CN102781997A - Method for producing polyurethanes - Google Patents
Method for producing polyurethanes Download PDFInfo
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- CN102781997A CN102781997A CN2011800117838A CN201180011783A CN102781997A CN 102781997 A CN102781997 A CN 102781997A CN 2011800117838 A CN2011800117838 A CN 2011800117838A CN 201180011783 A CN201180011783 A CN 201180011783A CN 102781997 A CN102781997 A CN 102781997A
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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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
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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
- C08G18/48—Polyethers
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
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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
- C08G2110/0025—Foam properties rigid
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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
The invention relates to a method for producing polyurethanes by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive with two isocyanate groups, characterized in that at least one polyether alcohol b1) having a functionality of 2-8 and a hydroxyl number of 200-600 mg KOH/g is used as the compounds having at least two hydrogen atoms reactive with two isocyanate groups, said alcohol having been produced by building up alkylene oxides b1b) on compounds having at least two hydrogen atoms reactive with alkylene oxides using an amine b1c) as a catalyst.
Description
The present invention relates to a kind of through POLYMETHYLENE POLYPHENYLISOCYANATE with have at least two compound reaction and method for producing polyurethanes that isocyanate groups are reactive Wasserstoffatoms.
Urethane is long-time known and extensively be described in the document.They are usually through making POLYMETHYLENE POLYPHENYLISOCYANATE and having at least two compound reactions that isocyanate groups is reactive Wasserstoffatoms and prepare.
Urethane can be used for many industrial circles.Can change initial compounds has different performance with preparation urethane.The urethane that so provides can be fine and close or be foaming through using whipping agent.
Because preferably having at least two compounds that isocyanate groups is reactive Wasserstoffatoms through change, the limited amount of commercially available POLYMETHYLENE POLYPHENYLISOCYANATE, the different performance of urethane realize.
Have at least two compounds that isocyanate groups is reactive Wasserstoffatoms and in most of the cases be the polyfunctional alcohol.Except polyesterols, Aethoxy Sklerol has maximum industrial significance.
Aethoxy Sklerol is in most of the cases through oxyalkylene, and preferred ethylene oxide and/or the addition of propylene oxide on polyfunctional alcohol and/or amine prepare.This addition reaction is carried out in the presence of catalyzer usually.
All these methods are known by those of ordinary skill in the art.
Invariable purpose is to improve the processing characteristics and the product performance of urethane.As being explained, this mainly becomes possibility via the modification of Aethoxy Sklerol.This modification can realize through the character of used polyvalent alcohol itself, but also realizes through the material that uses adding.
The method that the purpose of this invention is to provide the mobile urethane of component that a kind of preparation is characterized in that improving.Each component should have low-down viscosity and effectively pumping at low temperatures.Each component must have machinable viscosity after the load filler.In addition, each component is to whipping agent, more specifically should have good solubility for hydrocarbon and have the consistency of improving with isocyanic ester.Gained urethane should have low release and uniform texture, does not more specifically have space and crackle on the surface.
We find that this purpose shockingly realizes through the polyol component that use comprises the Aethoxy Sklerol that at least a use amine obtains as catalyzer.
US 20070203319 has described through oxyalkylene is added to be formed in by dimethylethanolamine with US 20070199976 and has been included in the Aethoxy Sklerol that obtains on the starter substance for the solid compound under the room temperature.Yet, the urethane that uses these polyvalent alcohols to obtain is not described.
Therefore; The invention provides a kind of method for producing polyurethanes; This method comprises makes a) POLYMETHYLENE POLYPHENYLISOCYANATE and b) have at least two compound reactions that isocyanate groups are reactive Wasserstoffatoms; Wherein saidly have at least two compound b that isocyanate groups are reactive Wasserstoffatoms) to comprise at least a functionality be that 2-8 and hydroxyl value are the Aethoxy Sklerol b1 of 200-800mg KOH/g), said alcohol is through using amine b1c) as catalyzer with oxyalkylene b1b) add to be formed in and have at least two compound-hereinafters that oxyalkylene is reactive Wasserstoffatoms and also be known as starter substance-go up and obtain.
Aethoxy Sklerol b1) can be used as components b) unique compound.
Preferred, polyethers alcohol b1) based on components b) weight use with the amount of 10-90 weight %.
Be preferred for preparing Aethoxy Sklerol b1) have at least two compounds that oxyalkylene is reactive Wasserstoffatoms comprise comprise at least a solid compound b 1ai that at room temperature is) mixture.
This compounds is known and is generally used for making Aethoxy Sklerol, especially in the hard polyurethane foams those.They are preferably selected from TriMethylolPropane(TMP), tetramethylolmethane, glucose, sorbyl alcohol, mannitol and sucrose; Polyphenol, resol, the for example oligomeric condensation product of phenol and formaldehyde; The oligomeric condensation product (MDA) of aniline and formaldehyde; The Mannich condensate of tolylene diamine (TDA) and phenol, formaldehyde and two alkanolamines also has melamine, and the mixture of at least two kinds of listed alcohol.
In a preferred embodiment of the invention, compound b 1ai) be selected from sucrose, sorbyl alcohol and tetramethylolmethane, more preferably sucrose or sorbyl alcohol.In special preferred embodiment of the present invention, b1ai) be sucrose.
As compound b 1ai) aromatic amine more specifically be selected from tolylene diamine (TDA) or diphenylmethanediisocyanate (MDA) or polymerization MDA (p-MDA).Under the situation of TDA, more specifically use 2,3-and 3, the 4-isomer also is known as ortho position TDA.
Useful starter substance b1a) further comprise comprise at least a compound b 1aii of liquid that at room temperature is) have at least two compounds that oxyalkylene are reactive Wasserstoffatoms.
In a preferred embodiment of the invention, components b 1) starter substance except compound b 1ai) also comprise at room temperature the compound b 1aii that oxyalkylene is reactive Wasserstoffatoms that comprises for liquid).
Compound b 1aii) can comprise alcohol or amine.These more specifically have 1-4, and preferred 2-4 is reactive Wasserstoffatoms to oxyalkylene.
This compound (b1aii) is preferably selected from glycerine, has monofunctional alcohol, ethanol, Ucar 35 and the higher homologue thereof of 1-20 carbon atom, terepthaloyl moietie and higher homologue thereof and also have single-, two-or trialkanolamine, more specifically be glycerine.
In another embodiment of the present invention, components b 1a) comprise at least a solid amine b1ai that at room temperature is) and at room temperature be the pure b1aii of liquid) mixture.At room temperature be solid alcohol b1ai) can preferably comprise MDA and polymerization MDA.The pure b1aii that at room temperature is liquid) can preferably comprise terepthaloyl moietie and higher homologue thereof and Ucar 35 and higher homologue thereof.The concentration of amine homologue depends on processing condition among the p-MDA.This distribution (in weight %) is common as follows:
Dicyclo MDA:50-80 weight %
Three ring MDA:10-25 weight %
Fourth Ring MDA:5-12 weight %
Five rings or more ring MDA:5-12 weight %
Preferred p-MDA mixture has following composition:
Dicyclo MDA:50 weight %
Three ring MDA:25 weight %
Fourth Ring MDA:12 weight %
Five rings or more ring MDA:13 weight %
Further preferred p-MDA mixture has following composition:
Dicyclo MDA:80 weight %
Three ring MDA:10 weight %
Fourth Ring MDA:5 weight %
Five rings or more ring MDA:5 weight %
In another preferred embodiment of the present invention, components b 1a) comprise at least a solid alcohol (b1ai) and a kind of alcohol (b1aii) that at room temperature is liquid of at room temperature being) mixture.At room temperature being solid alcohol (b1ai) and preferably including the sugar alcohol that is more specifically as above characterized, more specifically is sucrose.The compound (b1aii) that at room temperature is liquid preferably includes at least a compound b 1aii); It is selected from glycerine; Monofunctional alcohol with 1-20 carbon atom, ethanol, Ucar 35 and higher homologue thereof; Terepthaloyl moietie and higher homologue thereof and single-, two-or trialkanolamine, more specifically be glycerine.Components b 1a) can also comprise water.When making water, this amount is based on components b 1a) weight more specifically be no more than 25 weight %.
The aforesaid compound (b1aii) that at room temperature is liquid can also comprise having the compound that oxyalkylene is reactive Wasserstoffatoms and 1-20 carbon atom.Preferred here monofunctional alcohol is like methyl alcohol, ethanol, propyl alcohol, octanol, dodecanol.
Oxyalkylene b1b) preferably includes propylene oxide, ethylene oxide, oxybutylene, oxidation iso-butylene, Styrene oxide 98min. and wherein two kinds or more kinds of mixtures.Preferably the mixture with propylene oxide, ethylene oxide or propylene oxide and ethylene oxide is used as oxyalkylene b1b).Especially preferably propylene oxide is used as oxyalkylene b1b).
Aforesaid catalyzer b1c) comprise components b 1ai) and b1aii) in addition amine.This amine can comprise primary, the second month in a season or tertiary amine and aliphatic series or aromatic amine, more specifically is aliphatic series or aromatic uncle amine.In another embodiment, can consider in ring, to have at least one, the aromatic heterocycle compounds of a preferred nitrogen-atoms.
Amine b1c) being preferably selected from trialkylamine, more specifically is Trimethylamine 99, triethylamine, tripropyl amine; Tributylamine, dimethyl alkylamine more specifically is dimethylethanolamine, dimethyl-ethoxy ethanol amine, dimethylcyclohexylam,ne, dimethylethyl amine, dimethylbutyl amine, aromatic amine; More specifically be xylidine, Dimethylamino pyridine, dimethyl benzyl amine, pyridine, imidazoles (more specifically being imidazoles, N-Methylimidazole, glyoxal ethyline, 4-methylimidazole, 5-Methylimidazole, 2-ethyl-4-methylimidazole, 2,4-methylimidazole, 1-hydroxypropyl imidazoles, 2,4,5-tri-methylimidazolium, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, N-phenylimidazole, 2-phenylimidazole, 4-phenylimidazole); Guanidine, alkylation guanidine class (more specifically is 1,1; 3, the 3-tetramethyl guanidine), the 7-methyl isophthalic acid; 5, in 7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene, the amidine class (more specifically is 1; 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, 1,5-diazabicyclo [5.4.0] 11 carbon-7-alkene).
The mixture that can also use at least two kinds of said amine is as catalyzer.
In a preferred embodiment of the invention, be dimethylethanolamine catalyzer b1c).
In a preferred embodiment of the invention, be a kind of imidazoles catalyzer b1c).
Based on whole batch of material, this amine is preferably with 0.01-5.0 quality %, preferred 0.05-3.0 quality %, and more preferably the amount of 0.1-1.0 quality % is used for wherein.
In order to prepare Aethoxy Sklerol b1), usually with each composition b1a of starter substance mixture) and b1c) introduce in the reactor drum and mix.Then with the inerting therein of this mixture.Be metered into oxyalkylene then.
The addition reaction of oxyalkylene is preferably carried out under the pressure that temperature and the 0.1-8 of 90-150 ° of C cling to.The metered charge of oxyalkylene is afterwards through carrying out post-reaction period, to accomplish the reaction of this oxyalkylene.
Oxyalkylene carries out post-reaction period after being metered into and accomplishing usually, and reactions of alkylene oxide is to complete in this stage.Necessary, carry out post-reaction period after this.Usually distill after this to remove volatile matter, distillation is preferably under reduced pressure carried out.
Amine catalyst b1c) can remain in the Aethoxy Sklerol.This has simplified the method for preparing them, because the removing of catalyzer-and when using alkali-metal oxide compound necessary-necessity no longer with oxyhydroxide.This causes the improvement of space-time yield.Through removing by filter the salt formation filter cake.Polyvalent alcohol loss in the filter cake reaches certain percentage usually.Improved space-time yield helps to reduce manufacturing cost with the strainer loss of avoiding.
The combination of alkali metal hydroxide catalyzer and amine catalyst also is useful.This especially hangs down the selection scheme of the polyvalent alcohol of hydroxyl value for preparation.Products therefrom can be similar to and use the catalytic polyvalent alcohol of alkali metal hydroxide to carry out aftertreatment.Perhaps, they can also be through only carrying out neutralization procedure and aftertreatment with acid.At this moment, preferably use carboxylic acid, like lactic acid, acetate or 2 ethyl hexanoic acid.
Amine catalyst b1c) itself can be in reaction process alkoxylate.Therefore, oxyalkylated amine has the more volatility of HMW and reduction in product subsequently.Because the residual autoreaction property of alkoxylate amine catalyst, with the late phase reaction process of isocyanic ester in mix in the polymer backbone.The autoreaction property of the tertiary amine that forms is given the autoreaction property of polyvalent alcohol can advantageously using in some applications.
Do not hope to receive the constraint of any theory, it is believed that the Aethoxy Sklerol that uses amine to obtain as catalyzer has the structure various structure of the Aethoxy Sklerol that obtains with other catalyzer of use.This different molecular structure has advantage in the manufacturing of urethane.
Therefore, polyvalent alcohol of the present invention is used at urethane, particularly in the method for manufacture of polyurethane foam, has tangible advantage.
As described, with Aethoxy Sklerol b1) be used to make urethane.
The raw material that is used for this can more specifically be described below:
Used organic multiple isocyanate a) is preferably the aromatics polyfunctional isocyanate.
Specific examples is: 2, and 4-and 2,6-tolylene diisocyanate (TDI) and corresponding isomer mixture, 4; 4 '-, 2,4 '-with 2,2 '-diphenylmethanediisocyanate (MDI) and corresponding isomer mixture; 4,4 '-with 2, the mixture of 4 '-diphenylmethanediisocyanate and in the manufacturing of hard polyurethane foams particularly 4; 4 '-, 2,4 '-with 2, the mixture of 2 '-diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates (thick MDI).
Aethoxy Sklerol of the present invention is usually to use with the mixtures with at least two other compounds that isocyanate groups are reactive Wasserstoffatoms.
Can be with the used Aethoxy Sklerol b1 of the present invention) use and have at least two compounds that isocyanic ester is reactive Wasserstoffatoms and especially comprise Aethoxy Sklerol and/or the polyesterols of OH value as 100-1200mg KOH/g.
With the used Aethoxy Sklerol b1 of the present invention) polyesterols that uses has 2-12 carbon atom through making usually; The polyfunctional alcohol of preferred 2-6 carbon atom; Preferred diol with have the polyfunctional carboxylic acids of 2-12 carbon atom, for example succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dioctyl phthalate, toxilic acid, fumaric acid and preferably phthalic acid, m-phthalic acid, terephthalic acid and isomery the naphthalic acid condensation and prepare.
With the used Aethoxy Sklerol b1 of the present invention) Aethoxy Sklerol that uses has 2-8 usually, more specifically is the functionality of 3-8.
Preferred especially the use through currently known methods, for example through oxyalkylene at catalyzer, the anionoid polymerization under preferred alkali metal hydroxide exists and the Aethoxy Sklerol for preparing.
Used oxyalkylene in most of the cases is ethylene oxide and/or propylene oxide, and is preferred pure 1, the 2-propylene oxide.
Used starter molecules especially has at least 3 in molecule, preferred 4-8 hydroxyl or have the compound of at least 2 primary aminos.
As in molecule, having at least 3, the starter molecules of preferred 4-8 hydroxyl is preferably used TriMethylolPropane(TMP); Glycerine, tetramethylolmethane, sugar compounds such as glucose, sorbyl alcohol, sugar alcohol and sucrose; Polyphenol, resol, the for example oligomeric condensation product of phenol and formaldehyde; The oligomeric condensation product (MDA) of aniline and formaldehyde, the Mannich condensate of tolylene diamine (TDA) and phenol, formaldehyde and two alkanolamines and also have melamine.
The functionality of Aethoxy Sklerol is preferably 3-8 and hydroxyl value is preferably 100-1200mg KOH/g, more preferably 120-570mg KOH/g.
Through in polyol component, using the difunctionality polyvalent alcohol of molecular weight as 500-1500, for example polyoxyethylene glycol and/or W 166 can change the viscosity of polyol component.
Have at least two compounds that isocyanic ester is reactive Wasserstoffatoms and also comprise optional chainextender and the linking agent that uses.Hard polyurethane foams can use or not use under chain extension and/or the linking agent and make.The adding of difunctionality chainextender, trifunctional and Geng Gao functional crosslinker or optional its mixture in addition possibly prove favourable for changing mechanical property.Used chain extension and/or linking agent be preferably alkanolamine and more specifically for molecular weight below 400, be preferably glycol and/or the triol of 60-300.
Chainextender, linking agent or its mixture advantageously based on this polyol component with 1-20 weight %, the amount of preferred 2-5 weight % is used.
Polyurethane foam is made in the presence of whipping agent usually.Used whipping agent preferably can be water, and it reacts with isocyanate groups through eliminating carbonic acid gas.Another common chemical whipping agent is a formic acid, its through release of carbon dioxide and carbonic acid gas and and isocyanate reaction.Except or replace chemical foaming agent also can use so-called pneumatogen.Pneumatogen generally includes the compound that at room temperature is liquid, and it is inertia to feed component and under the urethane reaction condition, vaporizes.The boiling point of these compounds is preferably at 50 ° below the C.Pneumatogen also comprises at room temperature for gaseous state and adding to depress to be introduced and/or is dissolved in the compound in the feed component; Instance is a carbonic acid gas, and paraffinic hydrocarbons more specifically is lower boiling paraffinic hydrocarbons and fluoro paraffinic hydrocarbons; Preference chain alkane more specifically is lower boiling paraffinic hydrocarbons and fluoro paraffinic hydrocarbons.
Pneumatogen is selected from paraffinic hydrocarbons and/or the naphthenic hydrocarbon with at least 4 carbon atoms, dialkyl ether, ester usually; Ketone; Acetal, the tetraalkyl silane that has the fluoro paraffinic hydrocarbons of 1-8 carbon atom and in alkyl chain, have 1-3 carbon atom more specifically is TMS.
Instance is propane, normal butane, Trimethylmethane, tetramethylene, Skellysolve A, iso-pentane, pentamethylene, hexanaphthene, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl-formiate, acetone, and can in the troposphere, degrade in addition and the therefore fluoro paraffinic hydrocarbons harmless to ozonosphere, like trifluoromethane, methylene fluoride, 1,1,1,3; 3-3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1; 1,2,3-five fluorine propylene, 1-chloro-3,3,3-trifluoro propene, 1,1; 1,2-Tetrafluoroethane, C2H4F2 C2H4F2 and 1,1,1,2; 3,3, the 3-HFC-227, and also have the perfluoroalkane hydrocarbon, like C3F8, C4F10, C5F12, C6F14 and C7F16.Preferred especially pentane more specifically is a pentamethylene.Said pneumatogen can use separately or use with any required combination each other.
Can use the mixture of physics and chemical foaming agent in a preferred embodiment of the invention.The mixture of preferred especially pneumatogen and water more specifically is the mixture of hydrocarbon and water.Preferred especially pentane in hydrocarbon, wherein pentamethylene especially.
Necessary, can and also have routine to assist and/or add at catalyzer, fire retardant and make urethane in the presence of the material.Other details of relevant used initial compounds for example can be at Kunststoffhandbuch, the 7th volume, " urethane ", and G ü nter Oertel edits, and Carl-Hanser-Verlag Munich, finds in 1993 by the 3rd edition.
Urethane obtained by the method for the present invention more specifically comprises polyurathamc, more specifically is rigid foam.In a particular embodiment of the present invention, rigid foam has dense layer surface and cellular core and also is known as skinning rigid foam or high density structures foam usually.This class A foam A is produced in the presence of whipping agent in closed mould usually.The combination of pressure and die temperature makes the foamy surface densification become cortex.This class A foam A has many application, for example is used for automobile decoration and turbulence generator zone (spoilerbereich), for example is used for the section bar of window, accessory, counter body and press filtration plate (filterdruckplatten).The foamy surface quality is conclusive in these are used.
Rigid foam for example comprise be used for adiabatic those.Aethoxy Sklerol b1) excellent compatibility and the good flow behavior with whipping agent here is favourable.Usually advantageously has excellent compatibility between polyol blends and the isocyanic ester.Bad polyvalent alcohol/isocyanate-compatible possibly cause the separation of reactive component in some cases, and particularly in relating to the system in long reaction times, and this possibly cause the poor bonding of the coarse abscess property of foamy and foam and base material again.
Another embodiment of the present invention is utilized rigid foam in vehicle structure, for example in engine room or in inside.The engine room Application Design becomes when having an accident, to absorb energy.Rigid foam is used for inside makes polymer sheet, and for example
foamed at vinyl polymer (vinylfolien) the sheet material back side, and this is for example like this really for side door panel or panel board.The major advantage of urethane obtained by the method for the present invention is lower mist formation here.
Another advantage that mist formation reduces is because Aethoxy Sklerol b1) autoreaction property, can reduce the catalyst consumption that is similarly the mist formation source.
At the skinning rigid foam, the special demands that also are known as in the manufacturing of thermosetting foams are Aethoxy Sklerol b1) and whipping agent, particularly hydro carbons, like the excellent compatibility of pentamethylene.
The manufacturing of thermosetting foams further utilizes filler usually.One group of filler is to have those of flame retardant properties, like ammonium polyphosphate, seal red phosphorus or aluminum trihydrate (aluminumtrihydrat).
Another kind of filler is inorganic salt, like lime carbonate, calcium sulfate or permanent white.
It is ground spun glass, thomel, carbon nanotube, glass microsphere, silicon, carbon black, wollastonite, talcum, clay, pigment such as titanium oxide that important filler is gone up in other industry.
The following example explanation the present invention.
The preparation polyvalent alcohol:
Embodiment 1 (the present invention):
Measurement charging device and the 960L pressurized reactor that is used for device and the vacuum system of nitrogen inerting that will be equipped with whisking appliance, chuck heating and cooling, is used to comprise solid and the liquid substance of oxyalkylene is heated to 80 ° of C with dry and with nitrogen inerting repeatedly.Add 102.75kg glycerine, start whisking appliance and be metered into 154.3kg sugar.This reactor drum is heated to 95 ° of C.After adding 6.03kgDMEOA, begin to be metered into 541.57kg PO and temperature of reactor owing to reaction heat rises to 112 ° of C.Under 90 ° of C after the reaction 3 hours, this product under 100 ° of C in nitrogen gas stream stripping and obtain the polyvalent alcohol that 776kg has following specification:
Hydroxyl value 483mg KOH/g
Viscosity is 6600mPas under 25 ° of C
Water-content 0.023%
Embodiment 2 (contrast):
Measurement charging device and the 960L pressurized reactor that is used for device and the vacuum system of nitrogen inerting that be equipped with whisking appliance, chuck heating and cooling, is used to comprise solid and the liquid substance of oxyalkylene is heated to 88 ° of C with dry and with nitrogen inerting repeatedly.Add 91.18kg glycerine and start whisking appliance.Add 3.32kg 48%KOH and 139.26kg sucrose then.Under 105 ° of C, add 96.91kg PO.Be warming up to 112 ° of C then and be metered into other 373.54kg PO.After afterreaction 2 hours, this product with nitrogen stripping under 100 ° of C, is mixed with water then, with neutralization of 80% phosphoric acid and filtration.Output is the 682kg polyvalent alcohol, and it is analytically characterizing by following:
Hydroxyl value 497mg KOH/g
Viscosity is 8400mPas under 25 ° of C
Water-content 0.016%
Potassium 35.7ppm
Only if description is arranged in addition, the viscosity of polyvalent alcohol and polyol blends is used Rheotec RC 20 rotational viscosimeters (the spindle diameter: 12.5mm with spindle CC 25DIN; Measure the right cylinder internal diameter: 13.56mm) under 25 ° of C, measure with the shearing rate of 50l/s.
Hydroxyl value is measured according to DIN 53240.
Pentane solubility is measured:
50g polyvalent alcohol or polyol blends are introduced in the 100mL Glass Containers.Add a certain amount of pentamethylene.With this Glass Containers sealing, shaken 5 minutes left standstill 1 hour then then.Detect the outward appearance of this sample then.When sample is clarified, repeat this test with more pentamethylene.When this mixture is muddy, repeat this test with pentamethylene still less.Confirm to dissolve in the pentamethylene maximum in polyvalent alcohol or the polyol blends in this way.This amount is the pentane solubility of polyvalent alcohol or polyol blends.The accuracy of this method is 1%.
Table 1: used polyvalent alcohol
| Polyvalent alcohol | Starter substance | Catalyzer | Hydroxyl value | Pentane solubility | Viscosity |
| mg?KOH/g | % | [mPas] | |||
| 1 | Sucrose PO, Fn=4.3 | DMEOA | 483 | 12 | 6600 |
| 2 | Sucrose PO, Fn=4.3 | KOH | 497 | <10 | 8400 |
| 3 | Glycerine PO | KOH | 230 | Uncorrelated | Uncorrelated |
Fn – average functionality
PO – propylene oxide
Isocyanate-compatible:
The polymeric MDI that is used for the inventive method is non-miscible usually like
(isocyanic ester (I)) and polyvalent alcohol from BASF SE.Isocyanic ester (II); NCO content be 23 weight % based on 4; The prepolymer of 4 '-MDI; Commercial with
, dissolve mixed fully with these polyvalent alcohols.The mixture of isocyanic ester I and II depends on that its ratio of mixture can or cannot be molten mixed with these polyvalent alcohols.This is the basis of the method for the miscibility of mensuration polyvalent alcohol and isocyanic ester.The program that is adopted is following: it is on the watch-glass of 4cm that the 1.00g polyvalent alcohol is placed diameter.The mixture that adds 1.00g isocyanic ester I and isocyanic ester II then stirs 1 minute not form bubble because of stirring with spatula then.Stir and stop after 1 minute the naked eyes test sample.It is muddy or transparent that this mixture seems to be.When this mixture was muddy, being used in this mixture more, the isocyanic ester II of vast scale repeated this test.When this mixture was transparent, being used in this mixture more, the isocyanic ester I of vast scale repeated this test.
Confirm the isocyanic ester I maximum in this mixture when this mixture is just still transparent in this way.The accuracy of measuring isocyanic ester I amount in this mixture is 2%.
Under the situation of polyvalent alcohol 1 of the present invention, the ratio of mixture of isocyanic ester I:II is 15/85.For the contrast polyvalent alcohol, the ratio of mixture of isocyanic ester I:II is 5/95.
Embodiment 3: rigid foam applications
The foam production that is used for mechanical test
To comprise 100pbw polyvalent alcohol or polyol blends, 2.4pbw gets from the base foam body system of
tensio-active agent of Goldschmidt and 0.85pbw water and makes starting point.
(
of BASFSE is used as isocyanic ester with whipping agent and with polymkeric substance MDI as catalyzer with dimethylcyclohexylam,ne and pentamethylene.At isocyanate index is 100 times production foams.The hand mix raw material.Confirm the amount of dimethylcyclohexylam,ne, so that the foamy gel time is 55 seconds.Confirm the amount of pentamethylene, so that the free foam density of foamy is 35kg/m.Use and in 11.4L cube steel die, to produce the 500g foam sample by prescription.After 20 minutes with this sample demoulding.Then this sample is stored 3 days, then test.According to ISO 845 standard test density and according to ISO604 standard test compressive strength.
Table 2: foam formulation
| Polyvalent alcohol 1 | Part | 100 | |
| Polyvalent alcohol 2 | Part | 100 | |
| Tegostab?B?8467 | Part | 2.4 | 2.4 |
| DMCHA | Part | 5 | 5.2 |
| Zero(ppm) water | Part | 0.85 | 0.85 |
| CP | Part | 14.5 | 14.8 |
| Cup test | |||
| Time of coagulation | s | 55 | 56 |
| Density | kg/m 3 | 38 | 38 |
| Cubes | |||
| Compressive strength/stress | N/mm 2 | 0.27 | 0.28 |
| Core density | kg/m 3 | 34.5 | 35 |
In the explanation of table 2: in foaming, polyvalent alcohol of the present invention presents the autocatalysis performance and realizes equal densities needs still less catalyzer and whipping agent still less.
Embodiment 4: thermoset is used
Table 3: catalytic amount is to reactive influence
| Polyvalent alcohol 1 | Weight part | 87.7 | 87.7 | 87.7 | |||
| Polyvalent alcohol 2 | Weight part | 87.7 | 87.7 | 87.7 | |||
| Polyvalent alcohol 3 | Weight part | 7.8 | 7.8 | 7.8 | 7.8 | 7.8 | 7.8 |
| Tegostab?B?2219 | Weight part | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Tap water | Weight part | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 |
| Dabco?33LV | Weight part | 1.1 | 1.1 | 0.5 | 0.5 | 0.25 | 0.25 |
| Cup test | |||||||
| Time of coagulation | s | 133 | 94 | 305 | 150 | 540 | 190 |
In the explanation of table 3: in foaming, polyvalent alcohol of the present invention presents the autocatalysis performance and than non-polyvalent alcohol needs of the present invention catalyzer still less.Catalyst concn reduces, and this effect increases.
Table 4: filler is to the influence of viscosity
| Polyvalent alcohol 1 | Weight part | 87.7 | 83.3 | 78.9 | 70.2 | ||||
| Polyvalent alcohol 2 | Weight part | 87.7 | 83.3 | 78.9 | 70.2 | ||||
| Polyvalent alcohol 3 | Weight part | 7.8 | 7.8 | 7.4 | 7.4 | 7.0 | 7.0 | 6.2 | 6.2 |
| ?Tegostab?B?2219 | Weight part | 1.5 | 1.5 | 1.4 | 1.4 | 1.4 | 1.4 | 1.2 | 1.2 |
| Tap water | Weight part | 1.9 | 1.9 | 1.8 | 1.8 | 1.7 | 1.7 | 1.5 | 1.5 |
| Dabco?33LV | Weight part | 1.1 | 1.1 | 1.0 | 1.0 | 1.0 | 1.0 | 0.9 | 0.9 |
| CaCO3 | Weight part | 0.0 | 0.0 | 5.0 | 5.0 | 10.0 | 10.0 | 20.0 | 20.0 |
| Viscosity under 20 ° of C | mPas | 8200 | 6700 | 9100 | 7300 | 9800 | 8000 | ?12000 | 9700 |
Polyvalent alcohol viscosity is measured according to ISO 3219 under 20 ° of C.In the explanation of table 4: add various fillers.The limiting viscosity of polyvalent alcohol of the present invention also can be measured in infill system.Plate is made:
The preparing A component also leaves standstill half a hour at least.After adding isocyanic ester, under maximum agitator speed with this mixture mechanical stirring 13 seconds.Then under 50 ° of C with this mixture impouring mold heat (in 20 * 15 * 1cm).After 5 minutes with this plate demoulding.
Table 5: the mechanical property of foam formulation and plate
| System | 1 | 2 | |
| Polyvalent alcohol 1 | 87.7 | ||
| Polyvalent alcohol 2 | 87.7 |
| Polyvalent alcohol 3 | Part | 7.8 | 7.8 |
| Tegostab?B?2219 | Part | 1.5 | 1.5 |
| Tap water | Part | 1.9 | 1.9 |
| Dabco?33LV | Part | 1.1 | 1.1 |
| Plate | |||
| Density | kg/m 3 | 285 | 280 |
| Shore D hardness | 30 | 30 | |
| Flexural strength/stress | N/mm 2 | 8.3 | 8.1 |
| Sagging | mm | 20.6 | 20.2 |
Surface quality is estimated:
Place on each plate and use the circle carbon-point with the flat sides setting-out on an A4 paper.This page is put into scanner, with the threshold value binary (binarisiert) confirmed and remove little pixel.Confirm the area ratio of (black) protuberance then.(the present invention) is 1% and is 22% to system 2 (prior art) ratio of protuberance to system 1.
Claims (19)
1. method for producing polyurethanes; Comprise and make a) POLYMETHYLENE POLYPHENYLISOCYANATE and b) have at least two compound reactions that isocyanate groups are reactive Wasserstoffatoms; Wherein saidly have at least two compound b that isocyanate groups are reactive Wasserstoffatoms) to comprise at least a functionality be that 2-8 and hydroxyl value are the Aethoxy Sklerol b1 of 200-600mg KOH/g), said alcohol is through using amine b1c) as catalyzer with oxyalkylene b1b) add to be formed in to have at least two compounds that oxyalkylene are reactive Wasserstoffatoms and obtain.
2. according to the process of claim 1 wherein said Aethoxy Sklerol b1) based on said components b) weight use with the amount of 10-90 weight %.
3. be used to prepare said Aethoxy Sklerol b1 according to the process of claim 1 wherein) said have at least two compounds that oxyalkylene is reactive Wasserstoffatoms comprise comprise at least a solid compound b 1ai that at room temperature is) mixture.
4. according to the process of claim 1 wherein said compound b 1ai) be selected from tetramethylolmethane, glucose; Sorbyl alcohol, mannitol, sucrose; Polyphenol, resol, the condenses of aniline and formaldehyde; Tolylene diamine, the Mannich condensate of phenol, formaldehyde and two alkanolamines, at least two kinds mixture in melamine and the said compound.
5. according to the process of claim 1 wherein compound b 1a) be selected from sucrose, sorbyl alcohol and tetramethylolmethane.
6. be used to prepare said Aethoxy Sklerol b1 according to the process of claim 1 wherein) saidly have at least two compound b 1a that oxyalkylene are reactive Wasserstoffatoms) comprise comprise at least a compound b 1aii of liquid that at room temperature is) mixture.
7. according to the process of claim 1 wherein said compound b 1aii) be selected from glycerine, have monofunctional alcohol, Ucar 35 and the higher homologue thereof of 1-20 carbon atom, terepthaloyl moietie and higher homologue thereof and also have single-, two-or trialkanolamine.
8. according to the process of claim 1 wherein said compound b 1a) comprise at least a at room temperature for solid compound b 1ai) and at least aly at room temperature be the compound b 1aii of liquid) mixture.
9. according to the process of claim 1 wherein said amine b1c) be selected from trialkylamine, aromatic amine, pyridine, imidazoles, guanidine, alkylation guanidine, amidine class.
10. according to the method for claim 1, it is at whipping agent c) in the presence of carry out.
11. according to the method for claim 1, it utilizes water as whipping agent.
12. according to the method for claim 1, it utilizes pneumatogen.
13. according to the process of claim 1 wherein that said pneumatogen is selected from paraffinic hydrocarbons and fluoro paraffinic hydrocarbons.
14. according to the method for claim 1, it carries out in the presence of filler.
15. according to the process of claim 1 wherein that said filler is inorganic salt.
16. according to the process of claim 1 wherein that said filler is selected from ammonium polyphosphate, seals red phosphorus and aluminum trihydrate.
17. according to the process of claim 1 wherein that said filler is selected from ground spun glass, thomel, carbon nanotube, glass microsphere, silicon, carbon black, wollastonite, talcum, clay and pigment.
18. according to the process of claim 1 wherein that said polyurethane foam produces in closed mould.
19. urethane that can obtain according to each method among the claim 1-16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10155201.6 | 2010-03-02 | ||
| EP10155201 | 2010-03-02 | ||
| PCT/EP2011/052555 WO2011107366A1 (en) | 2010-03-02 | 2011-02-22 | Method for producing polyurethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102781997A true CN102781997A (en) | 2012-11-14 |
Family
ID=44064200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800117838A Pending CN102781997A (en) | 2010-03-02 | 2011-02-22 | Method for producing polyurethanes |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2542608A1 (en) |
| JP (1) | JP2013521354A (en) |
| KR (1) | KR20130004587A (en) |
| CN (1) | CN102781997A (en) |
| MX (1) | MX2012009742A (en) |
| SG (1) | SG183523A1 (en) |
| WO (1) | WO2011107366A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105756274A (en) * | 2014-09-22 | 2016-07-13 | 科思创聚合物（中国）有限公司 | Polyurethane based prefabricated concrete thermal insulation element and preparation method thereof |
| CN106832248A (en) * | 2017-01-23 | 2017-06-13 | 山东诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
| CN112175168A (en) * | 2020-10-14 | 2021-01-05 | 上海交通大学 | Terpolymer, block polymer and synthetic method of terpolymer |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2432815B1 (en) | 2009-05-19 | 2013-10-23 | Basf Se | Polyurea which can be produced from two polyetheramines and a prepolymer |
| US9126386B2 (en) | 2011-03-04 | 2015-09-08 | Basf Se | Composite elements |
| US9188384B2 (en) | 2011-03-31 | 2015-11-17 | Basf Se | Dynamically evacuable devices comprising organic aerogels or xerogels |
| CN102516523B (en) * | 2011-12-19 | 2014-05-14 | 山东海冠化工科技有限公司 | Phenolic polyol resin for producing flame-retardant polyurethane foam and preparation method for phenolic polyol resin |
| CN105308088B (en) * | 2013-06-18 | 2018-03-27 | 巴斯夫欧洲公司 | Polyalcohol, preparation method and use containing tannin |
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- 2011-02-22 SG SG2012063756A patent/SG183523A1/en unknown
- 2011-02-22 KR KR1020127025874A patent/KR20130004587A/en not_active Application Discontinuation
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- 2011-02-22 WO PCT/EP2011/052555 patent/WO2011107366A1/en active Application Filing
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| CN105756274A (en) * | 2014-09-22 | 2016-07-13 | 科思创聚合物（中国）有限公司 | Polyurethane based prefabricated concrete thermal insulation element and preparation method thereof |
| CN105756274B (en) * | 2014-09-22 | 2019-11-26 | 科思创德国股份有限公司 | Precast concrete warm keeping element based on polyurethane and preparation method thereof |
| CN106832248A (en) * | 2017-01-23 | 2017-06-13 | 山东诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
| CN106832248B (en) * | 2017-01-23 | 2019-01-29 | 山东一诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
| CN112175168A (en) * | 2020-10-14 | 2021-01-05 | 上海交通大学 | Terpolymer, block polymer and synthetic method of terpolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011107366A1 (en) | 2011-09-09 |
| JP2013521354A (en) | 2013-06-10 |
| SG183523A1 (en) | 2012-10-30 |
| KR20130004587A (en) | 2013-01-11 |
| EP2542608A1 (en) | 2013-01-09 |
| MX2012009742A (en) | 2012-09-12 |
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