmethanediisocyanate (2,2 '-MDI), 4,4 '-MDI and p-MDI or this p-MDI and other polyisocyanates mixture of ingredients of mixture with polymethylene polyphenylene polyisocyanates of 3 above phenyl ring, wherein, from the mechanical properties of the hard polyurethane foams that obtains and the viewpoint of price, especially preferably have 2 in the diphenylmethanediisocyanate of 2 phenyl ring, 4 '-MDI and 2, the total ratio of 2 '-MDI is 0～30 quality %, and this diphenylmethanediisocyanate is 25～70 quality %, and containing the above polyalkylene polyphenylene polyisocyanates of 3 phenyl ring is the p-MDI that 30～75 quality % form.
Among the present invention, as can be with the polyvalent alcohol of isocyanic ester radical reaction, promptly, has the active dydrogen compounds that contains active hydrogen functional group more than 2, so long as have the compound of the active hydrogen functional group of containing 2 above hydroxyls or amino etc., or the mixture of this compound more than 2 kinds, just can use known arbitrary substance.From the viewpoint of the mechanical properties of the hard polyurethane foams that obtains, preferred compound or its mixture with 2 above hydroxyls that use perhaps uses the mixture that further contains polyamine etc. with it as principal constituent among the present invention.But, just have the occasion of the unsaturated link(age) of adjacency and the low molecular compound of carboxyl (A) being pre-mixed to use, can not use material with primary amine groups with its reaction.
As aforementioned compound, polyether alcohol, polyester polyvalent alcohol, polyvalent alcohol are arranged, contain the diethylidene base polymer of hydroxyl etc. with the hydroxyl more than 2.Particularly preferably have only polyether alcohol more than a kind to form, or be principal constituent and usefulness polyester polyvalent alcohol, polyvalent alcohol, polyamine, alkanolamine, other active dydrogen compounds with it.As polyether alcohol, the preferred polyether alcohol that polyvalent alcohol, carbohydrate, alkylamine, alkanolamine, other initiator addition cyclic ethers, particularly epoxide of addition propylene oxide or oxyethane etc. are obtained.In addition, as polyvalent alcohol, also can use at polymer polyatomic alcohol or be called the polyhydric alcohol composition that graft polyol has disperseed the particulate of vinyl polymer in for main polyether alcohol.As the polyester polyvalent alcohol, the polyvalent alcohol of polyvalent alcohol, polyvalent carboxylic acid condensate class or the polyvalent alcohol of cyclic ester ring-opening polymerization system are arranged, as polyvalent alcohol ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, diethanolamine, trolamine etc. are arranged. as polycarboxylic acid, fumaric acid anhydride, terephthalic anhydride, dimethyl terephthalic acid acid anhydride, hexanodioic acid, hexachloro endoethylene tetrahydrophthalic acid etc. are arranged.
Used polyvalent alcohol is that hydroxyl value is the polyvalent alcohol of 15～2000 (mgKOH/g) among the present invention, so select according to all rerum naturas of the purposes of the hard polyurethane foams that obtains, i.e. requirement.
As this polyvalent alcohol, (for example for example can lift the commercially available polyether glycol that sucrose addition propylene oxide is obtained, GR-35 (hydroxyl value is 400 (mgKOH/g): military field medicine Co., Ltd. makes), the polyether glycol that tolylene diamine addition propylene oxide is obtained (for example, NT-400 (hydroxyl value is 400 (mgKOH/g): Mitsui Chemicals, Inc makes), the polyether glycol that glycerine addition propylene oxide and oxyethane are obtained (for example, FA-103T (hydroxyl value is 50 (mgKOH/g): Sanyo Chemical Industries, Ltd. makes) etc.As other this polyvalent alcohol, can lift the EX-425R (hydroxyl value is 420 (mgKOH/g)) that Asahi Glass Co., Ltd that sucrose and triethylenediamine addition propylene oxide are obtained makes.
Among the present invention, when polyvalent alcohol and organic multiple isocyanate reaction,, be necessary to use catalyzer in order to promote reaction etc.As catalyzer, use to promote to contain in the polyvalent alcohol metallic compound class catalyzer of organo-tin compound etc. of the group of active hydrogen and the isocyanic ester radical reaction in the organic multiple isocyanate and triethylenediamine (TEDA), tetramethyl-six subunit diamines (TMHMDA), five methyl diethylentriamine (PMDETA), dimethylcyclohexylam,ne (DMCHA), two dimethyl aminoethyl ether tertiary amine catalysts such as (BDMAEA).According to purpose, also make the trimerization catalyst of reacting between this isocyanate groups in addition.
In order to form good bubble, be necessary to use surfactant among the present invention, as this surfactant, so long as known surfactant in the polyurethane industrial can use any one. for example, silicon class surfactant is arranged or contain surfactant of fluorine cpd class etc.
Among the present invention, can also use for example weighting agent as auxiliary agent, stablizer, tinting material, fire retardant etc. according to necessity.Representative substances as fire retardant has three (chloropropyl) phosphoric acid ester (TCPP).
Among the present invention, use these raw materials to obtain polyurethane foam, urethane-modified polyisocyanurate foam, other foamed synthetic resins.The present invention to make hard polyurethane foams, urethane-modified poly-isocyanuric acid foam, other rigid foams are particularly useful.Wherein, the water foaming that the polyvalent alcohol that uses hydroxyl value about 40～900 (mgKOH/g) or polyol blends and aromatic polyisocyanate compound are obtained or and the manufacturing of the hard polyurethane foams that foams of water and HFC in particularly useful.
[effect]
This low molecular compound (A) does not react with amine catalyst, by adding, and owing to the speed of response that influences foams generations such as livering time, gelation time hardly, so even add any amount, also unnecessary consideration change catalytic amount etc.But, having the tendency that prolongs the non-caked time slightly, this is owing to reduce the embodiment of the fragility effect on surface.Further, hard polyurethane foams generally is by composition before composition (polyvalent alcohol premixture) before the moulding that will contain polyvalent alcohol when the moulding and the moulding that contains organic multiple isocyanate (perhaps, be separately organic multiple isocyanate) two kinds of liquid mixing obtain, perhaps before this two moulding, also have this low molecular compound (A) to wait three kinds of states mixing more than the liquid to obtain the composition by mixing when the moulding, but, this low molecular compound (A) by composition before being added on composition before the moulding that contains polyvalent alcohol in advance or containing the moulding of organic multiple isocyanate (perhaps, be separately organic multiple isocyanate) in, have the viscosity that makes these liquid and reduce, improve the blended effect of liquid.
This low molecular compound (A) and primary amine groups are reacted rapidly, but not with the isocyanic ester radical reaction of hydroxyl groups or organic multiple isocyanate.Therefore, also can in advance it be added to before the moulding that contains polyvalent alcohol in the composition, also can add in advance in addition before the moulding that contains organic multiple isocyanate in the composition (perhaps, being organic multiple isocyanate separately).In addition, even be not pre-mixed, when making rigid foam, also can obtain same effect.This low molecular compound (A) is although add in the raw material not and all reactions, after isocyanate group and water reaction generate primary amine groups, at once and the primary amine groups reaction generate secondary amine.Further, this secondary amine horse back and other isocyanic ester radical reactions.Therefore, this low molecular compound (A) enters in the molecular skeleton that forms the foamy resin, volatilization or stripping from foam unlike solvent.This low molecular compound (A) is owing to only reacting with primary amine groups, so do not participate in the reaction of hydroxyl and isocyanate group.Therefore, only relevant with the urea groups that becomes the reason that makes the deterioration of foamy binding property, particularly bring into play its effect, so do not influence the rerum natura of foam integral body at the foam surface layer.
Embodiment
Based on embodiment, further specifically describe the present invention, but the present invention is not limited to the content that following examples are explained.
The mensuration of expansion rate
Prepare the raw material of record in the table 1, according to the proportioning of record in the table 1, the preparation of concocting polyvalent alcohol premixture or isocyanate prepolymer composition etc.After it is adjusted the temperature to 20 ℃ separately, make gross weight be the 500g weighing to the デ ス cup of 2000ml, stirred 5 seconds with collar plate shape propeller mixing tank (rotation number 7000rpm).After stir finishing, the interior dimensions of injecting temperature adjustment to 40 in advance ℃ at once is the top opening aluminum mould of 250 * 250 * 250 (height) mm, measures free foaming foamy speed of response (livering time, gelation time, non-caked time, rise time).
The making of tabular frothing foam
Prepare the raw material of record in the table 1, proportioning according to record in the table 1, concoct the preparation of polyvalent alcohol premixture or isocyanate prepolymer composition etc. after it is adjusted the temperature to 20 ℃ separately, making gross weight is that the 500g weighing is to the デ ス cup of 2000ml, with collar plate shape propellar mixer (rotation number 7000rpm) stirring 5 seconds.After stir finishing, the interior dimensions of injecting temperature adjustment to 40 in advance ℃ at once is the aluminum mould of 500 * 500 * 60 (thick) mm, and tabular frothing foam is made in the demoulding after 10 minutes. after room temperature leaves standstill 24 hours, measure following project after the demoulding.
Tabular foaming density: the JIS A9511 (unit in the table 1: kg/m
3)
Fragility: following measuring method
High temperature size changing rate: the following measuring method (unit in the table 1: %)
Bond strength: the following measuring method (unit in the table 1: MPa)
Fragility
The tabular frothing foam of moulding after room temperature leaves standstill 24 hours, carries out the sense evaluation to the foam side after the demoulding.
In the table 1, zero: good
△: general going up well
*: bad
The high temperature size changing rate
Tabular frothing foam is cut into 50 * 50 * 50mm size.To the size changing rate of this foam sample that is cut into mensuration after 80 ℃ * 48 hours.
Bond strength
When the tabular frothing foam of moulding, in advance with the iron plate of degreasing (100 * 100mm) are fixed on the side, and method same as described above is made tabular frothing foam. after the demoulding, after room temperature leaves standstill 24 hours, use stretching trier (テ Application シ ロ Application), measure the bond strength of foam and iron plate.
Embodiment 1
Proportioning admixtured polyether polyvalent alcohol A, water, catalyzer, surfactant, fire retardant, property-modifying additive dibutyl maleinate according to table 1, blending polyvalent alcohol premixture. thereafter, the blending ratio that this premixture and organic multiple isocyanate is as shown in table 1 is mixed, according to aforesaid method, measure expansion rate, make tabular frothing foam and measure tabular foam density, high temperature size changing rate, bond strength.The result is as shown in table 1.
Embodiment 2～5, comparative example 1 and 2
According to method similarly to Example 1, implement embodiment 2～5 and comparative example 1,2, according to the blending ratio of table 1, measure expansion rate, make tabular frothing foam and measure tabular foam density, high temperature size changing rate, bond strength.The result is as shown in table 1.
Table 1
Mark in the table 1:
Polyether glycol A: the EL-430 (hydroxyl value is 400 (mgKOH/g)) that Asahi Glass Co., Ltd makes
Polyether glycol B: the EL-450ED (hydroxyl value is 450 (mgKOH/g)) that Asahi Glass Co., Ltd makes
Water: (city's water)
Catalyzer: Kao Corp makes カ オ ラ イ ザ-No.10
Surfactant: the Japanese ユ ニ カ-L-5420 of Co., Ltd.
Fire retardant: ア Network ゾ ノ-ベ Le corporate system Off ア イ ロ-Le PCF
Organic multiple isocyanate: Nippon Polyurethane Industry Co., Ltd. makes MR-200 (isocyanate group content 30.8 (%))
Shown in the embodiment 1～5 of table 1, use has the unsaturated link(age) of adjacency and the low molecular compound of carboxyl as properties-correcting agent, to reactive and not influence of dimensional stability, can improve water blown rigid polyurethane foam or and the fragility and the binding property of the hard polyurethane foams that foams of water and HFC significantly.
Claims (5)
1. hard polyurethane foams molding composition, it is characterized in that, in by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant and the composition formed as the water of whipping agent, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
2. hard polyurethane foams molding composition, it is characterized in that, in by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant, the composition formed as the water of whipping agent and hydrochlorofluorocarazeotropic class and/or hydrogen fluorine carbon, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
3. hard polyurethane foams molding composition, it is characterized in that, in by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant and the composition formed as water and other auxiliary agents of whipping agent, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
4. hard polyurethane foams molding composition, it is characterized in that, in the composition of forming by organic multiple isocyanate, polyvalent alcohol, catalyzer, surfactant, water, other auxiliary agents and hydrochlorofluorocarazeotropic class and/or hydrogen fluorine carbon as whipping agent, with respect to polyvalent alcohol 100 mass parts, also use maleic acid ester 0.01～20 mass parts as properties-correcting agent.
5. the manufacture method of a hard polyurethane foams is characterized in that, uses each described molding composition of claim 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100048613A CN100460436C (en) | 2004-02-10 | 2004-02-10 | Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100048613A CN100460436C (en) | 2004-02-10 | 2004-02-10 | Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654500A CN1654500A (en) | 2005-08-17 |
| CN100460436C true CN100460436C (en) | 2009-02-11 |
Family
ID=34892034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100048613A Expired - Fee Related CN100460436C (en) | 2004-02-10 | 2004-02-10 | Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100460436C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922575A (en) * | 2015-06-18 | 2018-04-17 | 巴斯夫欧洲公司 | The method for producing hard polyurethane foams |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002079340A1 (en) * | 2001-04-01 | 2002-10-10 | Dow Global Technologies, Inc. | Rigid polyurethane foams |
-
2004
- 2004-02-10 CN CNB2004100048613A patent/CN100460436C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002079340A1 (en) * | 2001-04-01 | 2002-10-10 | Dow Global Technologies, Inc. | Rigid polyurethane foams |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922575A (en) * | 2015-06-18 | 2018-04-17 | 巴斯夫欧洲公司 | The method for producing hard polyurethane foams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1654500A (en) | 2005-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101067018B (en) | New trimerization catalysts from sterically hindered salts | |
| CN1930202A (en) | Attached, high reactivity rigid polyurethane foams | |
| CN1404503A (en) | Rigid polyurethane foams | |
| CN101668787B (en) | Polyisocyanate composition for soft polyurethane foam and process for producing soft polyurethane foam from the composition | |
| CN1404492A (en) | Low emisson polyurethane polymers made with autocatalytic polyols | |
| US9321892B2 (en) | Blowing agent enhancers for polyurethane foam production | |
| CN1746203A (en) | Pur/pir rigid foams based on aliphatic polyester polyols | |
| CN101831043A (en) | Be used for catalyst composition water foaming, low density, hard polyurethane foams | |
| JP7053051B2 (en) | Polyol composition for rigid polyurethane foam and method for manufacturing rigid polyurethane foam | |
| CN1074007C (en) | Method for making insulating rigid polyurethane foams | |
| JP2020180169A (en) | Polyurethane foam-forming composition | |
| EP3426708B1 (en) | Polyurethane and polyisocyanurate foams and methods of producing the same | |
| JPS6392630A (en) | Production of open-cellular polyurethane foam and composition for producing the same | |
| CN100460436C (en) | Composition for rigid polyurethane foam forming and process for preparing the rigid polyurethane foam using the composition | |
| JP4461417B2 (en) | Polyisocyanate composition and method for producing rigid polyurethane foam | |
| KR101985105B1 (en) | Polyurethane composition, acoustic absorbent comprising the same and manufacturing method polyurethane foam | |
| EP0745627A2 (en) | A process for preparing open-cellular polyurethane modified polyisocyanurate foam | |
| JP2002155125A (en) | Process for producing polyurethane-modified polyisocyanurate foam | |
| JP2010222400A (en) | Polyol composition for rigid polyurethane foam | |
| JPH05271368A (en) | Improved process for producing polyurethane foam by means of portable foaming apparatus | |
| EP0635527A1 (en) | Process for producing polyisocyanurate foams | |
| JPH0440369B2 (en) | ||
| CN101646708A (en) | Flexible PU foam is with polyisocyantates composition and use the manufacture method of the flexible PU foam of said composition | |
| JP2007051280A (en) | Polyol composition and method for producing rigid polyurethane foam | |
| JP2526974B2 (en) | Method for producing foamed synthetic resin |
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 |
Granted publication date: 20090211 Termination date: 20220210 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |