CN1309678A - Process for rigid polyurethane foams - Google Patents
Process for rigid polyurethane foams Download PDFInfo
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- CN1309678A CN1309678A CN99808558A CN99808558A CN1309678A CN 1309678 A CN1309678 A CN 1309678A CN 99808558 A CN99808558 A CN 99808558A CN 99808558 A CN99808558 A CN 99808558A CN 1309678 A CN1309678 A CN 1309678A
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- polyester polyol
- isocyanate
- urethane
- acid
- glycol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Process for preparing rigid polyurethane or urethane-modified polyisocyanurate foams by reacting an organic polyisocyanate with a polyfunctional isocyanate-reactive component comprising more than 2 % by weight of water and from 5 to 50 % by weight of polyester polyols of average functionality below 3, especially crude polyester polyols.
Description
The present invention relates to the preparation method of urethane or urethane modified polyisocyanurate isocyanuric acid ester rigid foam, by the porous plastics of this method preparation and can be used for novel composition in this method.
Urethane and urethane modified polyisocyanurate isocyanuric acid ester rigid foam are generally by the preparation that reacts in the presence of whipping agent of suitable polyisocyanates and isocyanate activity compound (being generally polyvalent alcohol).A kind of purposes of this kind porous plastics is as heat insulation medium and filler, for example is used for the water heater structure.
The recyclable usability of water heater has become key property.Water heater must be convenient to dismounting, so that all differing materials that use will make water heater the time are easy to separately and recovery.
An object of the present invention is to provide a kind of polyurethane rigid foam plastic that from the cavity of filling porous plastics, reclaims easily.
Content was 5～50wt% polyester polyol when these purposes were benchmark by utilizing by polyisocyanates, isocyanate-reactive components with as the water of whipping agent and with the isocyanate-reactive components, the method of making urethane or urethane modified polyisocyanurate isocyanuric acid ester rigid foam reaches, and wherein the polyester polyol average functionality is less than 3.
, therefore be easy to from cavity, take out to almost not having sticking power by the porous plastics of the inventive method preparation with any recovery method such as metal as cavity wall.
Term as used herein " polyester polyol " is meant the product of being produced by suitable proportion two pure and mild higher functionality polyvalent alcohols and dicarboxylic acid or poly carboxylic acid condensation; This term comprises any no esterification polyvalent alcohol that adds on a small quantity after unreacted polyvalent alcohol residual after the polyester polyol preparation and/or this preparation.
Advantageously, the average functionality that is used for polyester polyol of the present invention is between about 1.5～3, and is preferred about 1.7～2.5, and more preferably from about 1.8～2.3.Their hydroxyl value is generally between about 15～750, and is preferred about 30～550, and more preferably 70～550, and 200～550mgKOH/g most preferably from about.The molecular weight of this polyester polyol is generally between about 400～about 10000, preferred about 1000～about 6000.Preferably, the acid number of polyester polyol is between 0.1～20mgKOH/g; Generally speaking, acid number can be up to 90mgKOH/g.
Advantageously, polyester polyol comprises the highest about 40wt% free diol.Preferably, free diol content is between 2～30, and more preferably 2～15wt% is a benchmark with polyester polyols alkoxide component gross weight.
The amount of this kind polyester polyol, with isocyanate-reactive components weight be benchmark preferably between 5～30%, more preferably 10～25%, and 16～23wt% most preferably.
Being used for polyester polyol of the present invention can be by known steps by poly carboxylic acid or acid derivative, and for example polycarboxylic acid anhydrides or ester are with any polyhydroxy-alcohol preparation.Poly carboxylic acid and/or polyol component can two or more compounds form of mixtures be used for the preparation of polyester polyol.
Polyvalent alcohol can be aliphatic series, cyclic aliphatic, aromatics and/or heterocyclic.The low molecular weight aliphatic polyhydroxy-alcohol, as contain the aliphatic dihydroxy alcohol that is no more than about 20 carbon atoms, be very gratifying.Polyvalent alcohol can randomly be included in and be the inert substituting group in the reaction, for example chlorine and bromine substituent, and/or can be undersaturated.Suitable amino alcohol, for example Monoethanolamine MEA BASF, diethanolamine, trolamine etc. also can use.The preferred polyhydric alcohols component is a dibasic alcohol.This dibasic alcohol can comprise heteroatoms (as, thiodiglycol), perhaps can only be made up of carbon, hydrogen and oxygen.Advantageously, they are that general formula is C
nH
2n(OH)
2Simple glycol or be the poly-dihydric alcohol of feature in hydrocarbon chain, to insert ehter bond, for example by general formula C
nH
2nO
x(OH)
2Those of representative.The example of suitable polyhydroxy-alcohol comprises: ethylene glycol, (1,2) propylene glycol and (1,3) propylene glycol, (1,4) butyleneglycol and (2,3) butyleneglycol, (1,6) hexylene glycol, (1,8) ethohexadiol, neopentyl glycol, 1, the two methylol hexanaphthenes of 4-, the 2-methyl isophthalic acid, ammediol, glycerine, trimethylolethane, hexanetriol-(1,2,6), trihydroxybutane-(1,2,4), quinhydrones, methyl glucoside, triglycol, Tetraglycol 99 and high-grade polyoxyethylene glycol more, dipropylene glycol and high-grade polypropylene glycol more, glycol ether, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), sorbyl alcohol, N.F,USP MANNITOL, dibutylene glycol and more senior polytetramethylene glycol.Especially suitable polyvalent alcohol is aklylene glycol and oxyalkylene glycol, for example ethylene glycol, glycol ether, dipropylene glycol, triglycol, tripropylene glycol, Tetraglycol 99, four propylene glycol, trimethylene, tetramethylene glycol and 1,4-cyclohexanedimethanol (1, the two methylol hexanaphthenes of 4-).
The poly carboxylic acid component can be aliphatic series, cyclic aliphatic, aromatics and/or heterocyclic, and can randomly replace, and is for example replaced by halogen atom, and/or can be undersaturated.Being fit to the carboxylic acid of preparation polyester polyol and the example of derivative thereof comprises: oxalic acid, propanedioic acid, hexanodioic acid, pentanedioic acid, succsinic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, Tetra hydro Phthalic anhydride, terephthalic anhydride, m-phthalic acid, terephthalic acid, 1,2, the 4-benzenetricarboxylic acid, Tetra Hydro Phthalic Anhydride, 1,2,4,5-pyromellitic acid dianhydride, hexahydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, carbic anhydride, Pyroglutaric acid, toxilic acid, maleic anhydride, dimethyl terephthalate (DMT), the two diol esters of terephthalic acid, fumaric acid, binary and ternary unsaturated fatty acids randomly mix with monobasic unsaturated fatty acids such as oleic acid.
Though polyester polyol can be by pure substantially reaction mass preparation, but also can use comparatively complicated composition, for example come side line, waste material or the tankage of the preparation process of phthalic acid, terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate and so on from the beginning.These compositions can adopt steps such as traditional transesterify or esterification, are converted into polyester polyol by reacting with polyvalent alcohol.
According to the present invention, can use aliphatic series and/or aromatic polyester polyvalent alcohol.
The mixture of two or more different polyester polyols also can be used.
Preferably, being used for polyester polyol of the present invention is thick polyester polyol.
Term " thick polyester polyol " is used to refer to any polyester polyol of being produced by crude reaction resistates or waste material vibrin in this article.
Generally speaking, they are made up of multiple mixture low and the high molecular hydroxy-containing component, its totally or molecular-weight average and average functionality respectively between about 255～about 5000 and about 2～about 6.Preferably, molecular-weight average between about 250～about 1500, corresponding average functionality is between about 2～about 4.The molecular-weight average of the thick polyester polyol of a most preferred class between about 250～about 1000, and average functionality is between about 1.5～about 3.
Those thick polyester polyols that obtained by the crude reaction resistates comprise many sources.One of these sources comprise by Tetra hydro Phthalic anhydride bottoms deutero-polyester polyol, as disclosed among the US 4521611.The best example in preferred source is to be set out by so-called DMT (dimethyl terephthalate (DMT)) residual processing thing, by carrying out transesterify and the deutero-mixture with the low molecular weight aliphatic glycol.Typical DMT polyester polyol for example is disclosed in US 3647759, wherein adopts the atmospheric oxidation that utilizes p-Xylol to produce deutero-resistates in the DMT process.This oxidation residues comprises the complex mixture of the hexichol base class, many phenyl class and the toluic acid benzyl ester class formation that are replaced by many methoxycarbonyies (polycarbomethoxy).This resistates carries out transesterify with aliphatic diol such as ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, generates the low cost various, that physicals is different, main component is the product of the polyester polyol of hydroxyl-functional.This kind DMT deutero-polyester polyol is also supplied by trade(brand)name TERATE production of resins by Hoechst Celanese.
The best example of the thick polyester polyol that those are produced by the waste material vibrin is the mixture that obtains with low molecular weight aliphatic glycol digestion (digesting) waste material polyethylene terephthalate (PET).Typical composition is by based on the aromatic ester of molecular weight between 62～500 organic diol and triol digestion polyalkylene terephthalates deutero-polyvalent alcohol, for example is disclosed among the US 4048104; By the aromatic polyester polyvalent alcohol that polyethylene terephthalate resistates and alkylene oxide react and obtained in the presence of basic catalyst, for example be disclosed among the US 4439549; By the materials flow of recovery polyethylene terephthalate refuse, aklylene glycol and diacid refuse materials flow deutero-aromatic polyester polyvalent alcohol, as be disclosed in US 4439550 and US4444918; By polyethylene terephthalate residue and alkylene carbonates deutero-aromatic polyester polycarbonate polyol, be disclosed among the US 4465793; By recovery or waste material polyethylene terephthalate and glycol ether and a kind or the liquid terephthalic acid ester polyol of multiple oxidative olefinic diols deutero-, as be disclosed among the US 4469824; At first react, react the polyester polyol made from alkylene oxide subsequently, as be disclosed among the US 4485196 by the polyethylene terephthalate waste material and the aklylene glycol that reclaim; The copolyester polyvalent alcohol, comprise the aromatic component that is selected from phthalic acid derivatives, polyethylene terephthalate or dimethyl terephthalate (DMT), with the reaction product of diprotic acid compound, at least a kind of primary hydroxyl glycol and at least a kind of a small amount of secondary hydroxyl glycol, it is medium to be disclosed in US 4559370.
Be preferred for thick polyester polyol of the present invention and comprise Terate 2541 and Terate2031, they are that DMT is the polyester polyol on basis, and the two all can be obtained by Hoechst Celanese, and Isoexter 3471, it is a waste material PET polyester, is sold by COIM.
Can use two or more different thick polyester polyols in the methods of the invention.
Except above-mentioned thick polyester polyol, also can use the other types polyester polyol to be generally used for producing polyurethane rigid foam plastic, but the total amount of preferred this kind polyester polyol is no more than 70% of isocyanate-reactive components total amount.
The isocyanate activity compound that other are suitable for the inventive method, comprise any be used to prepare urethane or urethane modified polyisocyanurate isocyanuric acid ester rigid foam production technology known those.To most important polyvalent alcohol of the preparation process that is used for rigid foam and polyol blends be: promptly their average hydroxyl value is between 300～1000, and 300～700mgKOH/g especially, hydroxy functionality be between 2～8, and especially 3～8.Suitable polyvalent alcohol has been done abundant description in prior art, comprise alkylene oxide, as oxyethane and/or propylene oxide, with the reaction product that comprises the initiator of 2～8 active hydrogen atoms on each molecule.Suitable initiator comprises: polyvalent alcohol, for example glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, sorbyl alcohol and sucrose; Polyamines, for example quadrol, tolylene diamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene polyphenylene polyamines; And alkamine, as thanomin and diethanolamine; And the mixture of this type of initiator.Other suitable polymers polyvalent alcohols comprise terminal hydroxy group polythioether, polymeric amide, polyesteramide, polycarbonate, polyacetal, polyolefine and polysiloxane.
Preferred polyethers comprises those that are caused by sorbyl alcohol or sucrose and/or glycerine.Preferably, polyether glycol adopts propylene oxide to prepare as unique alkylene oxide.
The organic multiple isocyanate that is suitable for the inventive method comprise any preparation urethane or urethane modified polyisocyanurate chlorinated isocyanurates rigid foam technology known those, particularly: aromatic polyisocyanate, '-diphenylmethane diisocyanate for example, comprise its 2,4 '-, 2,2 '-and 4,4 '-isomer and composition thereof form; The mixture of '-diphenylmethane diisocyanate (MDI) and its oligopolymer, they are known as " slightly " or polymeric MDI (polymethylene polyphenylene polyamines) in the art, and its isocyanate functionality is greater than 2; Tolylene diisocyanate, comprise its 2,4-and 2,6-isomer and composition thereof; 1, the 5-naphthalene diisocyanate; And 1, the 4-phenylene diisocyanate.Other organic multiple isocyanates that can enumerate comprise aliphatic vulcabond, as isophorone diisocyanate, 1, and 6-two isocyanato-hexanes and 4,4 '-two isocyanato-dicyclohexyl methyl hydrides.
Polyisocyantates composition and polyfunctional isocyanate's active composition consumption in reaction will depend on the urethane that will prepare or the characteristic of urethane modified polyisocyanurate isocyanuric acid ester rigid foam, and will be easy to be determined by those skilled in the art.
Water uses as whipping agent, randomly cooperates to account for whipping agent always to use the pneumatogen of quantity not sufficient 15wt%.When water during as whipping agent, the consumption of water is generally between 2～10wt%, and preferred 4～6wt% is a benchmark with isocyanate-reactive components weight.
As additional whipping agent, any preparation urethane or the known whipping agent of urethane modified polyisocyanurate isocyanuric acid ester rigid foam technology all can be used in the inventive method.This type of whipping agent comprises that boiling point is higher than-70 ℃ inertia low-boiling compound under other carbonic acid gas release compounds or the atmospheric pressure.
Suitable inertia whipping agent comprise know in this area and described those, hydro carbons for example, dialkyl ether, chain acid alkyl ester, aliphatic series and cyclic aliphatic fluorohydrocarbon, Chlorofluorocarbons (CFCs), Chlorofluorocarbons, chlorocarbon and fluorine-containing ether.
The consumption of whipping agent should be enough to make the porous plastics of formation to have the volume density of requirement, generally between 15～70kg/m
3, preferred 20～50kg/m
3, 25～40kg/m most preferably
3The typical amounts of whipping agent is benchmark between 2～25wt% with the reaction system total amount.
Except polyisocyanates and polyfunctional isocyanate's active composition and whipping agent (mixture), foam formation reaction mixture will contain other conventional adjuvants and additive commonly used in a kind or multiple preparation urethane or the urethane modified polyisocyanurate isocyanuric acid ester rigid foam prescription usually.The optional additive of this kind comprises linking agent, as low molecular weight polyols, as trolamine; Suds-stabilizing agent or tensio-active agent are as the siloxanes oxyalkylene copolymers; Ammonia ester catalyst such as tin compound or tertiary amines; Isocyanurate catalyst; Fire retardant is as halogenated alkyl phosphate, as tricresyl phosphate chloropropyl ester; And filler, as carbon black.
Preferably, employed auxiliary agent does not promote the adhesion to metal.
This method generally at isocyanate index between 0.8～2.5, carry out under preferred 1.0～1.5 the condition.
The operation that is used for preparing rigid foam of the present invention in present method, can adopt known single stage method prepolymer or semi prepolymer technology, cooperation is with the conventional hybrid method, prepared rigid foam can be piece material, mo(u)lded item, cavity filler, injection foaming foam plastics (Sprayedfoam), inflation (frothed) porous plastics or with the laminated thing of other materials such as hardboard, plasterboard (plasterboard), plastics, paper or metal.
By the preferable use of the porous plastics of the method for claim of the present invention preparation is cavity filler as water heater.
In many application scenarios be easily, all compositions that preparation urethane is used provide with the premix formula form, and prescription mainly comprises polyisocyanates or isocyanate-reactive components.Particularly, many reaction systems adopt the polyisocyanates active compositions, and wherein said composition also comprises main additive, for example whipping agent except comprising a kind or multiple polyisocyanates active ingredient or component.
All respects of the present invention are illustrated by following example but are not limited to these, wherein adopted following ingredients:
Polyvalent alcohol 1: glycerine polyether glycol that cause, hydroxyl value 540mgKOH/g.
Polyvalent alcohol 2: sorbyl alcohol polyether glycol that cause, hydroxyl value 460mgKOH/g.
Polyvalent alcohol 3: sorbyl alcohol causes, the polyether glycol of hydroxyl value 380mgKOH/g.
The polyether glycol of polyvalent alcohol 4: hydroxyl value 280mgKOH/g.
Fire retardant: halogenide fire retardant.
Terate 2541:DMT polyester polyol, hydroxyl value 240mgKOH/g, functionality 2 is supplied by Hoechst Celanese.
Isoexter 3471: waste material PET polyester, and hydroxyl value 350mgKOH/g, functionality 2～2.5 is supplied by COIM.
Arconate 1000: ethylene carbonate, supply by Arco.
Tensio-active agent: silicone surfactant.
Catalyzer: tertiary amine catalyst bag.
Isocyanic ester: polymeric MDI
Example 1
Prepare polyurethane rigid foam plastic by table 1 ingredients listed.Response curve depends on cream time and wire drawing phase (string time). the free initial density-emitting of foams is measured according to standard ISO 845.The adhesive power of foams is measured according to standard A STM D162.Adhesive power is 0, means that foams just come off.The result is stated from the table 1.Table 1
| The foam code name | ???1 | ???2 | ????3 | ???4 | ||
| Polyvalent alcohol 1 | pbw | ?9.40 | ?10.00 | ?10.00 | ?10.00 | |
| Polyvalent alcohol 2 | pbw | ?29.00 | ?28.70 | ?26.70 | ?26.70 | |
| Polyvalent alcohol 3 | pbw | ?33.30 | ?33.00 | ?30.00 | ?30.00 | |
| Polyvalent alcohol 4 | pbw | ?9.50 | ?9.50 | ?9.50 | ?9.50 | |
| Fire retardant | pbw | ?9.50 | ||||
| Terate?2541 | pbw | ?9.50 | ?14.5 | |||
| Isoexter 3471 | ?14.50 | |||||
| Arconate 1000 | pbw | ?2.80 | ?2.80 | ?2.80 | ?2.80 | |
| Tensio-active agent | pbw | ?1.60 | ?1.60 | ?1.60 | ?1.60 | |
| Catalyzer | pbw | ?0.50 | ?0.50 | ?0.50 | ?0.50 | |
| Water | pbw | ?4.40 | ?4.40 | ?4.40 | ?4.40 | |
| Isocyanic ester | pbw | ?149.4 | ?155.1 | ?153.0 | ?156.9 | |
| Index | ?107.5 | ?100 | ?100 | ?100 | ||
| Cream time | ?s | ?15 | ?15 | ?15 | ?15 | |
| The wire drawing phase | ?s | ?120 | ?110 | ?96 | ?110 | |
| Adhesive power | kPa | ?100 | ?0.0 | ?0.0 | ?30 | |
| Density | kg/m 3 | ?27.8 | ?27.8 | ?27 | ?26.5 | |
Claims (15)
1. the method for preparing urethane or urethane modified polyisocyanurate isocyanuric acid ester rigid foam, comprise the step that organic multiple isocyanate and polyfunctional isocyanate's active ingredient react, be characterised in that polyfunctional isocyanate's active ingredient comprises greater than 2wt% water and 5～50wt%, average functionality and is lower than 3 polyester polyol.
2. the process of claim 1 wherein that the average functionality of polyester polyol is between 1.7～2.5.
3. claim 1 or 2 method, wherein polyester polyol is thick polyester polyol.
4. the method for claim 3, wherein thick polyester polyol is selected from DMT polyester polyol and waste material PET polyester polyol.
5. the method for any one in the above claim, wherein the amount of polyester polyol is between about 5～30wt% of isocyanate-reactive components gross weight.
6. the method for claim 5, wherein the amount of polyester polyol is between about 10～25wt% of isocyanate-reactive components gross weight.
7. the method for any one in the above claim, wherein polyfunctional isocyanate's active ingredient also comprises polyether glycol.
8. the method for claim 7, wherein said polyether glycol are the initiator for reaction preparations that contains 2～8 active hydrogen atoms by propylene oxide and each molecule.
9. the method for claim 8, wherein said initiator is selected from glycerine, sorbyl alcohol, sucrose, tolylene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines.
10. the method for any one in the above claim, wherein water consumption is between 2～6wt% of the total consumption of isocyanate-reactive components.
11. the urethane or the urethane modified polyisocyanurate isocyanuric acid ester rigid foam that can obtain by the method for any one regulation in the above claim.
12. with the urethane of claim 11 regulation or the cavity of urethane modified polyisocyanurate isocyanuric acid ester rigid foam filling.
13. the cavity of claim 12, wherein this cavity is the part of water heater.
14. the isocyanate-reactive composition comprises that 5～50wt%, average functionality are lower than 3 polyester polyol and greater than 2wt% water.
15. the isocyanate-reactive composition of claim 14, wherein polyester polyol is thick polyester polyol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98202384.8 | 1998-07-15 | ||
| EP98202384 | 1998-07-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1309678A true CN1309678A (en) | 2001-08-22 |
Family
ID=8233937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99808558A Pending CN1309678A (en) | 1998-07-15 | 1999-06-22 | Process for rigid polyurethane foams |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1098922A1 (en) |
| CN (1) | CN1309678A (en) |
| AU (1) | AU4614799A (en) |
| WO (1) | WO2000004070A1 (en) |
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| CN1986593B (en) * | 2006-08-18 | 2010-05-12 | 南京红宝丽股份有限公司 | Hard polyurethane foam composition with fast demolding performace |
| CN102167897A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Rigid polyurethane foam special for laminboard |
| CN102167949A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | HFC-365mfc/227-type environment-friendly polyurethane composite paint and preparation method thereof |
| CN102947364A (en) * | 2010-04-23 | 2013-02-27 | 巴斯夫欧洲公司 | Method for producing polyurethane rigid foams |
| CN103554469A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Method of synthesizing polyether polyol by mineral water bottle pieces |
| CN104169318A (en) * | 2012-03-15 | 2014-11-26 | 陶氏环球技术有限责任公司 | Low density full water blown polyurethane rigid foam |
| CN105732949A (en) * | 2014-12-12 | 2016-07-06 | 沈阳洪海精细化工有限公司 | Process of low-water low-hydroxyl-value high-MDI-index flame-retardant rigid foam polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1046659B1 (en) * | 1999-04-21 | 2005-08-17 | Basf Aktiengesellschaft | Composite elements comprising polyisocyanate-polyaddition products, in particular a hot water storage comprising rigid polyurethane foam |
| DE102005039973A1 (en) * | 2005-08-23 | 2007-03-08 | Basf Ag | Composite element containing polyisocyanate polyaddition products, in particular hot water storage containing polyurethanes |
| EP2184305A1 (en) * | 2008-11-07 | 2010-05-12 | Bayer MaterialScience AG | PIR hard foams, method for their manufacture and application thereof |
| CN103387652A (en) * | 2013-08-08 | 2013-11-13 | 常熟市中腾塑胶有限公司 | Method for preparing environmentally-friendly polyurethane plastic for track |
| EP4089129A1 (en) * | 2021-05-12 | 2022-11-16 | Covestro Deutschland AG | Storage-stable polyester polyol formulations containing terephthalic acid based polyester |
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| US4442237A (en) * | 1982-11-22 | 1984-04-10 | Texaco Inc. | Novel aromatic amide polyols from the reaction of phthalic acid residues, alkylene glycols and amino alcohols |
| JPH0236217A (en) * | 1988-07-27 | 1990-02-06 | Hitachi Ltd | Rigid polyurethane foam, its production, heat-insulating material and refrigerator manufactured therewith |
| US5169877A (en) * | 1988-12-09 | 1992-12-08 | The Dow Chemical Company | Rigid polyurethane foams with low thermal conductivities |
| DE4007330A1 (en) * | 1990-03-08 | 1991-09-12 | Bayer Ag | METHOD FOR THE PRODUCTION OF URETHANE, UREA AND BIURET GROUPS IN THE ESSENTIAL CLOSED CELLS GROUP AND USE THEREOF |
| US5310766A (en) * | 1992-06-15 | 1994-05-10 | The Dow Chemical Company | Foam stabilizing additive and polyurethane foam prepared in the presence thereof |
-
1999
- 1999-06-22 EP EP99929299A patent/EP1098922A1/en not_active Ceased
- 1999-06-22 CN CN99808558A patent/CN1309678A/en active Pending
- 1999-06-22 WO PCT/EP1999/004316 patent/WO2000004070A1/en not_active Application Discontinuation
- 1999-06-22 AU AU46147/99A patent/AU4614799A/en not_active Abandoned
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| CN1986593B (en) * | 2006-08-18 | 2010-05-12 | 南京红宝丽股份有限公司 | Hard polyurethane foam composition with fast demolding performace |
| CN102947364A (en) * | 2010-04-23 | 2013-02-27 | 巴斯夫欧洲公司 | Method for producing polyurethane rigid foams |
| CN102947364B (en) * | 2010-04-23 | 2015-06-24 | 巴斯夫欧洲公司 | Method for producing polyurethane rigid foams |
| CN102167897A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Rigid polyurethane foam special for laminboard |
| CN102167949A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | HFC-365mfc/227-type environment-friendly polyurethane composite paint and preparation method thereof |
| CN102167949B (en) * | 2010-11-29 | 2012-07-25 | 山东东大一诺威新材料有限公司 | HFC-365mfc/227-type environment-friendly polyurethane composite paint and preparation method thereof |
| CN102167897B (en) * | 2010-11-29 | 2012-07-25 | 山东东大一诺威新材料有限公司 | Rigid polyurethane foam special for laminboard |
| CN104169318B (en) * | 2012-03-15 | 2016-08-31 | 陶氏环球技术有限责任公司 | Low-density water-blown polyurethane rigid foam body |
| CN104169318A (en) * | 2012-03-15 | 2014-11-26 | 陶氏环球技术有限责任公司 | Low density full water blown polyurethane rigid foam |
| CN103554469A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Method of synthesizing polyether polyol by mineral water bottle pieces |
| CN105732949A (en) * | 2014-12-12 | 2016-07-06 | 沈阳洪海精细化工有限公司 | Process of low-water low-hydroxyl-value high-MDI-index flame-retardant rigid foam polyurethane |
| CN105732949B (en) * | 2014-12-12 | 2017-12-05 | 沈阳洪海精细化工有限公司 | The fire retardant hard-foam polyurethane technique of the high MDI indexes of the low hydroxyl value of low wash water |
| CN107513149A (en) * | 2017-08-31 | 2017-12-26 | 苏州市苏真床垫有限公司 | A kind of preparation method of terylene foaming mattress |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000004070A1 (en) | 2000-01-27 |
| AU4614799A (en) | 2000-02-07 |
| EP1098922A1 (en) | 2001-05-16 |
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