CN100349844C - Initial compounds for producing polyurethanes - Google Patents

Initial compounds for producing polyurethanes Download PDF

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CN100349844C
CN100349844C CNB2004800111013A CN200480011101A CN100349844C CN 100349844 C CN100349844 C CN 100349844C CN B2004800111013 A CNB2004800111013 A CN B2004800111013A CN 200480011101 A CN200480011101 A CN 200480011101A CN 100349844 C CN100349844 C CN 100349844C
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reaction
compound
formaldehyde
oligopolymer
oxyalkylene
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CN1780805A (en
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P·格勒尔
R·亨德赖希
P·C·凯尔库斯
T·奥斯特洛夫斯基
E·施特勒费尔
K·蒂勒
C·施诺普法伊尔
E·M·德克斯哈姆尔
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
    • C07C47/263—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups acyclic
    • 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
    • C08G65/2603—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 the other compounds containing oxygen
    • C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms
    • 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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • 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
    • C08G18/56—Polyacetals
    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment
    • C08G2/34—Chemical modification by after-treatment by etherification
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/34—Oligomeric, e.g. cyclic oligomeric

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to initial compounds for producing polyurethanes and is characterised in that said polyurethanes can be produced by reaction of hydroxyl group containing formaldehyde oligomers.

Description

Produce the initial compounds of urethane
The present invention relates to novel initial compounds for preparing urethane and preparation method thereof.
Urethane and preparation thereof are known for a long time and have described many times in the literature.They are usually by making polyisocyanates and having at least two compound reactions that isocyanate groups is reactive hydrogen atom and prepare.
As having at least two isocyanate groups is the compound of reactive hydrogen atom, uses polyvalent alcohol usually.Wherein Aethoxy Sklerol and polyesterols have maximum industrial significance.
Polyesterols is usually by preparing dual functional at least alcohol and dual functional at least carboxylic acid reaction.
Aethoxy Sklerol obtains by oxyalkylene is added on OH-or the functional initiator compound of NH-usually.
The price of Chang Yong polyvalent alcohol is by used initiator compound and used oxyalkylene, especially propylene oxide and ethylene oxide decision up to now.
The obvious more cheap initial compounds that is used to prepare polyvalent alcohol is a formaldehyde.Known formaldehyde and himself reaction form the oligopolymer with terminal hydroxy group.Yet this reaction causes oligopolymer and mixture of polymers and formaldehyde with variable chain length to be balance usually.Compound with wide molecular weight distribution like this can not be used to prepare urethane.Another shortcoming of these compounds is its stability and unsatisfactory.Even after the short period of time, oligopolymer and polymkeric substance take place to dissociate again.
DD 247 223 has described a kind of method for preparing Aethoxy Sklerol, wherein makes formaldehyde condensation products (being known as formose) and other have the mixture and the reactions of alkylene oxide of the compound of active hydrogen atom.In the method, formose also has wide molecular weight distribution.
EP 1 063 221 has described a kind of method of formaldehyde oligomer of the formula (I) that is had narrow molecular weight distributions by prepared formaldehyde.This reaction according under establish an equation and carry out:
Here, n=2-19 wherein, the formaldehyde oligomer of the formula (I) of preferred 2-9 can obtain by the PARA FORMALDEHYDE PRILLS(91,95) solution dehydrates.These solution can contain at the most 80% paraformaldehyde and not have free-water.Can especially separate single fraction, the oligopolymer that promptly has certain chain lengths by separate procedure by distillation.Make oligopolymer and other substance reactions, wherein dissociating again of qualification taken place and formed formaldehyde in oligopolymer.
The oligomer mixture that gained comprises 2-9 formaldehyde unit (comprising polyoxymethylene) usually is unsettled.In 2 hours, form more high-molecular weight compound (paraformaldehyde), water and unit molecule hydration formaldehyde.
The objective of the invention is to reduce the cost of cost, the especially polyvalent alcohol of the raw material that is used to prepare urethane.
We find that this purpose is by realizing formaldehyde and oligopolymer thereof with plain mode as the initial substance of preparation urethane raw.
Therefore, the invention provides the initial compounds that is used to prepare urethane, hereinafter be also referred to as urethane raw, the reaction of the hydroxyl oligopolymer that they can be by formaldehyde prepares.
The present invention further provides a kind of method of prepared in reaction urethane raw of the hydroxyl by formaldehyde oligomer.
As formaldehyde oligomer, the mixture of the compound of use formula (I):
Figure C20048001110100041
Wherein n is the integer of 2-19, especially 2-9.
Formula (I) compound can prepare by currently known methods.Therefore, oligopolymer can be produced by the known polymerization of three  alkane (the ring reaction product of formaldehyde).This method is known by document.It is preferred for preparing polyoxymethylene (POM) and for example is described among the R  mpp Chemie Lexikon.Yet this method is not preferred to preparing urethane raw of the present invention, because preferentially form the high molecular reaction product.
In a preferred embodiment of the invention, oligopolymer is by the preparation of the method described in the EP 1 063 221, omitted this oligopolymer described in the document subsequently with the reaction of aniline.
The preparation of formaldehyde oligomer separates specific fraction the equilibrated solution and carries out by being from formaldehyde wherein and its oligopolymer.This separation is preferably undertaken by distillation, and this distills usually by film evaporator, especially by thin-film evaporator.The proper operation condition of this film evaporator normally temperature is 10-230 ℃, preferred 10-150 ℃, and absolute pressure is 0.5 millibar-2 crust.The preferred 20-100 of the fractionation of the PARA FORMALDEHYDE PRILLS(91,95) aqueous solution ℃ temperature and barometric point.
Isolating in this way formaldehyde oligomer fraction has very narrow molecular weight distribution usually.They have stability in storage as mentioned above and should further process to avoid its composition to change during this period in specified time.
In principle, specific oligopolymer can omit with separating of reaction mixture and this mixture can be directly used in preparation and is used to prepare the initial compounds of urethane.Yet shortcoming is that this mixture contains a large amount of free formaldehydes and water, causes side reaction degree height.
The oligopolymer of above-mentioned formula (I) in principle can also be as the initial compounds for preparing urethane under further not handling.If reaction is right after at its after separating, then avoided the DeR that causes formaldehyde to be eliminated.Yet, preferably carry out the reaction of the terminal hydroxy group of oligopolymer.
Be formed for preparing in the reaction of initial compounds of urethane at oligopolymer, its terminal hydroxy group reacts.
In one embodiment of the invention, make terminal hydroxy group and reactions of alkylene oxide form Aethoxy Sklerol.This reaction is usually as carrying out the known preparation of the Aethoxy Sklerol that uses conventional alcohols starter substance.
The hydroxyl value of oligopolymer depends on the formaldehyde unit number, in the 389mg KOH/g scope for the 1436mg KOH/g when the n=2 during to n=9.Because oligopolymer is not moisture at after separating, oligopolymer separate and itself and reactions of alkylene oxide between no longer need drying step.
As industrial common, the catalyzer that is reflected at of formaldehyde oligomer and oxyalkylene carries out under existing.Operable catalyzer is generally basic cpd such as amine, alkaline metal oxide and metal hydroxides, especially potassium hydroxide.
Preferred catalyzer is a multi-metal cyanide, is also referred to as dmc catalyst.This compounds is for a long time known and for example be described among EP 654 302 or the EP 862 947.Use the advantage of dmc catalyst to be that at first they can remain in the product after reaction, next is opposite with basic catalyst, and they can not promote dissociating again of oligopolymer.
As oxyalkylene, can use known and be usually used in the compound of this purpose.Can use separately or have maximum industrial significance with ethylene oxide and propylene oxide that each other any mixture uses.When using ethylene oxide and propylene oxide, these two kinds of oxyalkylenes can be introduced together to produce the atactic polyether chain or to introduce successively to form the oxyalkylene block.
The type of the oxyalkylene of introducing and amount especially depend on the practical use of Aethoxy Sklerol.In order to be used for rigid foam, Aethoxy Sklerol has short chain.The hydroxyl value of this Aethoxy Sklerol is generally 300-600mg KOH/g, especially 400-500mg KOH/g.As oxyalkylene, preferably use propylene oxide.
In order to be used for flexible foam, use long-chain polyether alcohol usually.The hydroxyl value of these Aethoxy Sklerols is generally 30-120mg KOH/g, preferred 30-60mg KOH/g.As oxyalkylene, use the mixture of ethylene oxide and propylene oxide usually.Under the situation of application-specific, for example, add the pure zirconia ethylene block at the polyethers end of the chain in order to produce the cold curing foam.
When dmc catalyst was used to prepare Aethoxy Sklerol, preferably the random mixture with propylene oxide or propylene oxide and ethylene oxide was used as oxyalkylene.In the preferred embodiment of this method, be metered into the random mixture of ethylene oxide and propylene oxide and in the metered charge process, change the ratio of two kinds of oxyalkylenes in this mixture, as described in WO 01/44347.
This process program makes and can prepare the glycol that have narrow molar mass distribution in wide molar mass scope with plain mode by the oligopolymer that uses different molecular weight.
Formaldehyde oligomer can be separately or with other H-officials can starter substance mixture and reactions of alkylene oxide.As extra starter substance, preferred dual functional at least alcohol such as glycerine, TriMethylolPropane(TMP), ethylene glycol, propylene glycol or its higher homologue of using.
The reaction of starter substance and oxyalkylene is carried out under the temperature commonly used of the pressure of the 0.1-1.0Mpa that is usually used in this purpose and 80-140 ℃ usually.Post-reaction period normally after the introducing of oxyalkylene is to finish the reaction of oxyalkylene.In the favourable embodiment of the inventive method, when post-reaction period begins, preferably after the introducing of oxyalkylene is finished immediately with another catalyzer, especially amine catalyst adds in the reaction mixture.
After the addition reaction of oxyalkylene, by distillation Aethoxy Sklerol is carried out simple process usually, with separating volatile impurity.If need, can the subsequent filtration Aethoxy Sklerol to remove any solid impurity that exists.If basic cpd as catalyzer, is then removed this catalyzer after the addition reaction of oxyalkylene.This can be by carrying out with acid neutralization or use sorbent material.Then by removing by filter salt or sorbent material.
In the particular embodiment of the inventive method, the reaction of formaldehyde oligomer and oxyalkylene especially also can be carried out when using dmc catalyst continuously.At this moment, with isolating oligomer mixture and oxyalkylene and catalyzer are introduced in the reactor continuously and take out the Aethoxy Sklerol that forms continuously from this reactor.Such continuation method for example is described among DD 203 235 and the WO 98/03571.This successive reaction for example can be carried out in tubular reactor, stirred vessel or loop reactor.In this scheme of the inventive method, Aethoxy Sklerol can be immediately following the same after separating continuously at oligopolymer by the continuous preparation that makes oligopolymer and reactions of alkylene oxide.
The Aethoxy Sklerol that obtains in this way can obtain urethane by ordinary method and the reaction of isocyanic ester no problem ground.Here, Aethoxy Sklerol of the present invention can use separately or preferred and other compounds such as extra alcohol, especially short chain polyfunctional alcohol, Aethoxy Sklerol and/or polyesterols, and preferred, polyethers alcohol mixes use.As short chain alcohol, use difunctionality or the polyfunctional alcohol of molecular weight usually, for example ethylene glycol, propylene glycol and higher homologue thereof or glycerine as 62-400g/mol.
As Aethoxy Sklerol and polyesterols, can use known and be usually used in the compound of this application.The molecular weight Mn that they have usually is higher than 400g/mol, is preferably 400-15000g/mol.These polyvalent alcohols are by conventional and known method preparation, undertaken by the reaction of polyfunctional alcohol and polyfunctional carboxylic acids under the situation of polyesterols and situation at Aethoxy Sklerol under undertaken by the addition of oxyalkylene and H-official's energy starter substance.This reaction depends on that the type of required urethane can carry out in the presence of catalyzer, whipping agent and conventional auxiliary agent and/or additive.
In another embodiment of the present invention, make itself and isocyanate reaction form prepolymer with the reaction mixture after separating at formaldehyde oligomer.
For this reason, make the terminal hydroxy group and the isocyanate reaction of isolating as mentioned above formula (I) oligopolymer.Because oligopolymer only can the stable storing finite time, if the product that will obtain having narrow molar mass distribution, this reaction also must be carried out immediately at the after separating of oligopolymer in this case.
If oligopolymer is stored the long time, then not only molar mass distribution becomes wideer, and also forms formaldehyde and water in this oligomer mixture.Although the formaldehyde that forms can be removed by stripping in principle, it forms for further processing oligopolymer is disadvantageous to form prepolymer, because it causes undesirable side reaction.
Because all hydroxyl reactions of oligopolymer, dissociating again of this oligopolymer suppressed fully.Prepolymer be stable storing and can as the prepolymer that is derived from other polyvalent alcohols that are usually used in polyurethane chemistry, process.
The reaction of hydroxyl oligopolymer and isocyanic ester is carried out in the mode that is usually used in preparing the prepolymer that contains isocyanate groups.For this reason, make the isocyanate reaction of this oligopolymer and the amount of the hydroxyl complete reaction that is enough to make oligopolymer at least.This reaction can form in the presence of the catalyzer at conventional urethane and carry out.In order to carry out this reaction, usually,,, preferably isocyanate compound is placed reaction vessel under 50-80 ℃ at 40-100 ℃ if the words that need are in the presence of catalyzer.Under agitation be metered into oligomer mixture, make reaction mixture subsequently at 60-140 ℃, preferred 80-100 ℃ of further reaction down, reaction is 2 hours at the most usually, if the reaction of suitable words is to transforming fully.
The NCO content of prepolymer depends on excessive, reaction times, the residence time, temperature of reaction and the catalyst system therefor of the molar mass of oligopolymer, used isocyanic ester.
The NCO content of prepolymer is generally 10-30 weight %, preferred 15-25 weight %.
Formaldehyde oligomer separately or with have at least two mixture and isocyanate reactions that isocyanate groups are other compounds of reactive hydrogen atom.Can be especially pure with the component that forms prepolymer with formaldehyde oligomer and isocyanate reaction.The practical use that depends on prepolymer can 0-90 weight %, and the amount of preferred 0-60 weight % is used various alcohol, in each case based on formaldehyde oligomer with have at least two summations that isocyanate groups are other compounds of reactive hydrogen atom.
Use for great majority, used extra alcohol is short chain polyfunctional alcohol, Aethoxy Sklerol and/or polyesterols, preferred, polyethers alcohol.As short chain alcohol, use difunctionality or the polyfunctional alcohol of molecular weight usually, for example ethylene glycol, propylene glycol and higher homologue thereof or glycerine as 62-400g/mol.
As Aethoxy Sklerol and polyesterols, can use to be usually used in this application and the top alcohol of having described in detail.Can also be with formaldehyde oligomer and isocyanate reaction by the Aethoxy Sklerol that oxyalkylene is added prepare on the oligopolymer of the formula of being formed in (I).
The isocyanic ester that can be used for the inventive method is all isocyanic ester that have two or more isocyanate groups in molecule.Can use the mixture of aliphatic isocyanate such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) or preferred aromatic isocyanate such as tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) or diphenylmethanediisocyanate and polymethylene polyphenylene(poly)isocyanate (P-MDI), preferred TDI and MDI.Can also use the isocyanic ester of modification by mixing urea diketone (uretdione), isocyanuric acid ester, allophanate, uretonimine (uretonimine) and other groups.These compounds are also referred to as modified isocyanate usually.
The prepolymer for preparing in this mode can with in molecule, have at least one, preferred at least two are the compound reaction of reactive hydrogen atom to obtain urethane to isocyanate groups.The type that depends on used polyvalent alcohol and isocyanic ester can be processed prepolymer to produce rigid foam, flexible foam, tackiness agent, coating or elastomerics.
The present invention illustrates by the following example.
Embodiment 1
By thin-film evaporator under 80 ℃ wall temperature and 120 millibars is that to be evaporated to theoretical formaldehyde content be 73 weight % for the formalin solution of 37 weight % with formaldehyde content.This solution is stored down and further processing in 1 hour at 80 ℃.Mixed being incorporated in the pilot scale autoclave is metered into the 1010g propylene oxide under 100 ℃ in 6 hours with this solution of 961g and 38.4g dimethylcyclohexylamine.Reaction mixture was further reacted 2 hours under uniform temp.Under reduced pressure remove volatile component then.The hydroxyl value that residual liquid reacting product has is that 685mg KOH/g and water-content are 0.011 weight %.Gpc analysis shows that the molar mass that oligomerization product has is 100-500g/mol.Show the adducts that forms two molecular oxidation propylene and two molecule formaldehyde by vapor-phase chromatography with the detection of the mass spectroscopy (GC-MS) of its coupling.
Embodiment 2
By thin-film evaporator under 80 ℃ wall temperature and 120 millibars is that to be evaporated to theoretical formaldehyde content be 73 weight % for the formalin solution of 37 weight % with formaldehyde content.This solution is stored down and further processing in 1 hour at 80 ℃.Mixed being incorporated in the pilot scale autoclave is metered into the 1600g propylene oxide in 9 hours with this solution of 1110g and 70g potassium hydroxide.The hydroxyl value that this liquid reacting product has is that 868mg KOH/g and water-content are 0.014 weight %.Show that by gel permeation chromatography the molar mass that oligomerization product has is 100-500g/mol.GC-MS shows the adducts that forms two molecular oxidation propylene and two molecule formaldehyde.

Claims (13)

1. initial compounds that is used to prepare urethane, the prepared in reaction of the formaldehyde oligomer that it can be by hydroxyl, used formaldehyde oligomer has wherein n to be the formula (I) of the integer of 2-19 and to separate with formalin by distillation:
Figure C2004800111010002C1
2. according to the compound of claim 1, it can be by the hydroxyl of formaldehyde oligomer and the prepared in reaction of oxyalkylene.
3. according to the compound of claim 2, wherein the mixture with ethylene oxide, propylene oxide or ethylene oxide and propylene oxide is used as oxyalkylene.
4. according to the compound of claim 1, it prepares by the hydroxyl of formaldehyde oligomer and the reaction of isocyanic ester.
5. according to the compound of claim 4, wherein NCO content is 10-30 weight %.
6. according to the compound of claim 4, wherein NCO content is 15-25 weight %.
7. a method for preparing according to the compound of claim 1 comprises the steps:
A) formaldehyde oligomer of preparation formula (I), it separates with formalin by distillation,
B) make the hydroxyl reaction of formaldehyde oligomer.
8. according to the method for claim 7, this distillation is thin film distillation.
9. according to the method for claim 7, wherein carry out with being reflected in the step b) of oxyalkylene.
10. according to the method for claim 7, wherein carry out with being reflected in the step b) of isocyanic ester.
11. according to the method for claim 7, wherein step a) and b) carry out continuously.
12. method for producing polyurethanes comprises the compound and the isocyanate reaction that make according to claim 2.
13. method for producing polyurethanes, comprise make according to the compound of claim 4 with have at least two compound reactions that isocyanic ester are reactive group.
CNB2004800111013A 2003-04-28 2004-04-16 Initial compounds for producing polyurethanes Expired - Fee Related CN100349844C (en)

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SU767122A1 (en) * 1978-04-10 1980-09-30 Предприятие П/Я А-3957 Method of preparing formose polyglycolic ethers
DD247223A1 (en) * 1986-03-06 1987-07-01 Schwarzheide Synthesewerk Veb PROCESS FOR THE PREPARATION OF POLYETHERAL COCOOLS
CN1276263A (en) * 1999-06-07 2000-12-13 Basf公司 Reaction of mixture solution

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EP1620383A1 (en) 2006-02-01
WO2004096746A1 (en) 2004-11-11

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