CN104039858A - Method for producing rigid polyurethane foams - Google Patents
Method for producing rigid polyurethane foams Download PDFInfo
- Publication number
- CN104039858A CN104039858A CN201280050821.5A CN201280050821A CN104039858A CN 104039858 A CN104039858 A CN 104039858A CN 201280050821 A CN201280050821 A CN 201280050821A CN 104039858 A CN104039858 A CN 104039858A
- Authority
- CN
- China
- Prior art keywords
- particle
- aethoxy sklerol
- polyvalent alcohol
- ethylenically unsaturated
- unsaturated monomer
- 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.)
- Pending
Links
Classifications
-
- 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
- C08G18/4829—Polyethers containing 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
- 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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- 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
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- 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
-
- 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
Landscapes
- 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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to polyurethane foams containing particles and characterised in that the particles are predominantly embedded in the cell walls.
Description
The present invention relates to a kind of method of preparing hard polyurethane foams, described method by polyisocyanates with contain at least two compounds that isocyanate groups is had to a hydrogen atom of reactive behavior and react and carry out.
Hard polyurethane foams is long-term known and be recorded in widely in document.By polyisocyanates,---particularly polyfunctional alcohol---reacts and prepares with containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior conventionally for they.Hard polyurethane foams is preferred for vibration damping in refrigeration equipment or for building element.
The characteristic of improving hard polyurethane foams is a lasting task.Particularly, should reduce the thermal conductivity of foam, and should improve the mechanical property of foam, particularly should improve compressive strength.
A feasible method realizing this target is to use containing Packed polyvalent alcohol in rigid foam is produced.Normally used is those that prepare by the ethylenically unsaturated monomer (particularly vinylbenzene and/or vinyl cyanide) in in-situ polymerization polyvalent alcohol (particularly Aethoxy Sklerol) containing Packed polyvalent alcohol.These products normally known and be known as polymer polyatomic alcohol or graft polyol.
The hard polyurethane foams that uses graft polyol to prepare is recorded in for example WO2005/097863 and WO2004/035650.The rigid foam of wherein recording shows shorter demould time, good mechanical property and lower thermal conductivity.
For foaming properties, particle being uniformly distributed in foam matrix is particularly important.Good being distributed in the first step refers to, do not form the aggregate by multiple granulometric composition, but uniform filling be distributed in polymer materials.Only just can a kind of economically viable mode use filler by this way.The distribution of this particle can be by being used the graft polyol being for example recorded in WO2005/097863 and WO2004/035650 to realize.
Except avoiding aggregate, for distribution for particle in foam, be a bit important in addition: conventionally, in the cell struts (cell strut) of rigid foam, the polyurethane material of existence at least 80% is (referring to D.W.Reitz, M.A.Sch ü tz, L.R.Glicksman " A basic study of aging of foam insulation ", Journal of cellular plastics, 1984,20 (2), 104-113).Therefore, nearly all particle is all present in cell struts, and only has minority filler particles to see in cell wall.In the time that foam stands high mechanically compress or tensile stress, material starts at weakness place (, at very thin cell wall place) and lost efficacy, and keeps complete and obvious stronger cell struts is initial.If realize the enhancing to foam by filler, need most fillers to be present in cell wall, this is because only this part has enhancement in whole fillers used.According to prior art, the filler distribution of this granule density in cell wall with increase is unknown.
Optimize hard polyurethane foams characteristic with filler and need to control fully the distribution of each particle in foam.
An object of the present invention is to provide polyurethane foam, specifically hard polyurethane foams, described foam presents good mechanical property, low thermal conductivity and good processing characteristics, and for example demould time reduces.Especially, the compressive strength of foam should be improved, thereby the density of foam can be reduced.In addition also should realize, the high-compatibility of starting ingredient (particularly polyol component) for the preparation of urethane and whipping agent (specifically referring to non-polar hydrocarbon here).
Unexpectedly, this object can realize by the cell wall that particle is mainly introduced into foam, the polymkeric substance that wherein said particle is ethylenically unsaturated monomer or inorganic particle, and particle surface has carried out modification by surfactant.
Therefore the invention provides the polyurethane foam that contains particle, wherein particle is mainly introduced into cell wall, the polymkeric substance that wherein said particle is ethylenically unsaturated monomer or inorganic particle, and particle surface has carried out modification by surfactant.
Herein, the particle that term " mainly " means at least 50 % by weight based on particle gross weight meter is introduced into cell wall.
The present invention also provides a kind of method of preparing hard polyurethane foams, and the method is carried out in the following manner: will
A) polyisocyanates, with
B) contain at least two compounds isocyanate groups to the hydrogen atom of reactive behavior,
C) whipping agent
Existence under react,
Wherein at least one a) or b) of component comprises surface by the particle of surfactant modification.
The present invention also provides the Aethoxy Sklerol that contains particle, and described Aethoxy Sklerol can be prepared by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and wherein at least one ethylenically unsaturated monomer has surface active properties.
The present invention also provides a kind of method of preparing the Aethoxy Sklerol that contains particle, and the method is undertaken by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and wherein at least one ethylenically unsaturated monomer has surface active properties.
For the present invention, surfactivity mean described compound can the immiscible material of increase-volume, particularly immiscible liquid or immiscible liquids and gases.This compound have with a kind of group of substances compatible and with the group of another kind of substances compatible.Therefore, surface active cpd is attached to the interface between unmixing material.
Described particle preferably has the size that is less than 50 μ m, particularly 0.5-10 μ m.
Described particle is preferably selected from organic granular, for example organic polymer or thermoplastic granulates; And inorganic particle, be particularly rich in for example carbon black of particle or the graphite of carbon or oxide compound, particularly inorganic oxide.
As mentioned above, described particle surface is owing to having surface active properties by surface mass modification.Particularly, this can be by realizing particle surface application surface promoting agent.Tensio-active agent can be realized by non covalent bond or preferably covalently key adhering to of particle.
In a preferred embodiment of the present invention, described particle is inorganic particle.They are preferably the above-mentioned particle that is rich in carbon, for example carbon black or graphite, or inorganic oxide, particularly metal oxide.
In the situation of inorganic particle, described tensio-active agent preferably contacts with particle in the mode that is attached to particle surface.
In another preferred embodiment of the present invention, the polymkeric substance that described particle is ethylenically unsaturated monomer.
In this case, described particle can be and is scattered in component a) or the preferred thermoplastic granulates in b).Described method is also referred to as melting emulsification (melt emulsion) method, and the method is known and is for example recorded in WO2009/138379.
Herein, identical with the situation of inorganic particle, described tensio-active agent also preferably contacts with particle in the mode that is attached to particle surface.
In a particularly preferred embodiment of the present invention, described particle is prepared by the ethylenically unsaturated monomer in in-situ polymerization polyvalent alcohol (particularly Aethoxy Sklerol).The polyvalent alcohol of being prepared by the method normally known and be often called as graft polyol.
Be known and be recorded in lot of examples by the synthetic graft polyol of described two kinds of methods.For example, synthesizing graft polyol by Semi-batch Process is recorded in following patent: EP439755 and US4522976.The specific form of Semi-batch Process is the semi-batch seed law being recorded in for example EP510533 and EP698628, wherein graft polyol is used as to the seed in reaction initial charge extraly.By continuous processing, to synthesize graft polyol be known equally and be recorded in particularly in WO00/59971 and WO99/31160.
For the organic granular of preparing by polymerization, particularly for prepare by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol those, the monomer that described tensio-active agent preferably preferably contains surface active groups and at least one ethylenic group by least one is introduced in particle.
Described monomer can be by making to have at least one reactive group tensio-active agent this group is had to the group of reactive behavior and the compound of ethylenically unsaturated group react and prepare with containing.
Preferably use the tensio-active agent that makes liquids and gases increase-volume by noncovalent interaction.This compounds is used as suds-stabilizing agent conventionally in the preparation of urethane.
The preferred embodiment of described tensio-active agent is the polyether silicone with at least one side chain that contains at least one hydroxyl, the polyether silicone of for example following formula
Wherein, x, y, z, n and m are numeral, and R is the alkyl with 1 to 10 carbon atom, and M is divalent aliphatic, aromatics or the araliphatic group with 2 to 10 carbon atoms, and is connected on polyether chain through ether, ester, carbamate, acetal groups.Preferably select x, y, z sum with the molecular weight that makes the siloxane chain in these compounds for for example 2000 to 6000g/mol, preferably 4000 to 5500g/mol.Z is preferably 1 or 0, average 0.9, and y is preferably 3 to 20.X defines thus.According to the present invention, preferably select n and m to make the molecular weight of side chain as 400 to 2500g/mol.The ratio of n/ (n+m) is preferably 10 to 90%; The value of m/ (n+m) is preferably similarly.
Therefore the present invention preferably provides such the inventive method: wherein the polyether silicone with at least one side chain that contains at least one hydroxyl is used as to tensio-active agent.
In addition, the present invention preferably provides such foam of the present invention: wherein surfactant is the polyether silicone with at least one side chain that contains at least one hydroxyl.
In addition, the present invention preferably provides such Aethoxy Sklerol that contains particle of the present invention: it can be prepared by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and wherein at least one ethylenically unsaturated monomer is because the polyether silicone that use has at least one side chain that contains at least one hydroxyl has surface active properties.
The present invention also preferably provides such the present invention the method for the preparation of the Aethoxy Sklerol that contains particle: described method is undertaken by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and wherein at least one ethylenically unsaturated monomer is because the polyether silicone that use has at least one side chain that contains at least one hydroxyl has surface active properties.
The molecular weight of the siloxane chain in these compounds is for for example 2000 to 6000g/mol, and preferably 4000 to 5500g/mol.The molecular weight of these compounds is for for example 10000 to 25000g/mol, and preferably 11000 to 22000g/mol, and particularly preferably 11000 to 20000g/mol.
Described oh group can with contain at least one unsaturated compound that isocyanate groups is had to the group of reactive behavior and react.These groups can be acid groups or anhydride group.The example of described undersaturated acid and acid derivative is maleic anhydride (MAn), fumaric acid, acrylate derivative and methacrylate derivative.Preferably MAn.This group can be preferably isocyanate groups, and this is because the carbamate groups obtaining is more stable to hydrolysis than ester group.The example of described unsaturated isocyanate is 3-pseudoallyl-1,1-dimethylbenzyl based isocyanate (TMI) and methacrylic acid isocyanato ethyl ester, preferably TMI.These compounds that contain ethylenically unsaturated group are commonly referred to as macromonomer or stablizer.
Other macromonomers that can suitably use or preferably be combined with above-claimed cpd are generally molecular weight Mw for 1000g/mol and comprise at least one usually in the straight or branched Aethoxy Sklerol of the reactive ethylenically unsaturated group of end.Described ethylenic unsaturated group can be by reacting and embed in existing polyvalent alcohol with ethylenic unsaturated carboxylic acid and/or carboxylic acid anhydride and undersaturated isocyanate derivates, described carboxylic acid and/or carboxylic acid anhydride are for example maleic anhydride, fumaric acid, acrylate derivative and methacrylate derivative, described isocyanate derivates is for example 3-pseudoallyl-1,1-dimethylbenzyl based isocyanate and methacrylic acid isocyanato ethyl ester.To be the starting molecule that contains hydroxyl and unsaturated ethylene linkage by use carry out alkoxylate to propylene oxide and oxyethane to another route prepares polyvalent alcohol.
The case history of described macromonomer is in US4390645, US5364906 and US6013731.
Described tensio-active agent can be introduced in macromonomer.
In another embodiment of the invention, described graft polyol is prepared by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, wherein grafted particles its preparation after by reacting and modification with surface active composition.
In one embodiment of the invention, described tensio-active agent does not comprise any halogen atom, does not particularly comprise any fluorine atom.
These monomers are attached to described particle surface in the preparation of graft polyol.
Consequently, the performance of described particle is similar to surfactant.
Surfactant granules used according to the invention can have functional group in addition, this functional group be preferably described particle can be via its chemical bonding the group to PU matrix.But particle of the present invention can also not have reactive functional group from the teeth outwards.
As mentioned above, foam of the present invention passes through a) polyisocyanates and b) contains at least two compounds that isocyanate groups is had to a hydrogen atom of reactive behavior and react and prepare, and wherein a) or b) at least one of component---preferred ingredient b)---contains described particle.
Not too preferably particle is introduced component a) in, this is because the polyisocyanates of greater activity can cause losing efficacy and undesired side reaction.
Therefore, components b) preferably comprise its surface by the particle of surfactant modification.
As mentioned above, in a preferred embodiment, described in contain particle polyvalent alcohol (particularly Aethoxy Sklerol), can prepare by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol (being commonly called carrier polyol).These polyvalent alcohols are commonly called graft polyol.
Described carrier polyol is preferably prepared by epoxy alkane (particularly oxyethane and/or propylene oxide) being added to H-functional compound (preferably containing hydroxyl or amino those).Described H-functional compound can be for containing the alcohol of 2 to 4 hydroxyls in molecule.Preferred embodiment has glycerine, TriMethylolPropane(TMP); And dibasic alcohol, for example ethylene glycol, Diethylene Glycol, propylene glycol and dipropylene glycol.In another embodiment of the invention, described H-functional compound is primary amine or the secondary amine that contains 2 to 4 hydrogen atoms.The example of aliphatic amine has quadrol, propylene diamine and thanomin.Preferably use arylamine, preferably tolylene diamine and herein ortho isomer particularly.
Described carrier polyol preferably has the hydroxyl value of 40 to 250mg KOH/g.
The solid content of described graft polyol is preferably 30 to 55 % by weight, based on the weighing scale of graft polyol.
For ethylenically unsaturated monomer, preferably use vinylbenzene and/or vinyl cyanide, particularly preferably the mixture of vinylbenzene and vinyl cyanide.The acrylonitrile content of these mixtures is particularly preferably 30 to 80 % by weight, based on mixture meter.
Graft polyol b1) preferably there is 0.1 to 8 μ m, the preferably polymkeric substance particle diameter of 0.2 to 4 μ m, the maximum value of particle diameter is 0.2 to 3 μ m, preferably 0.2 to 2.0 μ m.
In another preferred embodiment, graft polyol b1) size distribution be bimodal (bimodal), that is, the distribution curve of particle diameter has two maximum values.Described graft polyol can be for example mixed and prepares in the proper ratio by (monomodal) size distribution unimodal by having and the graft polyol with different-grain diameter, or by preparing as carrier polyol with the polyvalent alcohol of the polymkeric substance that has comprised ethylenically unsaturated monomer in the initial charge of reaction.In this embodiment, described particle diameter is equally in above-mentioned scope.
In one embodiment of the invention, described graft polyol can continuous production.
In another preferred embodiment, described graft polyol is prepared by Semi-batch Process.
About the preparation of polyurethane foam, particularly rigid foam, can provide following details.
Feasible organic multiple isocyanate a) is preferably aromatics polyfunctional isocyanate.
Specific examples has: toluene 2,4-and 2,6-vulcabond (TDI) and corresponding isomer mixture, ditane 4,4 '-, 2,4 '-and 2,2 '-vulcabond (MDI) and corresponding isomer mixture, ditane 4,4 '-and 2, the mixture of 4 '-vulcabond, polyphenyl polymethylene polyisocyanates, ditane 4,4 '-, 2,4 '-and 2, the mixture (thick MDI) of 2 '-vulcabond and polyphenyl polymethylene polyisocyanates, and the mixture of thick MDI and tolylene diisocyanate.Organic diisocyanate and polyisocyanates can use separately or with the form of mixture.
Conventionally also use the polyfunctional isocyanate of modification, the product obtaining by the chemical reaction of organic diisocyanate and/or polyisocyanates.The example that can mention is vulcabond and/or the polyisocyanates that comprises isocyanuric acid ester and/or carbamate groups.The polyisocyanates of modification be optionally mixed with each other or with unmodified organic multiple isocyanate (as ditane 2,4 '-, 4,4 '-vulcabond, thick MDI, toluene 2,4-and/or 2,6-vulcabond) mix.
In addition, also can use the reaction product of polyfunctional isocyanate and poly-hydroxy polyvalent alcohol and the mixture with other vulcabond and polyisocyanates thereof.
Find that NCO content is that the viscosity of 29-33 % by weight and the 25 DEG C thick MDI within the scope of 150-1000mPas is particularly advantageous as organic multiple isocyanate.
The polyvalent alcohol bi1 that contains particle) can be used as in principle unique compound that contains at least two hydrogen atoms isocyanate groups to reactive behavior b).But, this compound b1) preferably contain at least two compound uses isocyanate groups to the hydrogen atom of reactive behavior with other.
For this reason, can use conventional and known at least two compounds isocyanate groups to the hydrogen atom of reactive behavior that contain.Preferably by Aethoxy Sklerol and/or polyesterols and polyvalent alcohol b1) be combined with.
With polyvalent alcohol b1) together with the polyesterols of use conventionally prepare by containing 2 to 12 carbon atoms, the preferably polyfunctional alcohol of 2 to 6 carbon atoms and the condensation of the polyfunctional carboxylic acids that contains 2 to 12 carbon atoms, described polyfunctional alcohol's preferred diol, described polyfunctional carboxylic acids is succinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, toxilic acid, fumaric acid for example, and the naphthalene dicarboxylic acids of preferred phthalic acid, m-phthalic acid, terephthalic acid and isomery.
With polyvalent alcohol b1) together with use Aethoxy Sklerol conventionally have 2 to 8, be in particular 3 to 8 functionality.
Particularly use the Aethoxy Sklerol of preparing by currently known methods, for example, by the Aethoxy Sklerol that under the existence in catalyzer, preferred alkali metal hydroxide prepared by anionoid polymerization epoxy alkane.
As epoxy alkane, conventionally use oxyethane and/or propylene oxide, preferred pure 1,2 epoxy prapane.
As initial substance, use especially and in molecule, contain at least 3, the preferred compound of 4 to 8 hydroxyls or at least 2 primary amine groups.
As containing at least 3, the preferred starting molecule of 4 to 8 hydroxyls in molecule, preferably use TriMethylolPropane(TMP), glycerine, tetramethylolmethane, sugar compounds (for example glucose, sorbyl alcohol, N.F,USP MANNITOL and sucrose), polyphenol, resol (the oligomeric condensed products of for example phenol and formaldehyde, and Mannich (Mannich) condenses of phenol, formaldehyde and dioxane hydramine) and trimeric cyanamide.
As the starting molecule that contains at least two primary amino groups in molecule, preferably use aromatic diamine and/or polyamines, for example phenylenediamine, 2,3-, 2,4-, 3,4-and 2,6-tolylene diamine (TDA) (particularly 2,3-and 3,4-TDA) and 4,4 '-, 2,4 '-and 2,2 '-diaminodiphenyl-methane, and aliphatic diamine and such as quadrol of polyamines.2 of TDA, 3-and 3,4-isomer are also called as adjacent TDA.
The functionality of described Aethoxy Sklerol is preferably 3 to 8, and hydroxyl value is preferably 100mg KOH/g to 1200mg KOH/g, in particular for 240mg KOH/g to 570mg KOH/g.
In a preferred embodiment of the inventive method, by graft polyol bi1) and at least one use the Aethoxy Sklerol bii2 of aliphatic amine initial (initiated)) mixture as containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior.Described Aethoxy Sklerol bii2) preferably there is the hydroxyl value of 375 to 525mg KOH/g.
In another preferred embodiment of the inventive method, by graft polyol bi1) and at least one use arylamine initial Aethoxy Sklerol bii3) mixture as containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior.Described Aethoxy Sklerol bii3) preferably there is the hydroxyl value of 375 to 525mg KOH/g.In addition, utilizing the initial and hydroxyl value of adjacent TDA is that the Aethoxy Sklerol of 100 to 250mg KOH/g can be used as polyvalent alcohol bii3).
In another preferred embodiment of the inventive method, by graft polyol bi1) and at least one use sugar (particularly sorbyl alcohol or sucrose) initial Aethoxy Sklerol bii4) mixture as containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior.Described Aethoxy Sklerol bii4) preferably there is the hydroxyl value of 300 to 700mg KOH/g.
In another preferred embodiment of the inventive method, by graft polyol bi1) and at least one use trivalent alcohol (particularly glycerine and/or TriMethylolPropane(TMP)) initial Aethoxy Sklerol bii5) mixture as containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior.Described Aethoxy Sklerol bii5) preferably there is the hydroxyl value of 100 to 250mg KOH/g.
In another preferred embodiment of the present invention, polyvalent alcohol bi) or bii) comprise and use the initial Aethoxy Sklerol bii6 of two functional alcohol).
In another preferred embodiment of the present invention, described compound b) comprises at least one polyvalent alcohol bii1), at least one polyvalent alcohol bii4) and at least one polyvalent alcohol bii2) and/or bii3).
Polyvalent alcohol bii1, the polyvalent alcohol bii2 of 0-15 % by weight ratio, bii3, the bii4 of 25-60 % by weight ratio and the bii5 of 0-15 % by weight ratio of 15-40 % by weight ratio that preferred polyol component comprises 10-30 % by weight ratio.
The compound that contains at least two hydrogen atoms isocyanic ester to reactive behavior b) also comprises chainextender and the linking agent that can optionally accompany and use.Described hard polyurethane foams can with or do not prepare with chainextender and/or linking agent.Add difunctionality chainextender, trifunctional and Geng Gao official can linking agent or optionally its mixture can be conducive to improve mechanical property.As chainextender and/or linking agent, preferably use alkanolamine, and particularly molecular weight lower than 400, preferably 60 to 300 glycol and/or triol.
B) count based on containing at least two compounds isocyanate groups to the hydrogen atom of reactive behavior, chainextender, linking agent or its mixture are advantageously with 1-20 % by weight, the preferably amount use of 2-5 % by weight.
Described reaction is carried out conventionally under catalyzer, whipping agent and the auxiliary agent of routine and/or the existence of additive.
As catalyzer, special use violent isocyanate groups and the compound reacting of group isocyanate groups to reactive behavior of accelerating.
This class catalyzer is strong basicity amine, for example aliphatic secondary amine, imidazoles, amidine and alkanolamine or organometallics, particularly organo-tin compound.
If also isocyanurate group is introduced in hard polyurethane foams, need the specific catalyzer for this object.As isocyanurate catalyst, conventionally use metal carboxylate, particularly potassium acetate and solution thereof.
Described catalyzer can use as required and separately or use with any mixture form each other.
As whipping agent, preferably make water, it reacts to remove carbonic acid gas with isocyanate groups.Also the pneumatogen that can be combined or replace water to use with water.These whipping agents are compounds that starting ingredient is inertia and is conventionally at room temperature vaporized under urethane reaction condition for liquid.The boiling point of these compounds is preferably lower than 50 DEG C.Pneumatogen also comprises under room temperature being gaseous state and the compound that is introduced into or is dissolved in starting ingredient under superatmospheric pressure, for example carbonic acid gas, lower boiling alkane and fluoric ether.
Described compound is selected from the tetraalkyl silane, particularly tetramethylsilane that in the alkane that contains at least 4 carbon atoms and naphthenic hydrocarbon, dialkyl ether, ester, ketone, acetal, the fluoric ether that contains 1-8 carbon atom and alkyl chain, contain 1-3 carbon atom conventionally.
The example that can mention is propane, normal butane, Trimethylmethane and tetramethylene, Skellysolve A, iso-pentane and pentamethylene, hexanaphthene, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl-formiate, acetone and the fluoric ether that can degrade and therefore can not damage the ozone layer in troposphere, for example trifluoromethane, methylene fluoride, 1,1,1,3,3-3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-Tetrafluoroethane, C2H4F2 C2H4F2 and 1,1,1,2,3,3,3-heptafluoro-propane, and perfluoro alkane, for example: C
3f
8, C
4f
10, C
5f
12, C
6f
14or C
7f
17.The above-mentioned pneumatogen of mentioning can be used alone or uses with any combination thereof each other.
Described whipping agent particularly preferably comprises at least one aliphatic hydrocrbon that preferably contains at least 4 carbon atoms.In a preferred embodiment of the inventive method, the combination of water and aliphatic hydrocrbon is as whipping agent.Preferred hydrocarbon Skellysolve A, iso-pentane and pentamethylene.
Especially, if use hydrocarbon as whipping agent, particle can be introduced to cell wall best.
If needed, method of the present invention can be carried out under the existence of fire retardant and conventional auxiliary agent and/or additive.
As fire retardant, can use organophosphate and/or phosphonic acid ester.Preferably use compound isocyanate groups to without reactive behavior.Preferred compound also comprises chloride phosphoric acid ester.
The Typical Representative thing of this based flame retardant is triethyl phosphate, di(2-ethylhexyl)phosphate phenyl cresyl ester, tricresyl phosphate (chloropropyl) ester and diethyl ethane phosphoric acid ester.
In addition, also can use brominated fire retardant.As brominated fire retardant, preferably use and have the respond compound of active group of isocyanate groups.This compounds is, the ester of for example tetrabromophthalate and aliphatic diol, and the alkoxylated polymerization product of dibromo butyleneglycol.Also can use the compound derived from the bromination neo-pentyl compound that contains OH group.
As auxiliary agent and/or additive, use for the known material of this object itself for example surfactant, suds-stabilizing agent, pore regulator, filler, pigment, dyestuff, fire retardant, hydrolysis inhibitor, static inhibitor, fungistat and bacterial inhibitor.
Other details about the raw material for implementing the inventive method, whipping agent, catalyzer and auxiliary agent and/or additive is found in, for example Kunststoffhandbuch, the 7th volume, " Polyurethane " Carl-Hanser-Verlag, Munich, the 1st edition, 1966, the 2nd edition, 1983 and the 3rd editions, in 1993.
For preparing hard polyurethane foams, polyisocyanates a) with contain at least two compounds isocyanate groups to the hydrogen atom of reactive behavior and b) react with such amount: make isocyanate index in 100 to 220, preferably 115 to 195 scope.Described hard polyurethane foams can be by using known mixing equipment intermittently or continuously to produce.
The production of polyisocyanurate foam can also, with high index more, preferably be carried out up to 350.
Hard PUR foam of the present invention is produced by two-pack method conventionally.In the method, by the compound that contains at least two hydrogen atoms isocyanate groups to reactive behavior b) with fire retardant, catalyzer c), whipping agent d) and other auxiliary agents and/or additive mix to form polyol component, then make it react with the mixture---also referred to as isocyanate component---of the optional whipping agent using with polyisocyanates or polyisocyanates.
Described starting ingredient conventionally 15 to 35 DEG C, preferably at the temperature of 20 to 30 DEG C, mix.Described reaction mixture can be by high pressure or low-voltage metering equipment and is dropped into the support tool of sealing.
In addition, described reaction mixture optionally can also be toppled over or be sprayed in the cavity of above surperficial or opening.Can carry out original position isolation to top and complicated container by this method.Also described reaction mixture can be introduced to the closed mould can with complex geometry at a point or while at multiple points.Described reaction mixture can inject by the multiple different positionss on mould.The time point that this mould can inject at reaction mixture has different three-dimensional space calibrations.A typical example of described method is to produce refrigeration plant.Described reaction mixture can similarly be poured in open mold, and this mould is being filled closure after described mixture.This method is for example generally used for producing the door of refrigeration plant.
Prepare graft polyol
The graft polyol of using in following examples can continuous processing and interrupter method prepare.Known by the synthetic graft polyol of these two kinds of methods.Synthesize graft polyol by Semi-batch Process and be recorded in for example EP439755.The specific form of Semi-batch Process is the semi-batch seed law being recorded in EP510533 for example, wherein by graft polyol extraly as the seed in reaction initial charge.There is the synthetic WO03/078496 of being recorded in of the graft polyol of bimodal particle size distribution.By continuous processing, to synthesize graft polyol be known equally and be recorded in for example WO00/59971.
The embodiment preparing by Semi-batch Process and comparative example's graft polyol
Graft polyol by Semi-batch Process Preparation Example and comparative example carries out in 2 liters of autoclaves being furnished with double speed agitator, internal condensation coil pipe and electric heating cover.Before reaction starts, pack the mixture of carrier polyol and macromonomer into reactor, with nitrogen purging and be heated to 125 or 130 DEG C of synthesis temperatures.In some is synthetic, except carrier polyol and macromonomer, add extraly the initial charge of reaction using graft polyol as seed.In another group experiment, only part macromonomer is introduced in reactor at first.Its surplus is introduced reactor through incoming flow independently in building-up process.
The remainder of the reaction mixture that comprises other carrier polyol, initiator, monomer and reaction negative catalyst (reaction moderator) is placed at least two feed containers.Synthesizing by starting material are transferred to reactor and are carried out from feed containers with constant feeding rate through the embedded mixing tank of static state (static in-line mixer) of described graft polyol.The joining day of monomer/negative catalyst mixture is 150 or 180 minutes, and polyvalent alcohol/initiator mixture was metered in reactor through 165 or 195 minutes.Under temperature of reaction, further rear reaction, after 10 to 30 minutes, is transferred to thick graft polyol in glass flask by outlet at bottom valve.Unreacted monomer and other volatile compounds in removing product under decompression (<0.1 millibar) subsequently at the temperature of 135 DEG C.Stablize final product with antioxidant subsequently.
Specific macromonomer is for graft polyol 5-7.This is the polyether silicone corresponding to following formula
Wherein, x, y, z, n and m are the number with the value providing in this specification sheets, and R is the alkyl with 1 to 10 carbon atom, M is divalent aliphatic, aromatics or the araliphatic group with 2 to 10 carbon atoms, and be connected on polyether chain through ether, ester, carbamate, acetal groups, for example, utilize the molecular defect of dimethyl-m-pseudoallyl benzyl isocyanate ester (TMI), Tegostab B8462 is reacted at 80 DEG C with TMI so that each polyether silicone molecular reaction falls to be no more than statically 1 OH group.
Prepare rigid foam (Foaming by the machine)
With ratio shown in table 1, various polyvalent alcohols, stablizer, catalyzer and water and whipping agent are mixed.By in 100 weight part polyol components and table 1 separately shown in the mixture of diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates---NCO content is that 31.5 % by weight and viscosity are 200mPas(25 DEG C)---of amount exist
in HD30 (Elastogran GmbH) high-pressure foam machine, mix.Described reaction mixture is injected and is of a size of the mould of 200cm x20cm x5cm or 40cm x70cm x9cm and described mixture is foamed therein.Characteristic and the characteristic of gained foam are listed in table 1.
Based on mutually stable polyol component, prepared by the demould time that the hard polyurethane foams of being prepared by method of the present invention can be very short, and this can shorten cycle time significantly.Although there is graft polyol, a large amount of pneumatogens is dissolvable in water in this polyol component, thereby can obtain the foam density lower than 30g/l in component.The foaming properties of compressive strength, thermal conductivity and foam surface quality (forming shrinkage hole (sinkhole)) aspect is excellent.
Polyurethane reactive mixture is poured into and is of a size of 200x20x5cm
3in the mould of (excessively filling 10%), after several hours, from shearing, centre is of a size of 20x20x2cm
3test sample.
Compressive strength is measured according to DIN53421/DIN EN ISO604.
The ratio of particle in cell wall looks like to measure by the scanning electron microscopy of quantitative evaluation foam.
The mensuration of the ratio of particle in cell wall: scanning electron microscopy picture, the statistical estimation of particle.
By following examples, the present invention is described.Unless otherwise, all data are in weight part.Exponential sum orifice coefficient does not have unit.
The Aethoxy Sklerol that polyvalent alcohol 1 – is obtained by adjacent TDA, oxyethane and propylene oxide, hydroxyl value is 390mg KOH/g
The Aethoxy Sklerol that polyvalent alcohol 2 – are obtained by sucrose, glycerine and propylene oxide, hydroxyl value is 440mg KOH/g
The Aethoxy Sklerol that polyvalent alcohol 3 – are obtained by adjacent TDA, oxyethane and propylene oxide, hydroxyl value is 160mg KOH/g
Polyvalent alcohol 4 – graft polyols, hydroxyl value is 19mg KOH/g, by the vinylbenzene in in-situ polymerization Aethoxy Sklerol (obtained by glycerine and propylene oxide, hydroxyl value is 35mg KOH/g) and vinyl cyanide preparation.Macromonomer is the reaction product of sorbyl alcohol and ethylene oxide/propylene oxide and TMI, and molecular weight is 18000g/mol.
Polyvalent alcohol 5 – are similar to the graft polyol of polyvalent alcohol 4, under the existence of the polyether silicone surfactants macromonomer of above-mentioned chemical formula (, corresponding to), prepare.The molal weight of siloxane chain in this compound is 4400g/mol, has 81% oxyethane and 19% propylene oxide in side chain, and the molecular weight of these compounds is 13000g/mol.
Polyvalent alcohol 6 – are similar to the graft polyol of polyvalent alcohol 4, under the existence of the polyether silicone surfactants macromonomer of above-mentioned chemical formula (, corresponding to), prepare.The molal weight of siloxane chain in this compound is 5050g/mol, has 60% oxyethane and 40% propylene oxide in side chain, and the molecular weight of these compounds is 19000g/mol.
Polyvalent alcohol 7 – are similar to the graft polyol of polyvalent alcohol 4, under the existence of the polyether silicone surfactants macromonomer of above-mentioned chemical formula (, corresponding to), prepare.The molal weight of siloxane chain in this compound is 5050g/mol, has 60% oxyethane and 40% propylene oxide in side chain, and the molecular weight of these compounds is 16000g/mol.
Stablizer is Tegostab B8462
Catalyzer is N, N-dimethylcyclohexylamine, N, N, N', N ", N " five methyl diethylentriamine and Lupragen N600 (1,3,5-tri-(dimethylaminopropyl)-symmetry-Hexahydrotriazine; S-triazine) the mixture of 53:26:21 ratio.
Foam of the present invention has the compressive strength of raising.Therefore, the foam density of foam of the present invention further reduces the foam density than conventional foam.
Another advantage is the good solidification in foam surface region.Even after shorter demould time, described foam is also firm, and stronger and more not yielding than the foam of comparative formula.This provides advantage for processing freshly prepd foam.
Claims (17)
1. contain a polyurethane foam for particle, wherein said particle is mainly introduced in cell wall, the polymkeric substance that described particle is ethylenically unsaturated monomer or inorganic particle, and described particle surface has carried out modification by surfactant.
2. the foam of claim 1, wherein said surfactant is the polyether silicone with at least one side chain that contains at least one hydroxyl.
3. prepare a method for hard polyurethane foams, the method is carried out in the following manner: will
A) polyisocyanates, with
B) contain at least two compounds isocyanate groups to the hydrogen atom of reactive behavior,
C) whipping agent
Existence under react,
Wherein a) or b) at least one of component comprises its surface by the particle of surfactant modification.
4. the method for claim 3, wherein has the polyether silicone of at least one side chain that contains at least one hydroxyl as tensio-active agent.
5. the method for claim 3 or 4, wherein said particle is present in components b) in.
6. the method for any one in claim 3 to 5, wherein said components b) comprise the Aethoxy Sklerol bi that at least one contains particle), described Aethoxy Sklerol bi) contain at least two and isocyanate groups is had to the hydrogen atom of reactive behavior and prepare by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, wherein at least one monomer comprises ethylenic unsaturated bond and surface active groups.
7. the method for any one in claim 3 to 6, wherein said components b) comprise the Aethoxy Sklerol bi that at least one contains particle), described Aethoxy Sklerol bi) contain at least two and isocyanate groups had to the hydrogen atom of reactive behavior and prepare by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, wherein grafted particles after its preparation by reacting and modification with surface active composition.
8. the method for any one in claim 3 to 7, wherein said components b) comprise at least one other polyvalent alcohol bii).
9. the method for any one in claim 3 to 8, wherein said polyvalent alcohol bi) or bii) comprise and use the initial Aethoxy Sklerol bii2 of aliphatic amine).
10. the method for any one in claim 3 to 8, wherein said polyvalent alcohol bi) or bii) comprise and use the initial Aethoxy Sklerol bii3 of aromatic amine).
The method of any one in 11. claims 3 to 8, wherein said polyvalent alcohol bi) or bii) comprise the Aethoxy Sklerol bii4 that uses sugar initial).
The method of any one in 12. claims 3 to 8, wherein said polyvalent alcohol bi) or bii) comprise and use the initial Aethoxy Sklerol bii5 of trifunctional alcohol).
The method of any one in 13. claims 3 to 8, wherein said polyvalent alcohol bi) or bii) comprise and use the initial Aethoxy Sklerol bii6 of difunctional alcohol).
The method of any one in 14. claims 3 to 13, wherein compound b) comprises at least one polyvalent alcohol bii4) and at least one polyvalent alcohol bi1) and/or bii2).
15. 1 kinds of Aethoxy Sklerols that contain particle, it can be prepared by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and at least one in wherein said ethylenically unsaturated monomer has surface active properties.
Prepare the method for the Aethoxy Sklerol that contains particle for 16. 1 kinds, it is undertaken by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, and at least one in wherein said ethylenically unsaturated monomer has surface active properties.
The method of the Aethoxy Sklerol that the preparation of 17. claims 15 contains particle, it is undertaken by the ethylenically unsaturated monomer in in-situ polymerization Aethoxy Sklerol, wherein carries out described preparation by Semi-batch Process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11177819.7 | 2011-08-17 | ||
| EP11177819 | 2011-08-17 | ||
| PCT/EP2012/065915 WO2013024101A2 (en) | 2011-08-17 | 2012-08-14 | Method for producing rigid polyurethane foams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104039858A true CN104039858A (en) | 2014-09-10 |
Family
ID=46690505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280050821.5A Pending CN104039858A (en) | 2011-08-17 | 2012-08-14 | Method for producing rigid polyurethane foams |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP2744841A2 (en) |
| JP (1) | JP2014524493A (en) |
| KR (1) | KR20140052022A (en) |
| CN (1) | CN104039858A (en) |
| AU (1) | AU2012296911A1 (en) |
| BR (1) | BR112014003673A2 (en) |
| IN (1) | IN2014CN01171A (en) |
| MX (1) | MX2014001705A (en) |
| RU (1) | RU2014109848A (en) |
| WO (1) | WO2013024101A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129486A1 (en) * | 2019-12-24 | 2021-07-01 | 青岛海尔电冰箱有限公司 | Rigid polyurethane foam and preparation method therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9403963B2 (en) | 2011-08-23 | 2016-08-02 | Basf Se | Particle-comprising polyether alcohols |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4723026A (en) * | 1984-04-24 | 1988-02-02 | Bp Chemicals Limited | Preparation of polymer polyols |
| US6005016A (en) * | 1998-10-06 | 1999-12-21 | Bayer Corporation | Rigid polyurethane foam based on polyethers of TDA |
| CN101796178A (en) * | 2007-07-03 | 2010-08-04 | 多米尼克·德洛贝尔 | System for producing micro-organisms |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390645A (en) | 1979-11-23 | 1983-06-28 | The Dow Chemical Company | Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom |
| US4522976A (en) | 1984-05-17 | 1985-06-11 | Basf Wyandotte Corporation | Graft polymer dispersion in a mixture of low molecular weight polyols and polyether polyols and polyurethane foams prepared therefrom |
| US4797501A (en) * | 1986-12-31 | 1989-01-10 | Union Carbide Corporation | Silicone-based stabilizers useful in the preparation of improved polyurethane foams |
| US5086084A (en) * | 1989-08-29 | 1992-02-04 | Lee H. Ambrose | Polyvinyl chloride/polyurethane hybrid foams |
| ES2069664T3 (en) | 1990-01-29 | 1995-05-16 | Basf Corp | A PROCESS TO PREPARE GRAFT POLIOLS AND POLIOLS PREPARED BY THE SAME. |
| EP0510533A3 (en) | 1991-04-22 | 1993-05-26 | The Dow Chemical Company | Process for preparing polymer polyols, and polymer polyol so made |
| US5364906A (en) | 1993-08-20 | 1994-11-15 | Arco Chemical Technology, L.P. | Low viscosity polymer polyols with improved dispersion stability |
| US5488085A (en) | 1994-08-18 | 1996-01-30 | Arco Chemical Technology, L.P. | Semi-batch process for producing polymer polyols |
| US6013731A (en) | 1997-12-16 | 2000-01-11 | Arco Chemical Technology L.P. | Stabilizer based on high molecular weight polyols having low monol content for polymer polyol production |
| CN1178776C (en) * | 1999-03-04 | 2004-12-08 | 旭硝子株式会社 | Method for producing thermally insulating plate |
| US6172164B1 (en) | 1999-04-01 | 2001-01-09 | Basf Corporation | Process for making graft polyols using t-amyl peroxy free radical initiator |
| BR0308127B1 (en) | 2002-03-15 | 2012-07-10 | grafted polyol, processes for preparing it and polyurethanes, and use of a grafted polyol. | |
| ES2381663T3 (en) | 2002-10-15 | 2012-05-30 | Basf Se | Procedure for obtaining hard polyurethane foams with graft polyols |
| JP2005272806A (en) * | 2003-10-22 | 2005-10-06 | Sanyo Chem Ind Ltd | Rigid polyurethane foam |
| DE102004017294A1 (en) * | 2004-04-05 | 2005-10-20 | Basf Ag | Process for the production of polyurethane foams |
| CN101541851B (en) * | 2006-11-20 | 2012-07-04 | 旭硝子株式会社 | Method for producing polymer-dispersed polyol |
| JP2009057485A (en) * | 2007-08-31 | 2009-03-19 | Kao Corp | Method of manufacturing polyurethane foam |
| JP4851503B2 (en) * | 2007-10-10 | 2012-01-11 | 三洋化成工業株式会社 | Method for producing fine particle dispersed polyol and method for producing polyurethane resin |
| WO2009138379A2 (en) | 2008-05-13 | 2009-11-19 | Basf Se | Method for producing polyol dispersions |
| JP2011157469A (en) * | 2010-02-01 | 2011-08-18 | Asahi Glass Co Ltd | Rigid foamed synthetic resin and method for producing the same |
-
2012
- 2012-08-14 CN CN201280050821.5A patent/CN104039858A/en active Pending
- 2012-08-14 JP JP2014525436A patent/JP2014524493A/en active Pending
- 2012-08-14 BR BR112014003673A patent/BR112014003673A2/en not_active IP Right Cessation
- 2012-08-14 RU RU2014109848/04A patent/RU2014109848A/en not_active Application Discontinuation
- 2012-08-14 WO PCT/EP2012/065915 patent/WO2013024101A2/en active Application Filing
- 2012-08-14 MX MX2014001705A patent/MX2014001705A/en unknown
- 2012-08-14 AU AU2012296911A patent/AU2012296911A1/en not_active Abandoned
- 2012-08-14 KR KR1020147006470A patent/KR20140052022A/en not_active Application Discontinuation
- 2012-08-14 EP EP12748207.3A patent/EP2744841A2/en not_active Withdrawn
- 2012-08-14 IN IN1171CHN2014 patent/IN2014CN01171A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4723026A (en) * | 1984-04-24 | 1988-02-02 | Bp Chemicals Limited | Preparation of polymer polyols |
| US6005016A (en) * | 1998-10-06 | 1999-12-21 | Bayer Corporation | Rigid polyurethane foam based on polyethers of TDA |
| CN101796178A (en) * | 2007-07-03 | 2010-08-04 | 多米尼克·德洛贝尔 | System for producing micro-organisms |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129486A1 (en) * | 2019-12-24 | 2021-07-01 | 青岛海尔电冰箱有限公司 | Rigid polyurethane foam and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014524493A (en) | 2014-09-22 |
| AU2012296911A1 (en) | 2014-03-06 |
| WO2013024101A2 (en) | 2013-02-21 |
| BR112014003673A2 (en) | 2017-03-01 |
| MX2014001705A (en) | 2014-03-21 |
| WO2013024101A3 (en) | 2013-10-31 |
| IN2014CN01171A (en) | 2015-04-10 |
| EP2744841A2 (en) | 2014-06-25 |
| RU2014109848A (en) | 2015-09-27 |
| KR20140052022A (en) | 2014-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8293807B2 (en) | Method for the production of rigid polyurethane foam | |
| US7456229B2 (en) | Process for the production of rigid and semi-rigid foams with low amounts of diisocyanate using polymer polyols characterized by high solids and a high hydroxyl number and the resultant foams | |
| CN103154068B (en) | Prepare the method for low compression set and high gas flow '-diphenylmethane diisocyanate viscoelastic polyurethane foams | |
| EP2760905B1 (en) | Viscoelastic foam | |
| CN102239200B (en) | Foamable composition for polyurethane foam, and polyurethane foam | |
| JP7098614B2 (en) | Polyurethane rigid foam, its manufacturing method, and its uses | |
| CN109071752A (en) | Hard polyurethane foams | |
| CN103635503A (en) | Low density polyurethane foam | |
| CZ303184B6 (en) | Process for preparing rigid and flexible polyurethane foams containing fire suppressing substances | |
| CN107646042A (en) | The method for forming polyurethane foam product | |
| AU2012298513B2 (en) | Method for producing polyurethanes | |
| US20060058409A1 (en) | Method for producing rigid polyurethane foams by means of graft polyhydric alcohols | |
| CN105555850B (en) | The pure and mild polyol blend of polyester polyols and rigid polyurethane foams manufacture | |
| JP2004504425A (en) | Method for producing flexible polyurethane foam | |
| CN106103521A (en) | The polyether polyol balanced for the foamable gel that polyurethanes product prepared therefrom offer is good | |
| CN104039858A (en) | Method for producing rigid polyurethane foams | |
| US9403963B2 (en) | Particle-comprising polyether alcohols | |
| CN103890047A (en) | Polyether alcohols containing particles | |
| AU2012299689B2 (en) | Polyether alcohols containing particles | |
| US20130046037A1 (en) | Process for producing rigid polyurethane foams | |
| US20130072655A1 (en) | Process for producing polyurethanes | |
| CN107108481A (en) | surfactant for polyurethane foam | |
| CN105263982A (en) | Polyol formulations containing fillers and polyurethanes produced therefrom | |
| EP4204468A1 (en) | Rigid polyurethane foam and multilayer thermal insulation assemblies containing the foam | |
| CA3143005A1 (en) | Process for making a flexible polyurethane foam having a hardness gradient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140910 |