CN101437864A - Enhanced oligomeric polyols and polymers made therefrom - Google Patents
Enhanced oligomeric polyols and polymers made therefrom Download PDFInfo
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- CN101437864A CN101437864A CNA2007800151599A CN200780015159A CN101437864A CN 101437864 A CN101437864 A CN 101437864A CN A2007800151599 A CNA2007800151599 A CN A2007800151599A CN 200780015159 A CN200780015159 A CN 200780015159A CN 101437864 A CN101437864 A CN 101437864A
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Abstract
Enhanced oligomeric polyols are reported. The enhanced oligomeric polyols may be prepared by a method comprising the steps of: (a) providing an oligomeric polyol that comprises at least one glycerol fatty acid ester having at least one glycerol fatty acid ester bond; wherein at least 5% of the ethyldenyl groups (*C=C*) in the glycerol fatty acid ester are substituted with a bonding structure selected from the group consisting of: C-*C-C*-C; O-*C-C*-O; C=*C-C*-C, and mixtures thereof, where * is used to denote the original carbon atoms in the ethylidenyl group; and (b) cleaving at least a portion of the glycerol fatty acid ester bonds to form the enhanced oligomeric polyol. The enhanced oligomeric polyols are useful in making polymers such as polyurethanes.
Description
The cross reference of related application
The exercise question that the application requires on April 27th, 2006 to submit to is the U.S. serial 60/795 of " enhancing oligomeric polyols ", the exercise question of submitting on November 16th, 327 and 2006 is the U.S. serial 60/859 of " viscoelastic polyurethane foam that comprises amidation or transesterify oligomeric natural oil polyols ", 337 right of priority, these are disclosed in this and are incorporated herein by reference.
Background technology
The polyvalent alcohol that is derived from oil has been widely used in the manufacturing of polyurethane foam.Yet, recently in the manufacturing of polymkeric substance such as urethane to using the increase that focuses on of renewable resources.This causes the research of exploitation based on the polyvalent alcohol of natural oil, and it is suitable for the polyvalent alcohol that in polymkeric substance such as urethane all or part of replacement is derived from oil.
A kind of method from unsaturated natural oil manufacturing polyvalent alcohol is to make the natural oil epoxidation, then makes the open loop of at least a portion epoxide group to form the secondary hydroxyl side group.Open loop can be for example by make epoxidation natural oil with alcohol (for example methyl alcohol) at catalyzer (as HBF
4) existence down reaction finish.This synthetic route mainly causes the formation of secondary hydroxyl, and it is the side group of natural oil.Although the secondary hydroxyl side group can be used for forming urethane, expectation provides owing to existing some primary hydroxyls to have reactive faster polyvalent alcohol based on natural oil in polyvalent alcohol at least.
Summary of the invention
The present invention relates to enhancing oligomeric polyols by the natural oil preparation.Natural oil polyols can be used for making polymkeric substance, as urethane, polyester, polycarbonate etc.In exemplary, described natural oil polyols can be used for polyether polyols with reduced unsaturation, as polyurethane foam.
In some embodiments of the present invention, described enhancing oligomeric polyols prepares by the method that comprises the steps:
(a) provide a kind of oligomeric polyols, it comprises at least a glycerin fatty acid ester with at least one fatty acid glycerine ester bond; Wherein in glycerin fatty acid ester, at least 5% ethylidene (
*C=C
*) be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and its mixture replaces, wherein
*Be used for representing the former carbon atom of ethylidene; With
(b) disconnect at least a portion fatty acid glycerine ester bond to form described enhanced oligomeric polyols.
The example that can be used as the natural oil of starting raw material comprises plant based oil (as vegetables oil) and animal tallow.The example of plant based oil comprises soybean oil, Thistle oil, oleum lini, Semen Maydis oil, Trisun Oil R 80, sweet oil, Canola oil (canola oil), sesame oil, cottonseed oil, plam oil, rapeseed oil, tung oil, peanut oil, Viscotrol C, leprosy seed oil (jatropha oil) and their mixture.The example of animal tallow comprises fish oil, lard and tallow.
In exemplary, the low dimerization of natural oil can be finished by chemical low dimerization (as epoxidation and the low dimerization of open loop) or by the low dimerization of anaerobic heat (heating to form siccative oil as anaerobic).After the low dimerization, disconnect in the oligomeric natural oil at least a portion fatty acid glycerine ester bond to form enhanced polyvalent alcohol of the present invention.Disconnecting at least a portion fatty acid glycerine ester bond is in order to extra functionality (i.e. the functionality of " enhancing " oligomeric fatty acids ester) is incorporated in the oligomeric fatty acids ester.For example, in many embodiments, cleavage reaction is introduced the primary hydroxyl functionality to the enhanced oligomeric polyols.
The representative example of cleavage reaction comprises the reaction of oligomeric natural oil and nucleophilic reagent.Common nucleophilic cleavage reaction comprises amidation and transesterify.
Amidation relates to oligomeric natural oil and amine (for example polyamine, as diamines) or alkanolamine (as thanomin) reaction.During the amidation, at least a portion is present in amido in the polyamine and at least a portion and is present in ester group reaction in the oligomeric natural oil, and the result forms amide group and hydroxyl.
Transesterify relates to the reaction of oligomeric natural oil and polyvalent alcohol (as glycol) compound.During transesterify, at least a portion is present in ester group in the polyol compound and at least a portion and is present in ester group reaction in the oligomeric natural oil, and the result forms ester group and hydroxyl.
Run through the application, following term has following implication.
" polyvalent alcohol " in this application refers to a kind of molecule, and its per molecule on average has the hydroxyl above 1.0.It can be chosen wantonly and comprise other functionality.
" the low dimerization of anaerobic heat " in this application refers to by heat the process of hanging down dimerization fatty acid ester (as natural oil) under essentially no oxygen condition.
" chemistry low dimerization " of this application refer to process by the low dimerization fatty acid ester (as natural oil) of chemical process, described chemical process comprise by two keys of at least a portion in functionalized (as epoxidation) fatty acid ester and make at least a portion functional group reactions (as open loop) and between fatty acid chain generation crosslinked.
" natural oil " in this application refers to plant based oil (as vegetables oil) or animal tallow.
" oligopolymer " in this application refers to by low dimerization reaction two or more fatty acid ester monomeric units based on glyceryl ester of covalent bonding each other.Oligopolymer comprises the oligopolymer of dimer, tripolymer, the tetramer and the higher order of magnitude.Term " low dimerization " refers to comprise the raw material of oligopolymer.
Embodiment
The present invention relates to be derived from the polyvalent alcohol of natural oil such as vegetables oil or animal tallow.
In order to make the enhanced oligomeric polyols, the starting composition that comprises natural oil is hanged down dimerization by hanging down low dimerization of dimerization method such as chemistry or the low dimerization of anaerobic heat.After the low dimerization, at least a portion fatty acid glycerine ester bond in the low dimerization fatty acid ester is disconnected to introduce extra functionality in polyvalent alcohol.Disconnecting the lipid acid ester bond can be for example by finishing with the reaction of nucleophilic reagent.Common nucleophilic reaction comprises amidation and transesterify.The representative example of enhanced oligomeric polyols comprises: (a) the low dimerization polyvalent alcohol of anaerobic heat of the low dimerization polyvalent alcohol of amidated anaerobic heat, the low dimerization polyvalent alcohol of (b) amidated chemistry, (c) transesterify and (d) the low dimerization polyvalent alcohol of chemistry of transesterify.
In some embodiments, described enhanced oligomeric polyols prepares by the amidation of the low dimerization natural oil of anaerobic heat.Such polyvalent alcohol can make by the method that comprises the following steps: (a) provide natural oil; (b) anaerobic heats described natural oil so that its low dimerization forms the low dimerization natural oil of anaerobic heat; (c) the low dimerization natural oil of the described anaerobic heat of amidation is to form the enhanced oligomeric polyols.
In other embodiments, the enhanced oligomeric polyols prepares by the amidation of the low dimerization natural oil of chemistry.Such polyvalent alcohol can make by the method that comprises the following steps: (a) provide natural oil; (b) the low described natural oil of dimerization of chemistry is so that its low dimerization forms the low dimerization natural oil of chemistry; (c) the low dimerization natural oil of the described chemistry of amidation is to form the enhanced oligomeric polyols.
Also in other embodiments, the enhanced oligomeric polyols prepares by the transesterify of the low dimerization natural oil of anaerobic heat.Such polyvalent alcohol can make by the method that comprises the following steps: (a) provide natural oil; (b) anaerobic heats described natural oil so that its low dimerization forms the low dimerization natural oil of anaerobic heat; (c) the low dimerization natural oil of the described anaerobic heat of transesterify is to form the enhanced oligomeric polyols.
Also in other embodiments, the enhanced oligomeric polyols prepares by the transesterify of the low dimerization natural oil of chemistry.Such polyvalent alcohol can make by the method that comprises the following steps: (a) provide natural oil; (b) the low described natural oil of dimerization of chemistry is so that its low dimerization forms the low dimerization natural oil of chemistry; (c) the low dimerization natural oil of the described chemistry of transesterify is to form the enhanced oligomeric polyols.
To describe in detail now and make other details that strengthens oligomeric polyols.
Starting raw material (natural oil)
The natural oil starting raw material that can be used for polyvalent alcohol of the present invention comprises plant based oil (as vegetables oil) and animal tallow.The example of plant based oil comprises soybean oil, Thistle oil, oleum lini, Semen Maydis oil, Trisun Oil R 80, sweet oil, Canola oil, sesame oil, cottonseed oil, plam oil, rapeseed oil, tung oil, peanut oil, Viscotrol C, leprosy seed oil and their mixture.The example of animal tallow comprises fish oil, lard and tallow.Also available partially hydrogenated vegetables oil and transgenic plant oil comprise high oleic safflower oil, high oleic acid soybean oil, high oleic acid peanut oil, high oleic sunflower oil and high erucic acid rape seed oil (Crambe oil).These oil can be crude oil or treated oil.
The number of the two keys of per molecule can be determined by the iodine value (IV) of oil in natural oil.For example, the vegetables oil of per molecule with two keys is corresponding to about 28 iodine value.Soybean oil has about 4.6 two key/molecules usually and has the iodine value of about 120-about 140.Canola oil has about 4.1 two key/molecules usually and has about 115 iodine value.Usually, the iodine value of vegetables oil is about 40-about 240.In some embodiments, the iodine value that has of employed vegetables oil be higher than about 80, be higher than about 100 or be higher than about 110.In some embodiments, the iodine value that has of employed vegetables oil be lower than about 240, be lower than about 200 or be lower than about 180.
Available natural oil generally include lipid acid glyceryl ester (as list, two and Witepsol W-S 55), it contains the fatty acid glycerine ester bond, this key is connected to lipid acid on the glycerol molecule of glyceryl ester.Described lipid acid can be saturated fatty acid or unsaturated fatty acids, and it can contain the fatty acid chain length that is generally about 12 carbon (C12 just)-Yue 24 carbon (C24 just).Unsaturated fatty acids comprises single unsaturated and polyunsaturated fatty acid.Common saturated fatty acid comprises lauric acid (laurostearic acid), tetradecanoic acid (TETRADECONIC ACID), palmitinic acid (palmitic acid), stearic acid (stearic acid), eicosanoic acid (20 acid) and lignoceric acid (tetracosanoic acid).Common monounsaturated fatty acids comprises Zoomeric acid (C16 unsaturated acid) and oleic acid (C18 unsaturated acid).Common polyunsaturated fatty acid comprises linolic acid (C18 two unsaturated acid), linolenic acid (C18 three unsaturated acid) and arachidonic acid (C20 four unsaturated acid).Triglycerin ester oil comprises the fatty acid ester of glycerine, and wherein lipid acid is randomly dispersed on three positions of trifunctional glycerol molecule.Different triglycerin ester oils will have different fatty acid ratios and distribution.Also depend on following factor and change for the fatty acid ratio of given triglycerin ester oil: the place of such as grain growth, the ripening degree of cereal, the weather of the season of growth etc.Because all be difficult to the composition that provides concrete or unique for any given Witepsol W-S 55, consist of statistical average value so report this usually.For example, soybean oil contains palmitinic acid, stearic acid, the oleic acid of the 4:11:24:53:8 ratio of having an appointment, the mixture of linoleic acid plus linolenic acid.This is converted into the molecular-weight average of about 800-880Da, the double key number of the on average about 4.4-about 4.7 of each Witepsol W-S 55 and the iodine value of about 120-about 140.
Also available functionalized fatty acid glyceryl ester.The one of ordinary skilled in the art will recognize that many methods that make the fatty acid glycerine ester functional are arranged.For example functionalized fatty acid glyceryl ester can be included in the hydroformylation oil that plays alcohol during the low dimerization of glycerin fatty acid ester (seeing people's such as Herrington WO2005033167A2), epoxidized oil (as originate from Union Carbide " FLEXOL ") and part epoxidized oil (comprising those that people such as Herrington for example describes in WO2005033167 A2), unsaturated oil, polyunsaturated oil, partly or entirely use the nucleophilic reagent open loop epoxidized oil (as, part or all of epoxidised vegetables oil and MeOH react in the presence of acid catalyst).
The method of low dimerization
Can use various known low dimerization methods and can be used for oligomeric fatty acids ester of the present invention with formation.Typically, the method by aliphatic ester compositions manufacturing oligomeric fatty acids ester comprises use compound, the energy or their combination.The representative example of low dimerization method comprises:
(a) under oxygen free condition, at high temperature the low dimerization fatty acid ester of heat is to generate siccative oil;
(b) hang down dimerization epoxidized fatty acid ester (seeing, for example U.S. Patent Publication 2006/0041157A) with alcohol as monohydroxy-alcohol or polyvalent alcohol open loop;
(c) the positively charged ion catalysis ring-opening polymerization of epoxidized fatty acid ester (seeing, for example U.S. Patent Publication 2006/0041157A)
(d) exist
Or the low dimerization (seeing United States Patent (USP) 2,160,572 and 2,365,919) of fatty acid ester under the existence of Lewis acid catalyst;
(e) crosslinked with sulphur compound; With
(f) fatty acid ester of the crosslinked hydroxyl-functional of usefulness hydroxyl activity linking agent, described hydroxyl activity linking agent such as vulcabond (as tolylene diisocyanate), diacid, diester, two-(2-chloroethene sulfone), two-(2-chloroethyl) sulfoxide, two-(2-chloroethyl) ether, 1,3-butadiene diepoxide, epoxidized vegetable oil and their mixture.
Typically, the low dimerization of fatty acid ester is the crosslinked result of position generation of ethylidene group in the fatty acid chain of fatty acid ester.Crosslinkedly be formed at least one usually and form the carbon of ethylidene group and (a) between the fatty acid ester on the identical glycerol backbone (intramolecular crosslinking); (b) between the fatty acid ester on the different fatty acid glycerine ester molecules (intermolecular cross-linking); (c) between the multifunctional linking agent (as petrochemical industry or biologically-derived polyvalent alcohol); (d) between (a) and (b) and the combination (c).After being cross-linked to form, in fatty acid ester, form the no longer shared carbon-to-carbon double bond of two carbon atoms of ethylidene group.Usually, these two carbon atoms or all with the oxygen bonding, perhaps form separately new C-C (as carbon-to-carbon singly-bound or carbon-to-carbon double bond).
In some embodiments of the present invention, the oligomeric fatty acids ester comprises at least a glycerin fatty acid ester with at least one fatty acid glycerine ester bond; And at least 5% ethylidene group in glycerin fatty acid ester (
*C=C
*) be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and its mixture replaces.In shown structure,
*Be used for representing the position of the former carbon atom of described bonding structure ethylidene group.In some embodiments, in glycerin fatty acid ester, at least about 10%, 12%, 14%, 16%, 20%, 25%, 30%, 35% 40% or more ethylidene group (
*C=C
*) be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and its mixture replaces.
The low dimerization of heat
In some embodiments, the natural oil that comprises fatty acid ester is hanged down dimerization to form the oligomeric fatty acids ester by heat under oxygen free condition.The natural oil of the low dimerization of heat is called as siccative oil under oxygen free condition.Oxygen free condition means that fatty acid ester is hanged down dimerization under molecular oxygen that does not have fundamental quantity or air.The anaerobic heating is carried out in vacuum or inert gas atmosphere usually.In some embodiments, nitrogen is used as rare gas element.Also can spray by applying steam.The application of oxygen free condition reduces basically or has prevented from low dimerization fatty acid ester to form hydroperoxide and/or aldehyde.
During the low dimerization of anaerobic heat, the carbon-to-carbon double bond that is present in the fatty acid part of natural oil reacts crosslinked to form each other.Described crosslinked can be intramolecular (between the lipid acid of esterification just to the identical glycerol molecule) or intermolecular (between the lipid acid of esterification just to the different glycerol molecules).Intermolecular cross-linking causes forming oligopolymer in the low dimerization natural oil of heat, for example the oligopolymer of dimer, tripolymer, the tetramer and the Geng Gao order of magnitude.Result as the Diels-Alder reaction also may form crosslinked and intramolecular crosslinking between ring molecule.
For low dimerization fatty acid ester, heating is up to the low dimerization degree that reaches expectation in oxygen-free atmosphere.For example, can be under about 100 ℃-Yue 400 ℃ temperature heating natural oil about 2 hours-Yue 24 hours.Used temperature and time depends on the type that is present in the lipid acid in the natural oil and the low dimerization degree of expectation.
Hot siccative oil synthesizes by making natural oil (as oleum lini or soybean oil) stand high temperature (as 200 ℃-400 ℃) some hrs under oxygen free condition.In some embodiments, catalyzer (as acid or metal catalyst) is used to quicken low dimerization reaction.Usually application is higher than about 300 ℃ temperature, but the low dimerization of natural oil also can begin to take place under lower temperature, especially under the situation of applications catalyst.In many embodiments, the volatile matter that forms between the reaction period to remove is under reduced pressure carried out in multiviscosisty reaction.During reaction, sometimes by removing volatile matter with nitrogen or vapo(u)r blasting oil.Prevent that importantly any air leaks from advancing in the system, this will cause the quick oxidation and the degraded of oil, thereby form the high-caliber flavor compound that has, as aldehyde.The degree of low dimerization can for example be determined by the increase of measuring natural oil viscosity.
In some embodiments, the low dimerization fatty acid ester of heat contains residual two keys.That is to say that in some embodiments, when fatty acid ester was hanged down the dimerization fatty acid ester by low dimerization to form heat, not every pair of key all reacted.The amount of two keys can be determined by the iodine value of measuring the low dimerization fatty acid ester of heat.The iodine value of compound (IV) is the amount with the iodine of material sample reaction, with every gram material centigram iodine (I
2) (cg I
2/ gram) expression.The IV of the low dimerization natural oil of heat depends on the IV of initial natural oil usually, also depends on the degree of the low dimerization of natural oil.For soybean oil, IV typically originates in about 125-130, after the low dimerization of heat, reaches about 90.
Other details about the low dimerization natural oil of heat can for example find in following publication:
(a)Shiina，Hisako.Yukagaku 1982，Volume 31(7)：421-425；
(b)Rhoades，W.F.；Da Valle，A.J.Journal of the American Oil Chemists′Society(1951)，28，466-468；
(c)Radlove，S.B.；Falkenburg，L.B.Journal of the American OilChemists′Society(1948)，25，1-3；
(d) Wang, Chaohua; Erhan, Sevim, Journal of the American Oil Chemists ' Society (1999), 76 (10), 1211-1216; With
(e)Erhan，S.Z.；Bagby，M.O.Journal of the American Oil Chemists′Society(1994)，71(11)，1223-6.
The low dimerization of chemistry
In some embodiments, natural oil is by the low dimerization of chemistry.Can use any known method and come the low dimerization natural oil of chemistry.In illustrative methods, the low dimerization of epoxidised natural oil realizes by the low dimerization of open loop wholly or in part, for example, is reported in U.S. Patent application 2006/0041157A1 and open WO2006/012344A1 of PCT and WO2006/116456.The low dimerization of open loop can be undertaken by epoxidation natural oil and ring opening agent are reacted in the presence of the open loop acid catalyst.Describe these components below in detail.
Epoxidation natural oil can be by part or all of epoxidation.Part epoxidation natural oil can comprise at least about 10%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40% or more original bulies be present in two keys in the oil.Part epoxidation natural oil can comprise that as many as is about 90%, as many as is about 80%, as many as is about 75%, as many as is about 70%, as many as is about 65%, as many as about 60% or still less original bulk be present in two keys in the oil.Fully epoxidation natural oil can comprise that as many as is about 10%, as many as is about 5%, as many as is about 2%, as many as about 1% or still less original bulk be present in two keys in the oil.
The part epoxidation or fully epoxidation natural oil can natural oil and peroxy acid be prepared will partly or entirely oily two keys changing into the method for reacting under the condition of epoxide group by comprising.
The example of peroxy acid comprises peroxyformic acid, Peracetic Acid, trifluoro Peracetic Acid, benzyloxy peroxyformic acid, 3,5-dinitrobenzene benzoyl hydroperoxide, metachloroperbenzoic acid and their mixture.In some embodiments, use peroxyformic acid or Peracetic Acid.Peroxy acid directly can be added in the reaction mixture, perhaps can form in position as formic acid, phenylformic acid, lipid acid (as oleic acid) or acetic acidreaction by hydroperoxide and corresponding acid.The example of spendable hydroperoxide comprises hydrogen peroxide, the tert-butylhydroperoxide, triphenylsilyl hydroperoxy-, cumene hydroperoxide and their mixture.In exemplary, use hydrogen peroxide.Usually, the amount that is used to form the acid of peroxy acid is every mole of two about 1.0 equimolar acids of the about 0.25-of key in the vegetables oil, is more typically every mole of two about 0.55 equimolar acid of the about 0.45-of key in the vegetables oil.Usually, the amount that is used to form the hydroperoxide of peroxy acid is every mole of two about 1.5 moles of hydrogen superoxide of the about 0.5-of key in the vegetables oil, is more typically every mole of two about 1.2 moles of hydrogen superoxide of the about 0.8-of key in the vegetables oil.
Usually, in reaction mixture, also there is other sour composition.This type of other sour example comprises sulfuric acid, toluenesulphonic acids, trifluoroacetic acid, fluoroboric acid, Lewis acid, acid clay or acidic ion exchange resin.
Optional, solvent can be added in the reaction.The available solvent comprises unreactiveness solvent, for example aprotic solvent.These solvents do not comprise nucleophilic reagent, and not with acid-respons.Hydrophobic solvent as aromatic series or aliphatic hydrocarbon, is special ideal.The representative example of the solvent that is fit to comprises benzene,toluene,xylene, hexane, isohexane, pentane, heptane and chlorinated solvent (as tetracol phenixin).In exemplary, use toluene as solvent.Solvent can be used for reducing speed of response, or reduces the quantity of side reaction.Usually, solvent also is used as the viscosity-depression agent of resulting composition.
After the epoxidation reaction, can neutralize to reaction product.Can add neutralization reagent with any acidic component residual in the neutralization reaction product.The neutralization reagent that is fit to comprises weak base, alkali metal bicarbonate salt or ion exchange resin.The example of available neutralization reagent comprises the aqueous solution of ammonia, lime carbonate, sodium bicarbonate, magnesiumcarbonate, amine and resin and neutralization reagent.Usually, neutralization reagent is an anionite-exchange resin.An example of the weak-base ion-exchange resin that is fit to is the commodity (originating from Bayer) of trade mark " LEWATITMP-64 " by name.If use solid neutralization reagent (as ion exchange resin), the solid neutralization reagent can be removed from epoxidized vegetable oil by filtering.Perhaps, reaction mixture can neutralize by mixture being passed the neutralization bed that contains resin or other material.Perhaps, can the repetitive scrubbing reaction product from product, to separate and to remove acidic component.In addition, in neutralization reaction product, can be in conjunction with one or more described processes.For example, product can be washed, neutralize and after-filtration with resin material.
After the epoxidation reaction, can from reaction product (just complete epoxidized vegetable oil), remove excessive solvent.Described excessive solvent comprises the product that reaction produces or is added into those of reaction.Excessive solvent can be removed by separation, vacuum or other method.Preferably get off to finish the removal of excessive solvent by being in vacuum.
The complete epoxidised soybean oil of available comprises that commercially available trade mark is called those of EPOXOL 7-4 (originating from American Chemical Systems) and FLEXOL ESO (originating from Dow Chemical Co.).
In many embodiments, use ring opening catalyst.In some embodiments, acid catalyst is fluoroboric acid (HBF
4).Based on the gross weight of reaction mixture, the amount of acid catalyst is generally the about 0.3 weight % of about 0.01 weight %-, is more typically the about 0.15 weight % of about 0.05 weight %-.
Also be included in the reaction mixture is ring opening agent.Can use various ring opening agents, comprise that alcohol, water (water that comprises residual quantity) and other have the compound of one or more nucleophilic groups.Can use the mixture of ring opening agent.In some embodiments, ring opening agent is a monohydroxy-alcohol.Representational example comprises the monoalky lether (as methyl glycol, ethylene glycol monobutyl ether etc.) of methyl alcohol, ethanol, propyl alcohol (comprising n-propyl alcohol and Virahol) and butanols (comprising propyl carbinol and isopropylcarbinol) and ethylene glycol.In exemplary, alcohol is methyl alcohol.In some embodiments, ring opening agent is a polyvalent alcohol.When the polyvalent alcohol that obtains will be used to polyurethane foams, the usually preferred per molecule that uses had about 2 or the polyvalent alcohol of hydroxyl still less.The example of polyvalent alcohol ring opening agent comprises ethylene glycol, propylene glycol, 1, ammediol, butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, polyoxyethylene glycol and polypropylene glycol.Also available polyvalent alcohol based on vegetables oil.
Ring-opening reaction is carried out the ratio of epoxide with substoichiometric ring opening agent, to promote the low dimerization of epoxidation natural oil.In exemplary, epoxidised soybean oil (ESBO) is reacted in the presence of ring opening catalyst such as fluoroboric acid with methyl alcohol.Usually, methyl alcohol is about 3.0 for about 0.5-to the mol ratio of complete epoxidised soybean oil, is more typically about 1.0-about 2.0.In exemplary, methyl alcohol is about 1.3-about 1.5 to the mol ratio of epoxidised soybean oil.
Usually, when the reaction beginning, epoxidised soybean oil has the epoxide oxygen level (EOC) of about 6.8%-about 7.4% fully.Ring-opening reaction preferably stopped before whole epoxide rings are by open loop.For some ring opening catalysts, activity of such catalysts reduces during ring-opening reaction in time.Therefore, speed that can be controlled is added into ring opening catalyst in the reaction mixture, stops when making the terminal point EOC that is reflected at (or approaching) expectation.Can with known technology for example fixed (ASTM E1899-02) or EOC titration (AOCS Cd9-57 method) of hydroxyl value minim monitor ring-opening reaction.
Usually, when using loopful oxidation soybean oil, ring-opening reaction is about 6.0% for about 0.01%-at residual epoxide oxygen content (EOC), and for example about 0.5%-is about 5.5%, about 1%-is about 5.0%, about 2%-is about 4.8%, about 3%-about 4.6% or about 4.0%-were stopped in about 4.5% o'clock.When using other epoxidation natural oil, the residual epoxide oxygen content (EOC) of polyvalent alcohol can be different.For example, for plam oil, residual EOC can be about 3.5% for about 0.01%-, and for example about 0.2%-is about 3.0%, about 0.5%-about 2.0% or about 0.8%-about 1.5%.In " epoxide oxygen content " or the weight of " EOC " finger ring oxide compound oxygen in molecule of this application, represent with percentage ratio.
During ring-opening reaction, some hydroxyls of the polyvalent alcohol of open loop and the epoxide group reaction that is present on other molecule in the reaction mixture (as unreacted complete epoxidised soybean oil molecule or have the molecule of the polyvalent alcohol of unreacted epoxide group), cause low dimerization (just, forming the oligopolymer of dimer, tripolymer, the tetramer and the Geng Gao order of magnitude).The degree of low dimerization has been facilitated the expected performance of low dimerization natural oil.In some embodiments, low dimerization natural oil comprises about 40 weight % or higher oligopolymer (oligopolymer that comprises dimer, tripolymer and the Geng Gao order of magnitude).In some embodiments, oligomeric polyols comprises the monomer polyvalent alcohol of the about 45 weight % of about 35 weight %-and the oligopolymer (oligopolymer of dimer, tripolymer, the tetramer and the Geng Gao order of magnitude just) of the about 65 weight % of about 55 weight %-.For example, in some embodiments, low dimerization natural oil comprises three polyvalent alcohols of the monomer polyvalent alcohol of the about 45 weight % of about 35 weight %-, two polyvalent alcohols of the about 12 weight % of about 8 weight %-, the about 10 weight % of about 5 weight %-and the oligopolymer of the about 35 weight % or the more higher order of magnitude.
Can for example control low dimerization by the stoichiometry of catalyst concn, reactant and the stirring degree during the open loop.For example catalyst concn is high more or ring opening agent (as methyl alcohol) concentration is low more, and the degree that low dimerization often takes place is big more.In a single day ring-opening reaction finishes, and usually any unreacted methanol is removed by for example vacuum distilling.Unreacted methanol is not expected, because it is the simple function species, is forming between the reaction period of urethane blocked polyisocyanate.After removing excessive methanol, for example filter the polyvalent alcohol that obtains usually, to remove any solid impurity with 50 microns deep bed filter.
Except epoxidation and open loop, the low dimerization of chemistry also can realize by hang down dimerization natural oil in the presence of Bronsted or Lewis acid catalyst, and described catalyzer is as at United States Patent (USP) 2,160,572 and 2,365, and described in 919.Other technology that is used for the low dimerization of chemistry comprises the positively charged ion catalysis open loop of epoxidized fatty acid ester.Low dimerization by this method for example is described among the U.S. Patent Application Publication 2006/0041157A1.
The performance of oligomeric fatty acids ester
Usually, the oligomeric fatty acids ester comprises intermolecular cross-linking, and it may be directly crosslinked between two carbon atoms, or passes through linking agent.When two fatty acid glycerine ester molecules by the intermolecular cross-linking that between two fatty acid molecules, forms during bonding, it can be called as " dimer ".Similarly, when three different fatty acid glycerine ester molecules during by intermolecular cross-linking and bonding, it can be called as " tripolymer ".When four different fatty acid glycerine ester molecules during by intermolecular cross-linking and bonding, it can be called as " tetramer ".Higher oligopolymer also can form according to the quantity of the different fatty acid glycerine ester molecule of the bonding by intermolecular cross-linking.In some embodiments, the oligomeric fatty acids ester comprises dimer, tripolymer and higher oligopolymer.The oligomeric fatty acids ester can also be further processed to isolate the oligomeric species of expectation, for example isolates dimer by known fractionating process, makes to form the oligomeric fatty acids ester products of homogeneous basically.The example of fractionating process comprises solvent fractionation and chromatogram.
In some embodiments, the oligomeric fatty acids ester has about 50 or lower peroxide value (PV).Peroxide value can for example be measured with AOCS Cd 8b-90.In other embodiments, peroxide value is about 40 or lower, or about 30 or lower, or about 20 or lower, or about 10 or lower.
In some embodiments, the oligomeric fatty acids ester has residual epoxide group.In some embodiments, the oligomeric fatty acids ester has residual olefin group.In some embodiments, the oligomeric fatty acids ester not only has residual epoxide group but also have residual olefin group.The useful scope of residual epoxide group or olefin group is according to the epoxidation level of the type of used natural oil, natural oil and strengthen the end-use of oligomeric polyols and change.Usually, the residual pair of key (because vegetables oil only part epoxidation) can be about 75% for about 0-of initial pair of key in the vegetables oil, and residual epoxy content can be the about 6.0EOC% of about 0-.Degree of unsaturation can be passed through iodine value (IV) measurement, for example uses reported method in the AOCS Cd 1-25 method.EOC% can measure with reported method among the AOCS Cd 9-57.
The one of ordinary skilled in the art will recognize that the physicals of oligomeric fatty acids ester depends on makes its used technology.In some embodiments, the oligomeric fatty acids ester comprises at least about the oligopolymer of 40 weight % (referring to be higher than single glycerin fatty acid ester, for example dimer at this oligopolymer).In some embodiments, the oligomeric fatty acids ester comprise at least about the oligopolymer of 50 weight % (as, based on the integration at peak among the GPC).Usually, unsaturated or saturated oligomeric polyols can have a series of expected performance according to different parameters, and described parameter comprises the concentration of used composition, reaction times, temperature of reaction and ring opening agent.
In some embodiments, the oligomeric fatty acids ester have the number-average molecular weight (Mn) that surpasses about 1000Da (as, based on the integration at peak among the GPC).In other embodiments, the oligomeric fatty acids ester has the number-average molecular weight (Mn) of the about 6000Da of about 1500-.Usually, it is about 20 that the oligomeric fatty acids ester has about 2000Da-, the weight-average molecular weight of 000Da.
Usually, the polymolecularity of oligomeric fatty acids ester (Mw/Mn) is about 15 for about 1-, is more typically about 1-about 6.
In some embodiments, the oligomeric fatty acids ester has hydroxy functionality.In these embodiments, it is about 2000 that hydroxyl equivalent is generally about 500-, determined by number-average molecular weight and number-average.Usually, the oligomeric polyols that obtains has the hydroxyl value of the about 300mg KOH/g of about 10mg KOH/g-.Preferably, the hydroxyl value that oligomeric polyols has is at least about 20mg KOH/g or more, or at least about 30mgKOH/g or more, or at least about 40mg KOH/g or more, or at least about 50mg KOH/g or more.Preferably, the hydroxyl value that oligomeric polyols has is about 200mg KOH/g or lower, or about 180mgKOH/g or lower, or about 150mg KOH/g or lower, or about 100mg KOH/g or lower, or about 80mg KOH/g or lower, or about 60mg KOH/g or lower.The optimum range of hydroxyl value depends on the end-use of polyvalent alcohol.
Have in the embodiment of hydroxy functionality at the oligomeric fatty acids ester, the number average hydroxy functionality (Fn) that the oligomeric fatty acids ester has is about 10 or lower, for example about 9 or lower, about 8 or lower, about 7 or lower, about 6 or lower, about 5 or lower, about 4 or lower, about 3 or lower, about 2 or lower.Usually, number average hydroxy functionality (Fn) is about 0.9-about 3.0.In exemplary, number average hydroxy functionality (Fn) is about 1.0 or higher, or about 1.5 or higher.
When forming oligopolymer, low dimerization causes the viscosity of fatty acid ester to increase.Usually, when when measuring down for 25 ℃, the oligomeric fatty acids ester have about 20Pas (20,000cps) or lower viscosity, be more typically about 5Pas (5000cps)-15Pas (15,000cps).
Cleavage reaction strengthens oligomeric polyols to form
After the oligomeric fatty acids ester formed, the fatty acid glycerine ester bond that at least a portion is present in the oligomeric fatty acids ester was ruptured to form enhancing oligomeric polyols of the present invention.Cleavage reaction can be for example by finishing with nucleophilic reagent reaction (as transesterify and amidation), mercaptanization, hydrogenation or by the combination of these methods.These methods can be undertaken by route chemistry or enzyme.In illustrative methods, the lipid acid ester bond ruptures by amidation or transesterification reaction.
The one of ordinary skilled in the art will recognize, when fatty acid glycerine ester bond during by enzymatic breaking, can use various enzymes.The application of enzyme can make to be reflected under the mild conditions to be carried out.Two kinds of enzymes that can be used for this reaction are lipase and esterase (as NOVOZYM 435, a kind of Novozymes that comes from, Bagsvaerd, the lipase of the organism Candida antarctica of Denmark).
The one of ordinary skilled in the art will recognize, the breaking degree of fatty acid glycerine ester bond (as by transesterify or amidation) (for example will depend on performance of expecting in the enhancing oligomeric polyols (as hydroxyl value, functionality, molecular weight) and the functionality that ruptures reagent, if ethylene glycol is used as reagent and needs low hydroxyl value (as＜50), the amount of so used ethylene glycol will be in a small amount, cause low-level transesterify).In fact, one of benefit of the present invention is the functionality that can control hydroxyl value and gained polyvalent alcohol.
In some embodiments, low dimerization and transesterification reaction are carried out in independent reaction vessel, and in some embodiments, low dimerization are used identical catalyzer with transesterification reaction.For example, in exemplary, the epoxidised soybean oil spent glycol carries out open loop and low dimerization.After the low dimerization, add the ethylene glycol of second section, spent glycol carries out transesterify to form polyvalent alcohol of the present invention to low dimerization soybean oil.
In another embodiment, the epoxidation level of glycerin fatty acid ester does not need to be tending towards fully, thus in fatty acid ester and final enhancing oligomeric polyols residual pair of key.Another optional method is not make all epoxy functionalities open loops intentionally, thus residual epoxy functionalities, and if transesterify is carried out under alkaline condition, it is retained in the final low dimerization polyvalent alcohol.
In amidation, amido in the polyamine and ester bond (the fatty acid glycerine ester bond just) reaction that is present in the oligomeric fatty acids ester cause the ester group fracture and form amide group and hydroxyl.During transesterify, alcohol radical in the polyvalent alcohol and ester bond (the fatty acid glycerine ester bond just) reaction that is present in the oligomeric fatty acids ester cause the ester group fracture and form ester group and hydroxyl.No matter by amidation or transesterify, the formation of hydroxyl all makes oligomeric natural oil become the enhancing oligomeric polyols.The desirable exemplary reaction order of making the amidation polyvalent alcohol with the low dimerization natural oil of heat shows in following response diagram A.The desirable exemplary reaction order of making the transesterify polyvalent alcohol with low dimerization (just epoxidation and the open loop) natural oil of chemistry shows in following response diagram B.It being understood that the ideal structure that the response diagram representative can during reaction form.Known to the those skilled in the art be, actual composition expection can comprise except shown in those other chemical species.Although should also be noted that the key table between lipid acid is shown singly-bound among the figure, have singly-bound or multikey between the lipid acid in oligomeric carburetion.
Response diagram A
Response diagram B
In amidation or transesterification reaction, oligomeric fatty acids ester and polyamine or polyvalent alcohol be reaction about 24 hours of about 1-(being generally about 3-about 10 hours) under the temperature of about 50 ℃-Yue 250 ℃ (being generally 100 ℃-200 ℃) usually.Can use catalyzer to improve speed of reaction.The example of catalyzer comprises tin catalyst, alkaline catalysts, acid catalyst or enzyme.Representational alkaline catalysts comprises the alkoxide (as sodium methylate, sodium ethylate, sodium propylate, sodium butylate) and the dmc catalyst of NaOH, KOH, sodium and potassium.Representational acid catalyst comprises sulfuric acid, phosphoric acid, hydrochloric acid and sulfonic acid.An available catalyzer is dibutyl tin laurate (as the commodity of trade mark " FASCAT 4350 " by name).Usually, the addition of catalyzer is the about 5 weight % of about 0.1 weight %-(being generally the about 1 weight % of about 0.1 weight %-) of reactant.In some embodiments, catalyzer divides some batches of interpolations during amidate action.
In some embodiments, the step of fracture at least a portion fatty acid glycerine ester bond is finished by oligomeric fatty acids ester and nucleophilic reagent are reacted.Example comprise water, alcohol (as monohydroxy-alcohol, dibasic alcohol and polyvalent alcohol), sugar alcohol, amine (as monoamine, diamine and polyamine), alkanolamine (as monoethanolamine, diethanolamine, trolamine), mercaptan, its combination, and composition thereof.In some embodiments, nucleophilic reagent also can be functionalized glycerin fatty acid ester (comprising for example plant-derived and polyvalent alcohol animal tallow).
More specifically; in some embodiments; oligomeric fatty acids ester and nucleophilic reagent reaction; described nucleophilic reagent is selected from ethylene glycol; Diethylene Glycol; triethylene glycol; polyoxyethylene glycol; thanomin; diethanolamine; trolamine; amine-terminated polyether; 1; the 2-propylene glycol; 1; ammediol; 1; the 2-butyleneglycol; 1; the 4-butyleneglycol; 1; the 2-cyclohexanediol; dipropylene glycol; polypropylene glycol; the ethoxylation triol; the propoxylation triol; poly-(1; the 4-butyleneglycol); 2; 3-dihydroxyl dioxane; 1; the 4-xylenediol; glycerine; Polyglycerine; sorbyl alcohol; tetramethylolmethane; TriMethylolPropane(TMP); 1; 1, the 2-trimethylolethane; Viscotrol C; ethoxylated castor oil; hydroformylation polyvalent alcohol (polyvalent alcohol of making by the hydroformylation of natural oil just); alcohol open loop vegetable oil polyol (just by the epoxidized vegetable oil of pure open loop); polyvalent alcohol based on terephthalate; polyester polyol; its combination; and composition thereof.
Can be used for amidated polyamine compound and comprise the diamine compound that meets following general formula:
H
2N-R-NH
2
Wherein R is an organic group, for example fat group or aromatic group.
The example of diamines comprises the polyalkylene glycol diamines, for example polypropylene glycol diamine, polyethylene glycol diamines, quadrol, 1,3-propylene diamine and 1,4-butanediamine.Also available aromatic diamines comprises the aromatic compound that contains the amido that directly is connected with aromatic nucleus, and contains the hydrocarbon that is connected with amido or the aromatic compound of polyoxyethylene glycol.
In some embodiments, diamines is the amine end groups polypropylene glycol diamine.In some embodiments, the amine end groups polypropylene glycol diamine can be expressed as following formula:
H
2N-[-CH(-CH
3)-CH
2-O-]
x-CH
2-CH(-CH
3)-NH
2
Wherein x is about 2-about 70.
The example of amine end groups polypropylene glycol comprises those commodity (originating from Huntsman Corp.) of trade mark " JEFFAMINE D " by name.For example, JEFFAMINE D-230 has about 2.5 x value and about 230 molecular weight; JEFFAMINE D-400 has about 6.1 x value and about 430 molecular weight; JEFFAMINED-2000 has about 33 x value and about 2000 molecular weight; Have about 68 x value and about 4000 molecular weight with JEFFAMINE D-4000.
Other available diamines comprises the polyalkylene glycol diamines.The example of polyalkylene glycol diamines comprises those commodity (originating from Huntsman Corp.) of trade mark " JEFFAMINE ED " by name.These polyalkylene glycol diamines can be expressed as general formula:
H
2N-CH(-CH
3)-CH
2-[-O-CH
2-CH(-CH
3)-]
x-[O-CH
2-CH
2-]
y-[-O-CH
2-CH(-CH
3)-]
z-NH
2
Wherein y is about 2-about 40; (x+z) be about 1-about 6; And the molecular weight of this diamines (MW) is about 200-about 2000.
The example of JEFFAMINE ED diamines comprises JEFFAMINE HK-511 (y=2.0; (x+z) ≌ 1.2; And MW=220); JEFFAMINE ED-600 (y ≌ 9.0; (x+z) ≌ 3.6; And MW=600); JEFFAMINE ED-900 (y ≌ 12.5; (x+z) ≌ 6.0; And MW=900); And JEFFAMINE ED-2003 (y ≌ 39; (x+z) ≌ 6.0; And MW=2000).
Other available diamine compound is no steric hindrance diamines, as those commodity (originating from Huntsman Corp.) of trade mark " JEFFAMINE EDR " by name.These no steric hindrance diamines can be expressed as following general formula:
H
2N-(CH
2)
x-O-CH
2-CH
2-O-(CH
2)
x-NH
2
Wherein x is about 2-3; Molecular weight (MW) is about 140-about 180.
The example of JEFFAMINE EDR comprises JEFFAMINE EDR-148 (x=2.0; And MW=148) and JEFFAMINE EDR-176 (x=3.0; And MW=176).
The compound that can be used for transesterify comprises glycol, as ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, pentanediol, hexylene glycol etc.; And their mixture.Also can use polyoxyethylene glycol, polypropylene glycol and the polytetramethylene glycol of different lengths.
Also available chain triacontanol amine compound.Alkanolamine refers to the compound that not only comprises the carbinol-functional degree but also comprise the amine functionality.The chain triacontanol amine compound that contains the reactive hydrogen (as primary amine and secondary amine) of amino-contained can both participate in amidate action, participated in transesterification reaction again.Usually, when using these compounds, amidate action carries out sooner than transesterification reaction.Example comprises monoethanolamine and diethanolamine.The chain triacontanol amine compound (as trolamine) that comprises tertiary amine only participates in transesterify.
The amount of selecting polyamine or polyvalent alcohol is to provide amidation or the transesterify polyvalent alcohol with expected performance.If it is too low to be incorporated into the amount of polyamine in amidation or the transesterify polyvalent alcohol or polyvalent alcohol, polyether polyols with reduced unsaturation may not have the performance of expectation so.Usually, to the consumption of amidation or effective polyamine of transesterify or polyvalent alcohol be present in glycerin fatty acid ester in the oligomeric natural oil about 10% or higher.In other embodiments, to the consumption of amidation or effective polyamine of transesterify or polyvalent alcohol be present in glycerin fatty acid ester in the oligomeric natural oil about 50% or higher.Therefore, in amidation or transesterify polyvalent alcohol, about 90% or the glycerin fatty acid ester that is present in oligomeric natural oil at first still less after amidation or transesterify, remain unchanged.In other embodiments, about 50% or the glycerin fatty acid ester that is present in oligomeric natural oil at first still less after amidation or transesterify, remain unchanged.
In some embodiments, cleavage reaction is undertaken by hydrogenation.Hydrogenation can be for example by carrying out with ordinary method in the vegetables oil field of hydrogenation and catalyzer.In some cases, use metal catalyst to promote hydrogenation.The example of metal catalyst comprises nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium or iridium.Also can use the mixture of metal.The available catalyzer can be non-homogeneous or homogeneous.
Hydrogenation can be carried out in batches or carry out continuously.In representative batch processes, vacuumize the oligomeric fatty acids of packing in reaction vessel ester at the headspace of stirring reaction container.Then the oligomeric fatty acids ester is heated to desired temperatures.Usually, this temperature is about 50 ℃-350 ℃, for example about 100 ℃-300 ℃, or about 150 ℃-250 ℃.When the oligomeric fatty acids ester reaches desired temperatures, add hydrogenation catalyst to reaction vessel.Then hydrogen is charged in the reaction vessel to reach the H of expectation
2Air pressure.Usually, H
2Air pressure is for example about 15-3000psig.Under these conditions, hydrogenation begins, and makes temperature rise to the hydrogenation temperature of expectation, remains on that.When hydrogenation finished, the cooling reaction mass was discharged the enhancing oligomeric polyols that obtains from reaction vessel.The hydrogenant details can be at for example Bailey ' sIndustrial Oil ﹠amp; Fat Products (Hui, Y.H; 5
ThEdition; Volume 2) in find.
Similar with above-mentioned oligomeric fatty acids ester, enhancing oligomeric polyols of the present invention will comprise intermolecular cross-linking.Intermolecular cross-linking will be in order to will be bonded in a fatty acid ester on the glycerol molecule and to be bonded in second fatty acid ester bonding on the glycerol molecule.When two glycerol molecules and during bonding by crosslinked between two fatty acid molecules, a pair of being called as " dimer " of intermolecular cross-linking.Similarly, when three different fatty acid glycerine ester molecules passed through the intermolecular cross-linking bonding, it was called as " tripolymer ".The oligopolymer that also may have the higher order of magnitude.In many embodiments, enhancing oligomeric polyols of the present invention comprises the oligopolymer of dimer, tripolymer and the higher order of magnitude.In some embodiments, it is processed to isolate the oligomeric species of expectation to strengthen oligomeric polyols, for example, isolates the dimer species.In this way, can obtain the enhancing oligomeric polyols product of homogeneous basically.
The one of ordinary skilled in the art will recognize, if the oligomeric fatty acids ester is not crosslinked fully, the cleavage reaction of a part of fatty acid glycerine ester bond that ruptures (as amidation or transesterify) also may cause some fatty acid esters to rupture from the enhancing oligomeric natural oil polyols that obtains.This reaction may cause strengthening oligomeric polyols with respect to the oligomeric fatty acids ester that forms it, and molecular weight reduces.Thereby, in many embodiments, it is desirable to use the higher oligomeric fatty acids ester of molecular weight than final enhancing oligomeric natural oil polyols expectation.
Cleavage reaction (as amidation or transesterify) may cause forming primary hydroxyl and secondary hydroxyl in the enhancing oligomeric polyols that obtains.In some embodiments, strengthen the hydroxy functionality that oligomeric polyols has at least 10%, at least 15%, at least 20%, at least 25% and at least 50% primary hydroxyl form.In some embodiments, the amine functionality may be present in the enhancing oligomeric polyols that is made by amidation, owing to there is the cause of the polyamine compound of partial reaction.For example, the polyamine of partial reaction may cause the primary amine functionality to exist in the amidation polyvalent alcohol.The degree of cleavage reaction can be controlled the enhancing oligomeric polyols that has expectation functionality and hydroxyl value to provide.
In some embodiments, the number average hydroxy functionality (Fn) that the enhancing oligomeric polyols has is about 10 or lower, for example about 9 or lower, about 8 or lower, about 7 or lower, about 6 or lower, about 5 or lower, about 4 or lower, about 3 or lower, about 2 or lower.Usually, number average hydroxy functionality (Fn) is about 0.9-about 3.0.In exemplary, number average hydroxy functionality (Fn) is about 1.0 or higher, or about 1.5 or higher.
In some embodiments, the hydroxyl value (OH number) that the enhancing oligomeric polyols has is the about 200mg KOH/g of about 10-, or the about 100mg KOH/g of about 20-.Hydroxyl value represents can be used for the quantity of reactive activity hydroxyl.It is expressed as the milligram number of the potassium hydroxide of the hydroxy radical content that is equivalent to a gram sample.
In some embodiments, strengthen oligomeric polyols and have low acid number.Acid number equal the to neutralize milligram number (mgKOH/g just) of the potassium hydroxide (KOH) that is present in acid needs in the gram polyvalent alcohol sample.High acid value is not expected, because acid possibility neutralizing amine catalyzer causes isocyanic ester-polyol reaction speed to reduce.In some embodiments, the acid number that the enhancing oligomeric polyols has is lower than about 5 (mg KOH/g), for example, is lower than about 4 (mg KOH/g), is lower than about 3 (mg KOH/g), is lower than about 2 (mg KOH/g), or is lower than about 1 (mg KOH/g).In exemplary, acid number is lower than about 1 (mg KOH/g), for example, is lower than about 0.5 (mg KOH/g), or is about 0.5 (mgKOH/g) of about 0.2-.
In some embodiments, the number-average molecular weight (Mn just) that strengthens oligomeric polyols is about 1200Da or higher, for example, and about 1300Da or higher, about 1400Da or higher, or about 1500Da or higher.In some embodiments, Mn is about 6000Da or lower, for example about 4000Da or lower, or about 3500Da or lower.In some embodiments, Mn is the about 6000Da of about 1200Da-, for example, and the about 3500Da of about 1200Da-.Number-average molecular weight can for example be measured with GPC, scattering of light, vapor-pressure osmometry, end group titration and colligative property.
In some embodiments, the weight-average molecular weight (Mw just) that strengthens oligomeric polyols is about 2000Da or higher, for example, and about 3000Da or higher, about 4000Da or higher, about 5000Da or higher.In some embodiments, Mw is about 20, and 000Da or lower is for example about 10,000Da or lower, or about 6,000Da or lower.In some embodiments, Mw is about 20 for about 2000Da-, 000Da, and for example, about 2000Da-is about 6,000Da.Weight-average molecular weight can for example be measured by GPC, scattering of light, small-angle neutron scattering (SANS), X ray scattering and sedimentation rate.
Usually, it is about 15 for about 1-to strengthen polymolecularity (Mw/Mn) that oligomeric polyols has, is more typically about 1-about 6.
In some embodiments, the viscosity that the enhancing oligomeric polyols has under 25 ℃ is about 20Pas (20,000cps) or lower, about 15Pas (15,000cps) or lower, about 12Pas (12,000cps) or lower, about 10Pas (10,000cps) or lower, or about 5Pas (5000cps) or lower.
In some embodiments, strengthen oligomeric polyols if any, have residual pair of key seldom.A kind of measurement standard of the amount of two keys is its iodine value (IV) in the material.The iodine value of compound is the amount with the iodine of material sample reaction, with centigram iodine (I
2) every gram material represents (cg I
2/ g).When the low dimerization of chemistry and amidation or transesterify, the iodine value that polyvalent alcohol has usually is about 50 or lower, for example about 40 or lower, about 30 or lower, about 20 or lower, about 10 or lower, or about 5 or lower.When heat was hanged down the dimerization soybean oil by amidation or transesterify, polyvalent alcohol can have higher iodine value, and for example about 100 or lower.
Strengthen the polymkeric substance of oligomeric polyols
Polyvalent alcohol of the present invention is applicable to polymkeric substance, for example polyethers, polyester, polycarbonate, urethane and its combination (as multipolymer).
Polyurethane composition
In exemplary, enhancing oligomeric polyols of the present invention can be used for urethane.The example of urethane comprises foam, coating, tackiness agent, elastomer sealants etc.The example of polyurethane foam comprises block foam (as soft block foam) and molded foam.Rigid foam (as being used for insulation) also within the scope of the invention.The viscoelastic foam that comprises specific enhancing oligomeric polyols has report at the title of submission on November 16th, 2006 in the U.S. serial 60/859,337 of " Viscoelastic Polyurethane Foams ComprisingAmidated or Transesterified Oligomeric Natural Oil Polyols ".
In some embodiments, urethane can comprise following reaction product: (a) polymeric polyisocyanate; (b) comprise the isocyanate-reactive composition of enhancing oligomeric polyols of the present invention.The hydroxyl that exists on the enhancing oligomeric polyols and the isocyanate groups generation chemical reaction of polymeric polyisocyanate are to form amino-formate bond.Therefore, strengthen oligomeric polyols by Chemical bond in polyether polyols with reduced unsaturation.Polyurethane composition of the present invention can be used for polyurethane foam, for example soft bulk and molded polyurethane foam.
The amount of the enhancing oligomeric polyols that comprises in the isocyanate-reactive composition can be selected based on the expected performance of urethane.For example, in some embodiments, the isocyanate-reactive composition comprises the oligomeric polyols of the about 90 weight % of about 10 weight %-, the oligomeric polyols of the about 60 weight % of for example about 10 weight %-, or the oligomeric polyols of the about 40 weight % of about 15 weight %-.
In some embodiments, the isocyanate-reactive composition comprises the polyvalent alcohol of enhancing oligomeric polyols of the present invention and petroleum derivation.For example, in some embodiments, the isocyanate-reactive composition comprises the polyvalent alcohol of the petroleum derivation of the enhancing oligomeric polyols of the about 90 weight % of about 10 weight %-and the about 90 weight % of about 10 weight %-.In other embodiments, the isocyanate-reactive composition comprises the polyvalent alcohol of the petroleum derivation of the enhancing oligomeric polyols of the about 60 weight % of about 10 weight %-and the about 90 weight % of about 40 weight %-.Also in other embodiments, the isocyanate-reactive composition comprises the polyvalent alcohol of the petroleum derivation of the enhancing oligomeric polyols of the about 40 weight % of about 15 weight %-and the about 85 weight % of about 60 weight %-.
In some embodiments, the polyvalent alcohol of described petroleum derivation is a triol.Term " triol " in this application refers to a kind of polyvalent alcohol, and its per molecule has about 3.1 hydroxyls of average about 2.7-.In a particular, triol has the weight-average molecular weight (Mw) of the about 3500Da of about 3000Da-.The representative example of the triol of commercially available petroleum derivation comprises those trade marks ARCOL F3040, ARCOLF3022 by name and ARCOL 3222 (originating from Bayer); PLURACOL 1385 and PLURACOL 1388 (originating from BASF); The commodity of VORANOL 3322, VORANOL 3010, VORANOL 3136 and VORANOL 3512A (originating from Dow).
The representative example of available polymeric polyisocyanate comprises that per molecule on average has at least about those of 2.0 isocyanate groups.Aliphatics and aromatic poly-isocyanate all can use.The example of the aliphatic polymeric isocyanate that is fit to comprises 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane vulcabond, tetramethylene-1,3-vulcabond, hexanaphthene-1,3-and 1,4-vulcabond, 1,5-two isocyanatos-3,3,5-trimethyl-cyclohexane, hydrogenation 2,4-and/or 4,4 '-'-diphenylmethane diisocyanate (H12MDI), isophorone diisocyanate etc.The example of the aromatic poly-isocyanate that is fit to comprises 2,4 toluene diisocyanate (TDI), 2,6-tolylene diisocyanate (TD1) and its blend; 1,3-and 1,4-phenylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate (comprise itself and a small amount of 2,4 '-mixture of isomers) (MD1), 1,5-naphthalene diisocyanate, tritane-4,4 ', 4 ＂-triisocyanate, polyphenylene polymethylene polymeric polyisocyanate (PMDI) etc.The derivative of above-mentioned polymeric polyisocyanate and prepolymer, as contain those of carbamate, carbodiimide, allophanate, chlorinated isocyanurates, acidylate urea, biuret, ester and similar group, also can use.
The amount of polymeric polyisocyanate preferably is enough to provide about 60-about 120, the isocyanate index of preferred about 70-about 110, under the situation of high water prescription (just, in prescription per 100 weight parts other contain the active hydrogen raw material and contain prescription at least about 5 weight parts waters), be about 70-about 90.The tolerance that refers to the stoichiometric balance between the total yield of the equivalent of used isocyanic ester and water, polyvalent alcohol and other reactant at the term " isocyanate index " of this application.Index 100 means isocyanic ester that provides enough and the compound that all contain active hydrogen atom reaction.
The example of available catalyzer comprises tertiary amine compound and organometallic compound.The specific examples of available tertiary amine compound comprises triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocounut oil morpholine, 1-methyl isophthalic acid, 4-dimethylaminoethyl piperazine, 3-methoxyl group-N-dimethyl propylamine, N, N-diethyl-3-diethyl amino propylamine, dimethyl benzylamine, two (2-dimethylaminoethyl) ether etc.The favourable consumption of tertiary amine catalyst contains about 5 parts of the about 0.01-of active hydrogen raw material, about 2 parts of preferably about 0.05-for per 100 weight parts in the prescription.
The specific examples of available organo-metallic catalyst comprises the organic salt of metal such as tin, bismuth, iron, zinc etc., preferred organotin catalysts.The organotin catalysts that is fit to comprises two lauric acid tin methides, dibutyl tin laurate, stannous octoate etc.Other catalyzer that is fit to is for example at United States Patent (USP) 2,846, instructed in 408, and it is incorporated herein by reference at this.Preferably, for per 100 weight parts in the prescription contain the active hydrogen raw material, use the organo-metallic catalyst of about 1.0 weight parts of about 0.001-.Also can use the blend of catalyzer.
In some embodiments, use whipping agent.Whipping agent is gas or other can produce gas during urethane forms a material.Whipping agent is used to make polyurethane foam usually.The whipping agent that is fit to comprises water, Liquid carbon dioxide, acetone, methylene dichloride and pentane, preferably water.
The consumption of whipping agent is enough to provide the foam density of expectation and presses and fall into stress (IFD).For example, when water during as unique whipping agent, contain the active hydrogen raw material for other of per 100 weight parts in the prescription, use about 0.5-about 10, preferably about 1-is about 8, more preferably from about about 6 weight parts of 2-.
Other additive that can be included in the prescription comprises tensio-active agent, catalyzer, cell size control agent, pore-creating agent, tinting material, antioxidant, sanitas, static inhibitor, softening agent, linking agent, fire retardant etc.
The example of available tensio-active agent includes an alkali metal salt of organic silicon surface active agent and lipid acid.Preferably have organic silicon surface active agent, as the segmented copolymer of epoxy alkane and dimethyl siloxane, the organic silicon surfactant of preferred especially " ground fog (low fog) " level.
In some cases, during foam preparation, static inhibitor can be included in the prescription, or be used to handle the foam of making.The available example comprises non-volatile, ionizable metal-salt, chooses wantonly to combine with the toughener compound, and as United States Patent (USP) 4,806,571,4,618,630 and 4,617, described in 325.Interestedly especially be up to about the sodium tetraphenylborate of 3 weight percentage or have up to about the application of the sodium salt of the perfluorination aliphatic carboxylic acid of 8 carbon atoms.
In some embodiments, polyurethane composition is suitable for soft massive polyurethane foam.Soft massive polyurethane foam can be made with the piece material foaming machine of routine, the for example commercial box foaming machine of described equipment, high pressure or low pressure continuous foam machine, vault piece bubble technology, rectangular block bubble technology (are seen, for example, Draka, Petzetakis, Hennecke, Planiblock, EconoFoam, and Maxfoam technology) or vertical foam (verti-foam) technology.In some embodiments, block foam is produced under reduced pressure.For example, in varying pressure in foaming (VPF), in sealing shell, provide whole transport portions of foaming machine.This technology makes can control foam density and produce the foam rank that may be difficult to produce in other cases.The details of soft massive polyurethane foam and block foam process is in the news in the 5th Zhanghe the 9th chapter (second edition, 1997, DowChemical Company) of the Flexible Polyurethane Foams that for example Herrington and Hock edit.
Present invention is described referring now to following non-limiting example.
Embodiment 1: the transesterify of open loop epoxidised soybean oil (preparation of EOP-1)
The 1st step: the preparation of oligomeric open loop epoxidised soybean oil polyvalent alcohol (oligomeric polyols (OP-1))
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, the 1360 gram ethylene glycol of packing into, 0.52 gram HBF
4, and 136 the gram methyl alcohol.With this mixture heating up to 95 ℃, and add 1000 gram epoxidised soybean oil (FLEXOL EPO, Dow Chemical).Mixture in the flask was stirred 2.7 hours down at 95 ℃.Then reaction mixture is transferred to separating funnel, makes its separatory some hrs.Removal contains the lower floor of ethylene glycol, and the upper strata that will contain oligomeric polyols (OP-1) is transferred in the round-bottomed flask, neutralizes with volatile salt (0.1 weight % of oligomeric polyols) at this.Then the oligomeric polyols that will neutralize is transferred in the wiped film evaporator.The wall temperature of described vaporizer is 120 ℃.
Said procedure is specifically designed to the preparation of OP-1, but has also described the method for other sample in the table 1.1, has wherein carried out suitable modification as shown.
The reaction conditions of table 1.1 preparation oligomeric polyols (OP-1)
| Sample | ESBO(g) | Ethylene glycol (g) | Methyl alcohol (g) | HBF 4(g) [all pure % of mixture] | Reaction times (hour) |
| OP-1.1 | 1000 | 1360 | 136 | 0.52 [0.01] | 2.7 |
| OP-1.2 | 1000 | 1360 | 136 | 0.52 [0.01] | 5.0 |
| OP-1.3 | 1000 | 1360 | 136 | 1.00 [0.02] | 3.0 |
| OP-1.4 | 1000 | 1360 | 136 | 0.52 [0.01] | 7.5 |
The characteristic of the oligomeric polyols of table 1.1 and performance are reported in table 1.1A and 1.1B.
The characteristic of table 1.1A oligomeric polyols (OP-1)
| Sample | OH number (mg KOH/g) | EOC (％) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| OP-1.1 | 183 | 3.35 | 0.75 [750] |
| OP-1.2 | 199 | 1.73 | 6.0 [6000] |
| OP-1.3 | 247 | 0.13 | 24.0 [24,000] |
| OP-1.4 | 251 | 0.72 | 22.8 [22,800] |
The characteristic of table 1.1B oligomeric polyols (OP-1)
| Sample | Oligopolymer (%) | Monomer (%) | Mn (GPC) | fn (GPC) | Mw (GPC) | Mw/Mn |
| OP-1.1 | 28 | 72 | 1156 | 3.77 | 1398 | 1.21 |
| OP-1-2 | 37 | 63 | 1329 | 4.71 | 1815 | 1.37 |
| OP-1.3 | 68 | 30 | 2015 | 8.87 | 6191 | 3.07 |
| OP-1.4 | 49 | 49 | 1798 | 8.04 | 3004 | 1.67 |
The 2nd step: strengthen the preparation (strengthening oligomeric polyols (EOP-1)) of oligomeric polyols
Oligomeric polyols (OP-1) strengthens oligomeric polyols (EOP-1) by reacting to change into ethylene glycol in the presence of potassium methylate.With the mixture heating up to 160 of oligomeric polyols, ethylene glycol and potassium methylate ℃, stirred 15 minutes.The concrete amount and the condition of sample are presented in the table 1.2.
Table 1.2 changes into oligomeric polyols (OP-1) reaction conditions that strengthens oligomeric polyols (EOP-1)
| Strengthen oligomeric polyols EOP-1 | Oligomeric polyols OP-1 | The amount of OP-1 (g) | Ethylene glycol (g) | Potassium methylate (g) [%] | Reaction times (min) | Temperature of reaction (℃) |
| EOP-1.1 | OP-1.1 | 950 | 40 (interpolations) | 0.5[0.05] | 15 | 160 |
| EOP-1.2 | OP-1.2 | 1000 | Residual | 0.5[0.05] | 15 | 160 |
| EOP-1.3 | OP-1.3 | 1000 | Residual | 0.5[0.05] | 15 | 160 |
| EOP-1.4 | OP-1.4 | 1000 | Residual | 0.5[0.05] | 15 | 160 |
The performance that strengthens oligomeric polyols is presented among table 1.2A and the 1.2B.
Table 1.2A strengthens the performance of oligomeric polyols (EOP-1)
| Polyvalent alcohol | OH number (mg KOH/gram) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| EOP-1.1 | 167 | 1.2 [1200] |
| EOP-1.2 | 217 | 7.0 [7000] |
| EOP-1.3 | 219 | 9.6 [9600] |
| EOP-1.4 | 224 | 8.7 [8700] |
Table 1.2B strengthens the performance of oligomeric polyols (EOP-1)
| Polyvalent alcohol | Oligopolymer (%) | Monomer (%) | Mn (GPC) | fn (GPC) | Mw (GPC) | Mw/Mn |
| EOP-1.1 | 20 | 54 | 937 | 2.79 | 1362 | 1.45 |
| HOP-1.2 | 36 | 54 | 1241 | 4.80 | 1955 | 1.57 |
| EOP-1.3 | 39 | 50 | 1390 | 5.42 | 2547 | 1.83 |
| EOP-1.4 | 39 | 50 | 1203 | 4.80 | 2194 | 1.82 |
Embodiment 2: the transesterify preparation of the open loop epoxide by being derived from soybean oil strengthens oligomeric polyols (EOP2.1)
The 1st step:
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, the 1360 gram ethylene glycol of packing into, 1.0 gram HBF
4With 136 gram methyl alcohol.With mixture heating up to 100 ℃, add 1000 gram epoxidised soybean oil (ESBO, Epoxol 7-4, ACS, EOC=7.0%).Mixture in the flask was stirred 3.0 hours down at 95 ℃.Then reaction mixture is transferred to separating funnel, makes its separatory some hrs.Removal contains the lower floor of ethylene glycol, and the upper strata that will contain oligomeric polyols is transferred in the round-bottomed flask, neutralizes with 0.5 gram potassium methylate at this.
The 2nd step:
The transesterify of OP-2.1 was carried out under 160 ℃ 15 minutes.After the transesterify, product is transferred in the wiped film evaporator.The wall temperature of described vaporizer is 120 ℃, and vacuum is set at 1mmHg.After removing ethylene glycol, the ethylene glycol (50g) of known weight is added in the mixture to reduce viscosity.From then on the characteristic of the isolated enhancing oligomeric polyols of process EOP-2.1 sees Table 2.1-2.3.
The performance of table 2.1 EOP-2.1
| Sample | OH number (mg KOH/gram) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| EOP-2.1 | 266 | 13 [13,000] |
The performance of table 2.2 EOP2.1 (adding 5% ethylene glycol)
| Sample | OH number (mg KOH/g) | Primary hydroxyl (%) | EOC (％) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Acid number (mg KOH/g) | Water (%) |
| EOP-2.1 | 335 | 59 | 0.13 | 8.0 [8000] | 0.55 | 0 |
The performance of table 2.3 EOP-2.1
| Sample | Oligopolymer (%) | Monomer (%) |
| EOP-2.1 | 42 | 43 |
Embodiment 3: the transesterify that is derived from the open loop epoxide of soybean oil strengthens oligomeric polyols (EOP-3) to form.(effect of transesterification catalyst)
The 1st step: in the 1st step, in order to prepare OP-3, synthetic three kinds of different oligomeric polyols (A, B and C)
Polyvalent alcohol A's is synthetic
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, HBF packs into
4, methyl alcohol and ethylene glycol.Mixture is preheated to 100 ℃.Then, add part epoxidised soybean oil (EOC=2.28; IV=79), mixture was stirred 6 hours.Then the mixture with polyvalent alcohol and reactant is transferred to separating funnel, and standing over night makes its gravity separation.Remove lower floor's (ethylene glycol/methanol layer just), the upper strata that will contain polyvalent alcohol is transferred in the round-bottomed flask, with volatile salt (every polyvalent alcohol weight 1%) neutralization.Mixture is transferred in the wiped film evaporator.The wall temperature of vaporizer is 120 ℃.Reaction conditions is listed in table 3.1, and the characteristic of polyvalent alcohol provides in table 3.2-3.3.
Table 3.1
| Sample | Part ESBO | EG (g) | Methyl alcohol (g) | HBF 4(g) [all pure % of mixture] | Temperature (℃) | Time (hour) |
| A | 900 | 600 | 60 | 1.65 [0.05％] | 100 | 6 |
The characteristic of table 3.2 polyvalent alcohol
| Sample | OH# (mg KOH/g) | EOC (％) | AV (mg KOH/g) | PV (meq/Kg) | IV | Water (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| A | 107.3 | 0.12 | 0.56 | 22 | 75 | 0 | 1.7 [1700] |
The characteristic of table 3.3 polyvalent alcohol
| Sample | Oligopolymer (%) | Monomer (%) | Fn | Mn (GPC) | Mw (GPC) | Mw/Mn |
| A | 37 | 63 | 2.46 | 1287 | 1857 | 1.44 |
Polyvalent alcohol B's is synthetic
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, HBF packs into
4, methyl alcohol and ethylene glycol.Mixture is preheated to 100 ℃.Then, add the mixture (part epoxidised soybean oil and 750 grams that 250 grams have EOC=3.39, IV=69 and PV=26.8 have the part epoxidised soybean oil of EOC=2.32, IV=87.7 and PV=21.7) of two kinds of part epoxidised soybean oil, mixture keeps 100 ℃ to stir 6 hours down.Then the mixture with polyvalent alcohol and ethylene glycol is transferred to separating funnel, leaves standstill some hrs.Remove lower floor's (ethylene glycol/methanol layer just), top polyvalent alcohol layer is transferred in the round-bottomed flask, with volatile salt (every polyvalent alcohol weight 1%) neutralization.Then material is transferred in the wiped film evaporator.The wall temperature of vaporizer is 120 ℃.Reaction conditions is listed in table 3.4, and the characteristic of polyvalent alcohol provides in table 3.5-3.6.
Table 3.4
| 1 | Part ESBO (g) | Ethylene glycol (g) | Methyl alcohol (g) | HBF 4(g) [all pure % of mixture] | Temperature of reaction (℃) | Reaction times (hour) |
| B | 1000 | 750 | 75 | 1.9 [0.05] | 100 | 6 |
The characteristic of table 3.5 polyvalent alcohol
| Sample | OH# (mg KOH/g) | Primary hydroxyl (%) | EOC (％) | AV (mg KOH/g) | PV (meq/Kg) | IV | Water (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| B | 111 | 32.2 | 0.064 | 0.77 | 7.0 | 83 | 0 | 0.7 [700] |
The characteristic of table 3.6 polyvalent alcohol
| Sample | Oligopolymer (%) | Monomer (%) | Fn | Mn (GPC) | Mw (GPC) | Mw/Mn |
| B | 35 | 62 | 2.47 | 1283 | 1806 | 1.41 |
Oligomeric polyols C's is synthetic
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, HBF packs into
4, methyl alcohol and ethylene glycol.Mixture is preheated to 100 ℃.Then, and adding part epoxidised soybean oil (EOC=2.40, PV=27.8, IV=81.2), the reaction times that stirs the mixture and keep being scheduled to.Then, the mixture of polyvalent alcohol and ethylene glycol is transferred to separating funnel, leaves standstill some hrs.Remove lower floor's (ethylene glycol/methanol layer just), top polyvalent alcohol layer is transferred in the round-bottomed flask, with volatile salt (every polyvalent alcohol weight 1%) neutralization.Then material is transferred in the wiped film evaporator.The wall temperature of vaporizer is 120 ℃.Reaction conditions is listed in table 3.7, and the characteristic of polyvalent alcohol provides in table 3.8-3.9.
Table 3.7
| Sample | Part ESBO (g) | Ethylene glycol (g) | Methyl alcohol (g) | HBF 4(g) [all pure % of mixture] | Temperature of reaction (℃) | Reaction times (hour) |
| C | 1000 | 1000 | 100 | 2.2 [0.05] | 100 | 6 |
The characteristic of table 3.8 polyvalent alcohol
| Sample | OH# (mg KOH/g) | Primary hydroxyl (%) | EOC (％) | Acid number (mg KOH/g) | PV (meq/Kg) | Water (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] |
| C | 104 | 16.5 | 0.165 | 0.42 | 9.7 | 0 | 0.50 [500] |
The feature of table 3.9 polyvalent alcohol
| Sample | Oligopolymer (%) | Monomer (%) | Fn | Mn (GPC) | Mw (GPC) | Mw/Mn |
| C | 33 | 65 | 2.19 | 1182 | 1629 | 1.38 |
Oligomeric polyols A, B and the C of equivalent are mixed to be formed for the present embodiment OP-3 in the 2nd step.
The 2nd step: strengthen the preparation of oligomeric polyols
In being furnished with three mouthfuls of round bottom jacketed reaction flasks of reflux exchanger and mechanical stirrer, the Fascat 4350 (AtofinaChemicals) with 4 gram ethylene glycol and 0.1 weight % mixes with 200gm oligomeric polyols (OP-3).Content is used Ca (OH) down at 200 ℃
2Hybrid reaction.Reactor during reaction fills nitrogen.After reaction stops, reaction mixture is transferred in the round-bottomed flask, with volatile salt (the 1 weight % of OP-3) neutralization.The material that will neutralize is transferred in the wiped film evaporator then.The wall temperature of vaporizer is 120 ℃.
Above program is understood the preparation of sample EOP-3.4 specifically, but the process of other sample in the table 3.10 also has been described, such as in table notes carried out suitable modification.
Table 3.10
| Sample | OP-3 (g) | Ethylene glycol (g) | Catalyzer (%) | Temperature (℃) | Outward appearance |
| EOP-3.1 | 200 | 4 | Fascat 4350(0.1) | 160 | Yellow is opaque |
| EOP-3.2 | 200 | 5 | Fascat 4350(0.1) | 160 | Yellow is opaque |
| EOP-3.3 | 200 | 4 | Potassium methylate (0.05) | 160 | Clarification, yellow |
| EOP-3.4 | 200 | 4 | Ca(OH) 2(0.1) | 200 | Opaque slightly, yellow |
| EOP-3.5 | 200 | 4 | Guanidinium carbonate (0.1) | 160 | Clarifying dark-brown |
| EOP-3.6 | 200 | 4 | Super base (0.1) | 160 | Yellow is opaque |
The characteristic of the isolated enhancing oligomeric polyols of this method sees Table 3.11.Shown characteristic simultaneously as the oligomeric polyols OP-3 of the 2nd starting raw material that goes on foot.
Table 3.11
| Sample | Reaction times (hour) | OH# (mg KOH/g) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%) | Monomer (%) | Digly+ Monogly (％) |
| OP-3 | -- | 110 | 0.66[660] | 35 | 63 | 2 |
| EOP-3.1 | 4 | 100 | 0.63[630] | -- | -- | -- |
| EOP-3.2 | 5 | 115 | 0.57[570] | 48 | 22 | 30 |
| EOP-3.3 | 2 | 135 | 0.52[520] | 36 | 49 | 15 |
| EOP-3.4 | 4 | 99 | 0.86[860] | 58 | 15 | 27 |
| EOP-3.5 | 4 | 127 | 0.56[560] | 36 | 47 | 16 |
| EOP-3.6 | 3 | 122 | 0.52[520] | 41 | 27 | 32 |
Embodiment 4
Embodiment 4.1 strengthens oligomeric polyols by the amidation preparation of the oligomeric polyols of methyl alcohol open loop.
The 1st step: prepare oligomeric polyols (OP-4.1) by ESBO
Is being furnished with mechanical stirrer, thermopair, in 10 liters of reactors of water condenser and cooling worm, to containing 4.4 gram fluoroboric acid (48% aqueous solution, be derived from Aldrich Chemicals, Milwaukee, WI) and 120 gram methyl alcohol (ACS levels, be derived from Fisher Scientific, Pittsburgh, adding 2034 gram ESBO in the mixture PA) (originate from the Flexol Plasticizer ESO of Dow Chemical Co., yellow viscous liquid, viscosity is 171cSt, the epoxide total amount is 7.0wt.%, IV is 0.9, and acid number is 0.2mgKOH/g, and hydroxyl value is 7mg KOH/g).Stir this mixture and be heated to 35 ℃, heat release takes place in this moment, although use water cooling, temperature rises to 84 ℃ and follow a large amount of foaming rapidly.When temperature is back to 60 ℃, stirred the mixture in addition 1 hour.Remove heating source, and 2 liters of toluene of adding and 50 gram weakly alkaline macroporous ion exchange resins in reactor (Lewatit MP 64 originates from SybronChemicals, Birmingham, NJ).Continue to stir one hour, and temperature is descended naturally.Filtering mixt places Rotary Evaporators to remove volatile matter the filtrate that obtains.Under 90 ℃, at first use vacuum diaphragm pump, then carried out 1 hour with the high vacuum oil pump.Obtain 2085 gram yellow viscous liquids.This analytical performance that strengthens oligomeric polyols (OP-4.1) is listed in table 4.1.
The performance of table 4.1 polyvalent alcohol
| Polyvalent alcohol | EOC (％) | OH# (mg KOH/g) | Acid # (mg KOH/g) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%). |
| OP-4.1 | 2.8 | 92 | 0.43 | 9.2 [9200] | 67 |
The 2nd step (EOP-4.1): the amidation preparation by oligomeric polyols (OP-4.1) strengthens oligomeric polyols (EOP-4.1)
In being furnished with 2 liter of three arm round-bottomed flask of water condenser, thermometer and magnetic stirring bar, (purity 99% originates from Acros Organics, and Geel Belgium) at room temperature mixes with 500mL toluene with 1005 gram OP-4.1 polyvalent alcohols, 81 gram diethanolamine.Flask is filled N
2After 10 minutes, the content in the flask under agitation is heated to about 125 ℃.Continue to stir and kept temperature totally 22 hours.Remove heating source, make temperature reduce to about 70 ℃.Then, content is transferred in another flask, and places on the Rotary Evaporators removing volatile matter, under 90 ℃ at first by vacuum diaphragm pump, then by high vacuum oil pump 2 hours.Obtain 1046 grams and strengthen oligomeric polyols (EOP-4.1).This oligomeric polyols is the reddish-brown viscous liquid.
The 2nd step (EOP-4.2): the amidation preparation by oligomeric polyols (OP-4.1) strengthens oligomeric polyols (EOP-4.2)
In being furnished with 2 liter of three arm round-bottomed flask of water condenser, thermometer and mechanical stirrer, 930 gram OP-4.1 polyvalent alcohols and 75 are restrained diethanolamine, and (purity 99% originates from Acros Organics, and Geel Belgium) at room temperature mixes.Flask is filled N
2After 10 minutes, the content in the flask under agitation is heated to about 125 ℃.Continue to stir and kept temperature totally 21 hours.Remove heating source, make temperature reduce to about 70 ℃.The enhancing oligomeric polyols (EOP-4.2) that obtains is the reddish-brown viscous liquid, weighs 997 grams.
The analytical performance of EOP-4.1 and EOP-4.2 is listed in table 4.2.
Table 4.2
| EOC (％) | OH# (mg KOH/g) | Acid # (mg KOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%) | The proportion of primary OH groups of measuring (%) | |
| EOP-4.1 | 2.7 | 188 | 0.18 | 0.084 | ]7.0 [17,000] | 51 | |
| EOP-4.2 | 2.4 | 195 | 0.19 | 0.042 | 17.8 [17,800] | 54 | 34 |
Embodiment 4.2 strengthens oligomeric polyols (EOP-4.3) by the amidation preparation of the oligomeric polyols of ethylene glycol open loop.
The 1st step: the preparation of oligomeric polyols (OP-4.2)
In being furnished with 10 liters of reactors of mechanical stirrer, condenser, thermometer and heating jacket, add complete epoxidised soybean oil (3,713g).Add ethylene glycol (185g) and HBF
4(48% aqueous solution 7.5g), and slowly is heated to about 80 ℃ with this mixture, keeps 2 hours.Reaction mixture reaches about 89 ℃ top temperature.Add Lewatite MP64 (100g) ion exchange resin, stirred 1 hour.Then, this mixture is filtered with help with 1 gallon of acetone diluted.Filtering mixt is to remove resin then.Then remove solvent with Rotary Evaporators.Material is further dry under high vacuum.The oligomeric polyols that obtains (OP-4.2) weighs 3791 grams.The residual ethylene glycol of trace is removed with wiped film evaporator.The performance of oligomeric polyols (OP-4.2) shows in table 4.3.
The performance of table 4.3 polyvalent alcohol
| EOC (％) | OH# (mg KOH/g) | Acid # (mg KOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%) | The proportion of primary OH groups of measuring (%) | |
| OP-4.2 | 4.3 | 70 | 0.58 | 0.001 | 19.8 [19,800] | 64 | 22 |
The 2nd step: amidation oligomeric polyols (OP-4.2) strengthens oligomeric polyols (EOP-4.3) to form
In being furnished with 2 liter of three arm round-bottomed flask of water condenser, thermometer and mechanical stirrer, 1001 gram oligomeric polyols OP-4.2 and 40 are restrained diethanolamine, and (purity 99% originates from Acros Organics, and Geel Belgium) at room temperature mixes.Flask is filled N
2After 10-15 minute, the content in the flask under agitation is heated to about 125 ℃.Continue to stir and kept temperature totally 18 hours.Then make temperature reduce to about 70 ℃.The enhancing oligomeric polyols EOP-4.3 that obtains is the reddish-brown viscous liquid, weighs 1,037 gram.The character that strengthens oligomeric polyols EOP-4.3 sees Table 4.4.
The performance of table 4.4 polyvalent alcohol
| EOC(％) | OH#(mg KOH/g) | Acid # (mgKOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligomer (%) | The proportion of primary OH groups of measuring (%) | |
| EOP-4.3 | 4.2 | 130 | 0.28 | 0.022 | 13.9[13,900] | 60 | 43 |
Embodiment 5
Embodiment 5.1 strengthens oligomeric polyols (EOP-5.1) by the amidation preparation of oligomeric dryness soybean oil
At first, be furnished with water condenser, thermometer, mechanical stirrer and N
2Adding 700 gram dryness soybean oil and 35 gram diethanolamine in 1 liter of three neck round-bottomed flask of import (purity 99% originates from AcrosOrganics, Geel, Belgium).Fill N
2After 15 minutes, the content in the flask is heated to 125 ℃, and kept 18 hours.Then the content in the flask is cooled to about 50 ℃ and migrate out.Brown viscous liquid weighs 732 grams.The performance that strengthens oligomeric polyols (EOP-5.1) sees Table 5.1.
Table 5.1
| I.V. | OH# (mg KOH/g) | Acid # (mg KOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligomer (%) | |
| EOP-5.1 | 88 | 71 | 0.83 | 0.046 | 4.5 [4500] | 61％ |
Embodiment 5.2 strengthens oligomeric polyols (EOP-5.2) by the amidation preparation of oligomeric polyols (OP-5.1)
The 1st step: by being prepared oligomeric polyols OP-5.1 by the complete epoxidised soybean oil of water open loop.The performance of polyvalent alcohol OP-5.1 sees Table 5.2.
The performance of table 5.2 polyvalent alcohol
| Ring opening agent (%) | Catalytic amount (%) | EOC (％) | OH# (mg KOH/g) | Acid # (mg KOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligomer (%) | |
| OP-5.1 | 1.5 | 0.10 | 3.8 | 89 | 0.73 | 0.007 | 14.0 [14,000] | 64 |
The 2nd step: at first, the epoxidised soybean oil (OP-5.1), 50 that adds 987 gram open loops in being furnished with 2 liter of three arm round-bottomed flask of water condenser, thermometer and magnetic stirring bar restrains diethanolamine, and (AcrosOrganics, Geel is Belgium) with 600mL toluene.Flask is filled N
2After 10 minutes, the content in the flask under agitation is heated to about 125 ℃.Continue to stir and kept temperature totally 20 hours.Then make temperature reduce to about 70 ℃, product is transferred in the Rotary Evaporators to remove volatile matter.Under 90 ℃, at first use vacuum diaphragm pump, carried out 1 hour with the high vacuum oil pump subsequently.The reddish-brown viscous liquid that obtains weighs 996 grams.The performance that strengthens oligomeric polyols EOP-5.2 sees Table 5.3.
Table 5.3
| EOC (％) | OH# (mg KOH/g) | Acid # (mg KOH/g) | Water content (%) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligomer (%) | |
| EOP-5.2 | 3.5 | 167 | 0.23 | 0.101 | 20.0 [20,000] | 58 |
Embodiment 6: by the synthetic general experimentation that strengthens oligomeric polyols of oligomeric vegetables oil
The starting raw material of embodiment 6 is made up of dryness oleum lini and dryness soybean oil.KCZ5/6 dryness oleum lini can be available from Cargill, and Incorporated (Minneapolis, MN).Z6 dryness oleum lini can available from Davis-Frost Company (Minneapolis, MN).The feature of dryness oleum lini and dryness soybean oil sees Table 6.1.
In the 450mL stainless steel reactor, add dry vegetable oil, transesterify polyvalent alcohol and catalyzer successively.The amount of each composition is listed in table 6.3-6.4.The closed reactor sealing, and continuing to charge into nitrogen in 10 minutes by continuous bubbling nitrogen under the stirring.At last, set up the protection of nitrogen gas inert atmosphere pressure of about 10-15p.s.i.Reactor is heated to 170 ℃ and remained on this temperature 4-6 hour, and 6.3-6.4 shows as table.Then with reactor cooling to 60-80 ℃, polyvalent alcohol is poured in the vial.The performance that strengthens oligomeric polyols sees Table 6.5 and 6.6.
As overview, be used for the polyvalent alcohol that only has primary hydroxyl (EG, DEG, PEG200, TEOA, the TMP etc.) catalyst concn (0.05-0.1% according to appointment) that needs are lower usually and the short reaction times (4h according to appointment) of transesterification reaction.Polyvalent alcohol (PG, DPG, sorbyl alcohol etc.) with primary hydroxyl and secondary hydroxyl needs higher catalyst concn (according to appointment 0.1%) and long reaction times (6h according to appointment) usually.
Table 6.1
| Title | KCZ5/6 | Z6 | BSBO |
| Type | The dryness oleum lini | The dryness oleum lini | The dryness soybean oil |
| Iodine value (mg I 2/g) | 100 | 89 | -- |
| Viscosity (Pa.s@25 ℃) [cps@25 ℃] | 9.6 [9600] | 13.6 [13,600] | 6 [6000] |
| Acidity (mg KOH/g) | 18 | 7.6 | -- |
| Mn | 1800 | 2819 | -- |
| Mw | 9750 | 18182 | -- |
| Mw/Mn | 5.4 | 6.44 | -- |
| Monomer content (%) | 25 | 21 | |
| Oligomer (%) | 71 | 75 | |
| Outward appearance | Yellow viscous liquid | Brown viscous liquid | -- |
Table 6.2
| Abbreviation | Compound |
| EG | Ethylene glycol |
| DEG | Diethylene Glycol |
| PG | Propylene glycol |
| DPG | Dipropylene glycol |
| TEG | Tetraglycol 99 |
| PEG200 | Polyoxyethylene glycol (MW=200) |
| TMP | TriMethylolPropane(TMP) |
| TEOA | Trolamine |
| Sorbitol | Sorbyl alcohol |
| PGL3(Solvay) | Polyglycerine (MW=240Da; Functionality=5; OH#=1166mg KOH/g) |
| HF Polyol | The polyvalent alcohol (OH number=233mg KOH/g) that makes by the soybean oil hydroformylation |
| PE Polyol | Polyethylene glycol adipate (MW=500; OH#=225mg KOH/g) |
Table 6.3
| Polyvalent alcohol | The type of oil | The amount of oil | Nucleophilic reagent (g) | Catalyzer (g) | Temperature (℃) | Time (hour) |
| 6.1 | KCZ 5/6 | 200 | EG(6.0g) | FC 4350(0.11g) | 170 | 4 |
| 6.2A | KCZ 5/6 | 300 | DEG(16.8g) | FC 4350(0.3g) | 170 | 4 |
| 6.2B | KCZ 5/6 | 225 | DEG(7.92g) | FC 4350(0.23g) | 170 | 4 |
| 6.2C | Z6 | 225 | DEG(8.0g) | CaH 2(1.165g) | 170 | 6 |
| 6.3 | Z6 | 200 | PG(7.7g) | FC 4350(0.2g) | 170 | 6 |
| 6.4 | Z6 | 145 | DPG(10.3g) | FC 4350(0.155g) | 170 | 6 |
| 6.5 | KCZ 5/6 | 300 | TEG(32g) | FC 4350(0.3g) | 170 | 4 |
| 6.6 | Z6 | 225 | PEG200(15g) | FC 4350(0.23g) | 170 | 4 |
| 6.7 | KCZ 5/6 | 180 | TMP(8.8g) | FC 4350(0.2g) | 170 | 4 |
| 6.8A | Z6 | 235 | TEOA(9.9g) | FC 4350(0.24g) | 170 | 4 |
| 6.8B | Z6 | 225 | TEOA(10.4g) | CaH 2(1.17g) | 170 | 6 |
| 6.8C | Z6 | 225 | TEOA(7.4g) | FC 4350(0.23g) | 170 | 4 |
| 6.9 | KCZ 5/6 | 200 | Sorbitol(5.1g) | FC 4350(0.2g) | 170 | 6 |
| 6.10 | Z6 | 200 | PGL3(Solvay 10.0g) | FC 4350(0.23g) | 170 | 6 |
| 6.11 | Z6 | 200 | PGL3(16.0g) | FC 4350(0.23g) | 170 | 6 |
| 6.12 | Z6 | 200 | HF polyol(36.5g) | FC 4350(0.23g) | 170 | 6 |
| 6.13 | Z6 | 200 | PE polyol(38g) | FC 4350(0.23g) | 170 | 6 |
Table 6.4
| The type of oil | The amount of oil | Nucleophilic reagent (g) | Catalyzer (g) | Temperature (℃) | Time (hour) | |
| 6.14 | BSBO | 225 | TEOA (9.5g) | FC 4350 (0.235g) | 170 | 4 |
| 6.15 | BSBO | 225 | DEG (7.0g) | FC 4350 (0.23g) | 170 | 4 |
| 6.16 | BSBO | 225 | PEG200 (24.5g) | FC 4350 (0.25g) | 170 | 4 |
Table 6.5
| OH# (mgKOH/g) | Acid (mg KOH/g) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%) | Monomer (%) | Mn | |
| 6.1 | 42 | 4.39 | 2.2[2200] | 63 | 15 | -- |
| 6.2A | 56-58 | 7.6 | 3.2[3200] | 67 | 1] | -- |
| 6.2B | 34 | 5.7 | 2.8[2800] | 67 | -- | 1790 |
| 6.2C* | 46 | 0.7 | 2.6[2600] | -- | -- | 1710 |
| 6.3 | 49 | 7.5 | 3.4[3400] | 69 | 13 | -- |
| 6.4 | 56 | 8.8 | 3.2[3200] | 65 | 13 | -- |
| 6.5 | 55 | 5.8 | 2.6[2600] | 63 | 15 | -- |
| 6.6 | 36 | 5.8 | 2.3[2300] | 66 | -- | 1800 |
| 6.7 | 56 | 0.3 | 7.7[7700] | 54 | 18 | -- |
| 6.8A | 44 | 6.7 | 5.1[5100] | 70 | 11 | -- |
| 6.8B* | 57 | 1.1 | 5.8[5800] | -- | -- | 2050 |
| 6.8C | 31 | 5.2 | 6.8[6800] | 69 | -- | 2084 |
| 6.9 | 42 | 10.4 | 10.6[10,600] | 76 | 19 | -- |
| 6.10 | 32 | 4.7 | 14[14,000] | -- | -- | 2200 |
| 6.11 | 49 | 4.1 | 14.9[14,900] | -- | -- | 2035 |
| 6.12 | 39 | 5.4 | 13.6[13,600] | -- | -- | 2360 |
| 6.13 | 25 | 2.0 | 5.7[5700] | -- | -- | 1800 |
*=pressure filtration is to remove solid Ca compound
Table 6.6
| OH# (mg KOH/g) | Acid number (mg KOH/g) | Viscosity (Pas@25 ℃) [cps@25 ℃] | Oligopolymer (%) | Monomer (%) | Mn (Da) | |
| 6.14 | 44 | 6.9 | 2.1[2100] | 69 | -- | 1658 |
| 6.15 * | 29 | 2.3 | 1.4[1400] | 69 | -- | 1723 |
| 6.16 ** | 55 | 1.1 | 1.9[1900] | 66 | -- | 1635 |
*=use CaH
2Neutralization
*=neutralize with dicyclohexylcarbodiimide
Embodiment 7: the enhancing oligomeric polyols that is derived from trolamine
Embodiment 7.1 is in being furnished with 12 liters of round-bottomed flasks of agitator, thermopair, temperature regulator and heating jacket, adding from the low dimerization soybean oil of Cargil (7578 grams, 11,470cp), trolamine (219 grams, Dow) and FasCat 4350 (7.8 the gram, Arkema).Reaction mixture is heated to 90-95 ℃, and by applying vacuum and charging into nitrogen with the degassing.Reaction is heated to 170 ℃ then.Viscosity is reducing during the entire reaction, and behind stable viscosity, reaction stops.Unfiltered amber product is for bright and clarifying.Product property sees Table 7.1.
Embodiment 7.2 should be synthetic by carrying out according to embodiment 7.1 described programs with low dimerization soybean oil (7579 gram), trolamine (446 gram) and FasCat 4350 (8.0 gram).Unfiltered amber product is for bright and clarifying.Product property sees Table 7.1.
Be derived from the enhancing oligomeric polyols of Tetraglycol 99 (PEG 200):
Embodiment 7.3 is in being furnished with 5 liters of round-bottomed flasks of agitator, thermopair, temperature regulator and heating jacket, adding from the low dimerization soybean oil of Cargil (2302 grams, 11,470cp), PEG 200 (199 grams, Dow) and FasCat 4350 (2.5 the gram, Arkema).Reaction mixture is heated to 90-95 ℃, and outgases by applying vacuum and charging into nitrogen.Then reaction is heated to 170 ℃ and remain on 170 ℃ following 6 hours, make it be cooled to room temperature afterwards.Unfiltered amber product is for bright and clarifying.Product property sees Table 7.1.
Embodiment 7.4 should be synthetic by carrying out according to embodiment 7.3 described programs with low dimerization soybean oil (2236 restrain), PEG 200 (266 restrain) and FasCat 4350 (2.5 restrain), the reaction times is 4.5 hours.Unfiltered amber product is for bright and clarifying.Product property sees Table 7.1.
Embodiment 7.5 should be synthetic by carrying out according to embodiment 7.3 described programs with low dimerization soybean oil (2168 restrain), PEG 200 (334 restrain) and FasCat 4350 (2.5 restrain), the reaction times is 4.5 hours.Unfiltered amber product is for bright and clarifying.Product property sees Table 7.1.
Table 7.1
1ASTM E1899
2The gel permeation chromatography of using polystyrol standard
Embodiment 8: comprise the preparation and the test of the polyurethane foam that strengthens oligomeric polyols
Stock chart
Triols polyvalent alcohol F3022-petroleum derivation, nominal 3000 molecular weight have the hydroxyl value of 54.3mgKOH/g and the acid number of 0.03mg KOH/g (commodity of trade mark " ARCOL F-3022 " by name originate from Bayer).
Amine BL11-a kind of kicker forms (commodity of trade mark " DABCO BL-11 " by name originate from Air Products) by 70% pair of (dimethylaminoethyl) ether and 30% dipropylene glycol.
Tin K29-stannous octoate catalyst (available from Degussa).
Silicone BF-2370-organic silicon surfactant (originating from Goldschmidt).
TDI-tolylene diisocyanate.
Comprise the foamy preparation of enhancing oligomeric polyols of the present invention and test as described below.
The foam preparation program:
The preparation of A side
The TDI of prescription requirement is weighed in the 50ml plastic beaker, is positioned over and mixes near the station.
The preparation of B side
The 400ml plastic beaker is placed on the electronic balance.Then, the polyvalent alcohol with the prescription requirement is added in the beaker.The organic silicon surfactant and the amine catalyst of the requirement of will filling a prescription then are added in the beaker.Then, tin catalyst and the water with the prescription requirement is added in this batch of material.The temperature of regulating the B side makes that when mixing with polymeric polyisocyanate mixture has 19.2 ℃ ± 0.3 ℃ temperature.With being furnished with 2 ＂ agitating vane (ConnBlade Brand, Model ITC, originate from Conn Mixers Co.) electronics, laboratory under 2340rpm, mixed this batch of material 19 seconds with agitator (Delta ShopMaster brand, Model DP-200,10 inches workshop drilling machines).
The preparation of polyurethane foam
Then, the A side is added into the B side, mixed 6 seconds.Subsequently, with mixture pour into 83 ounces the cup in, it is freely risen.Then, foam and cup are placed 100 ℃ temperature control furnace 15 minutes to solidify.Last at the stove solidified, foam curing is spent the night.After the solidify overnight, foam is regulated 72 hours under 25 ℃ and 50% relative humidity, then test its physicals.Foam formulation and physicals test data are reported in table 8.1-8.2.
Table 8.1
*The synthetic embodiment 6.14 that is similar to
*The synthetic embodiment 6.13 that is similar to
Table 8.2
| Strengthen oligomeric polyols | 6.9 | 6.9 | 6.7 * | 6.7 * | 6.2C ** | 6.2C ** | 6.8A | 6.8A | 6.5 *** | 6.5 *** | |
| OH#(mg KOH/g) | 42.3 | 42.3 | 39.3 | 39.3 | 48.5 | 48.5 | 44.3 | 44.3 | 56.6 | 56.6 | |
| Water (%) | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
| Acid # (mg KOH/g) | 10.6 | 10.6 | 0.3 | 0.3 | 6.2 | 6.2 | 6.7 | 6.7 | 7.3 | 7.3 | |
| Foam formulation | |||||||||||
| Arcol F-3022(pph) | 100 | 80 | 70 | 80 | 70 | 80 | 70 | 80 | 70 | 80 | 70 |
| EOP(pph) | 0 | 20 | 30 | 20 | 30 | 20 | 30 | 20 | 30 | 20 | 30 |
| Water (pph) | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | 3.98 | |
| The TDI index | 105 | 105 | 105 | 105 | 105 | 105 | 105 | 105 | 105 | 105 | 105 |
| Organosilicon (pph) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Amine catalyst (pph) | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 |
| Tin catalyst (pph) | 0.22 | 0.17 | 0.14 | 0.22 | 0.22 | 0.18 | 0.16 | 0.17 | 0.145 | 0.18 | 0.165 |
| Foaming properties | |||||||||||
| Density (lbs/ft 3) | 1.50 | 1.56 | 1.55 | 1.57 | 1.61 | 1.52 | 1.56 | 1.51 | 1.49 | 1.49 | 1.54 |
| Elasticity (%) | 40.2 | 37.3 | 34.3 | 38.3 | 35.5 | 37.8 | 34.5 | 35.5 | 35 | 37.2 | 35.5 |
| 25％IFD(N) | 22.53 | 30.60 | 32.06 | 22.15 | 21.87 | 25.36 | 26.20 | 31.05 | 30.42 | 24.24 | 25.45 |
| 65％IFD(N) | 39.60 | 55.35 | 57.87 | 46.115 | 51.43 | 45.32 | 48.84 | 53.95 | 55.19 | 44.31 | 46.23 |
| Support factor | 1.76 | 1.81 | 1.81 | 2.08 | 2.35 | 1.79 | 1.86 | 1.74 | 1.81 | 1.82 | 1.81 |
| Stretch (kPa) | 128 | 117 | 108 | 58 | 30 | 113 | 101 | 143 | 136 | 114 | 102 |
| Elongation (%) | 250 | 149 | 116 | 92 | 59 | 201 | 172 | 210 | 173 | 216 | 180 |
| Tear (N/m) | 482 | 298 | 240 | 206 | 132 | 406 | 367 | 415 | 384 | 424 | 414 |
| Perm(ft 3/min) | 3.48 | 2.19 | 2.31 | 3.84 | 1.86 | 3.23 | 2.82 | 1.51 | 2.09 | 2.28 | 2.58 |
| 90% compression set | 29.0 | 25.8 | 17.9 | 23.8 | 10.4 | 27.7 | 13.9 | 77.2 | 24.8 | 75.4 | 71.7 |
*The synthetic embodiment 6.7 that is similar to
*The synthetic embodiment 6.2C that is similar to
* *The synthetic embodiment 6.5 that is similar to
For those skilled in the art, according to this specification sheets or practice of the present invention disclosed herein, other embodiment of the present invention is obvious.Variation to embodiment described here is tangible to the technician in the association area of having read wooden specification sheets.The contriver expects that those technician suitably use this and change, and the present invention is obtained and the different enforcement that specifies at this.Therefore, the present invention includes the modification and the equivalent variations of the described theme of claim of whole governing laws permissions.At this whole patents, patent documentation of quoting be disclosed in this and be incorporated herein by reference.Under the situation of conflict, this specification sheets comprises definition, and control will be arranged.
Claims (90)
1. make the method that strengthens oligomeric polyols for one kind, described method comprises the steps:
(a) provide a kind of oligomeric fatty acids ester, this ester comprises at least a glycerin fatty acid ester with at least one lipid acid ester bond; Wherein in described glycerin fatty acid ester, at least about 5% or more ethylidene (
*C=C
*-) during low dimerization reaction be selected from C-with formation
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and its mixture; With
(b) disconnect the described fatty acid glycerine ester bond of at least a portion to form described enhancing oligomeric polyols.
2. the process of claim 1 wherein that described oligomeric fatty acids ester comprises the oligomeric natural oil that is selected from oligomeric vegetables oil and oligomeric animal tallow.
3. the method for claim 2, wherein said oligomeric fatty acids ester prepares by the low dimerization of natural oil, and described natural oil is selected from soybean oil, Thistle oil, oleum lini, Semen Maydis oil, Trisun Oil R 80, sweet oil, Canola oil, sesame oil, cottonseed oil, plam oil, rapeseed oil, tung oil, peanut oil, Viscotrol C, leprosy seed oil, fish oil, lard, tallow and composition thereof.
4. the process of claim 1 wherein that described oligomeric fatty acids ester prepares by the low dimerization of chemistry.
5. the process of claim 1 wherein that described oligomeric fatty acids ester prepares by the low dimerization of anaerobic heat.
6. the process of claim 1 wherein that described oligomeric fatty acids ester prepares by being selected from following method:
(a) at high temperature, fatty acid ester is carried out the low dimerization of anaerobic heat to produce siccative oil;
(b) with alcohol epoxidized fatty acid ester is carried out the low dimerization of open loop;
(c) epoxidized fatty acid ester is carried out the low dimerization of positively charged ion catalysis open loop; (with compatible)
(d) exist
Acid or Lewis acid catalyst hang down dimerization to fatty acid ester under existing;
(e) with the crosslinked fatty acid ester of sulphur compound; With
(f) fatty acid ester of the crosslinked hydroxyl-functional of usefulness hydroxyl activity linking agent.
7. the process of claim 1 wherein that described oligomeric fatty acids ester comprises hydroxyl.
8. the method for claim 7, wherein said oligomeric fatty acids ester comprises primary hydroxyl.
9. the process of claim 1 wherein that described oligomeric fatty acids ester comprises the blend of glycerin fatty acid ester.
10. the process of claim 1 wherein that described oligomeric fatty acids ester comprises:
(a) the dryness natural oil for preparing by the low dimerization of anaerobic heat;
(b) the oligomeric fatty acids ester for preparing of epoxidation and the open loop by fatty acid ester; Or
(c) its mixture.
11. the process of claim 1 wherein that the peroxide value (PV) of described oligomeric fatty acids ester is less than about 50.
12. the process of claim 1 wherein that the peroxide value (PV) of described oligomeric fatty acids ester is less than about 30.
13. the process of claim 1 wherein that the peroxide value (PV) of described oligomeric fatty acids ester is less than about 10.
14. the process of claim 1 wherein that described oligomeric fatty acids ester comprises residual epoxide group.
15. the process of claim 1 wherein that described oligomeric fatty acids ester comprises residual olefin group.
16. the process of claim 1 wherein that the number-average molecular weight (Mn) of described oligomeric fatty acids ester is the about 6000Da of about 1500Da-.
17. the process of claim 1 wherein that the weight-average molecular weight (Mw) of described oligomeric fatty acids ester is the about 20000Da of about 2000Da-.
18. the method for claim 7, wherein said oligomeric fatty acids ester has hydroxyl value; Has hydroxyl value with wherein said enhancing oligomeric polyols; With the hydroxyl value of wherein said enhancing oligomeric polyols than the hydroxyl value height of described oligomeric fatty acids ester at least about 10%.
19. the method for claim 18, the hydroxyl value of wherein said enhancing oligomeric polyols than the hydroxyl value height of described oligomeric fatty acids ester at least about 20%.
20. the process of claim 1 wherein that described oligomeric fatty acids ester has the primary hydroxyl functionality; Has the primary hydroxyl functionality with wherein said enhancing oligomeric polyols; Wherein compare with described oligomeric fatty acids ester, step (b) has increased the primary hydroxyl functionality of described enhancing oligomeric polyols.
21. the process of claim 1 wherein at least 10% or the fatty acid glycerine ester bond that more is present in the described oligomeric fatty acids ester in described enhancing oligomeric polyols, remain unchanged.
22. the process of claim 1 wherein at least 30% or the fatty acid glycerine ester bond that more is present in the described oligomeric fatty acids ester in described enhancing oligomeric polyols, remain unchanged.
23. the process of claim 1 wherein at least 50% or the fatty acid glycerine ester bond that more is present in the described oligomeric fatty acids ester in described enhancing oligomeric polyols, remain unchanged.
24. the method for claim 1, wherein step (b) comprises the reaction of described oligomeric fatty acids ester and nucleophilic reagent, and described nucleophilic reagent is selected from monohydroxy-alcohol, dibasic alcohol, polyvalent alcohol, sugar alcohol, ethylene glycol, polyalkylene glycol, monoamine, diamine, polyamine, alkanolamine, mercaptan and composition thereof.
25. the method for claim 1; wherein step (b) comprises the reaction of described oligomeric fatty acids ester and nucleophilic reagent; described nucleophilic reagent is selected from ethylene glycol; Diethylene Glycol; triethylene glycol; polyoxyethylene glycol; thanomin; diethanolamine; trolamine; amine-terminated polyether; 1; the 2-propylene glycol; 1; ammediol; 1; the 2-butyleneglycol; 1; the 4-butyleneglycol; 1; the 2-cyclohexanediol; dipropylene glycol; polypropylene glycol; the ethoxylation triol; the propoxylation triol; poly-(1; the 4-butyleneglycol); 2; 3-dihydroxyl dioxane; 1; the 4-xylenediol; glycerine; Polyglycerine; sorbyl alcohol; tetramethylolmethane; TriMethylolPropane(TMP); 1; 1, the 2-trimethylolethane; Viscotrol C; ethoxylated castor oil; the polyvalent alcohol of making by hydroformylation natural oil; alcohol open loop vegetable oil polyol; polyvalent alcohol based on terephthalic acid; polyester polyol; its combination; and composition thereof.
26. the step of the process of claim 1 wherein (b) comprises transesterify.
27. the step of the process of claim 1 wherein (b) comprises hydrogenation.
28. the step of the process of claim 1 wherein (b) comprises amidation.
29. the step of the process of claim 1 wherein (b) comprises amidation and transesterify.
30. the method for claim 28, wherein said amidation is carried out with polyamine.
31. the method for claim 30, wherein said polyamine has general formula:
H
2N-R-NH
2
Wherein R is fat group or aromatic group.
32. the method for claim 30, wherein said polyamine are the polyalkylene glycol diamines.
33. the method for claim 32, wherein said polyalkylene glycol diamines is polytetramethylene glycol diamines, polypropylene glycol diamine, polyethylene glycol diamines and composition thereof.
34. the method for claim 30, wherein said polyamine are the amine end groups polypropylene glycol diamine.
35. the method for claim 34, wherein said amine end groups polypropylene glycol diamine is expressed from the next:
H
2N-[-CH(-CH
3)-CH
2-O-]
x-CH
2-CH(-CH
3)-NH
2
Wherein x is about 2-about 70.
36. the method for claim 35, the molecular weight of wherein said amine end groups polypropylene glycol diamine is the about 4000Da of about 200Da-.
37. the method for claim 30, wherein said polyamine compound comprises polyethylene glycol diamines.
38. the method for claim 32, wherein said polyalkylene glycol diamines is expressed from the next:
H
2N-CH(-CH
3)-CH
2-[-O-CH
2-CH(-CH
3)-]
x-[O-CH
2-CH2-]
y-[-O-CH
2-CH(-CH
3)-]
z-NH
2
Wherein y is about 2-about 40; (x+z) be about 1-about 6; And the molecular weight of this diamines is the about 2000Da of about 200-.
39. the method for claim 30, wherein said polyamine is expressed from the next:
H
2N-(CH
2)
x-O-CH
2-CH
2-O-(CH
2)
x-NH
2
Wherein x is about 2-3; And molecular weight is the about 180Da of about 140-.
40. the process of claim 1 wherein that described enhancing oligomeric polyols comprises primary hydroxyl.
41. the process of claim 1 wherein that described enhancing oligomeric polyols comprises the oligopolymer of the about 70 weight % of about 10 weight %-.
42. the process of claim 1 wherein that the acid number (AV) of described enhancing oligomeric polyols is less than about 5mgKOH/g.
43. the process of claim 1 wherein that the number-average molecular weight (Mn) of described enhancing oligomeric polyols is the about 6000Da of about 1200Da-.
44. the process of claim 1 wherein that the weight-average molecular weight (Mw) of described enhancing oligomeric polyols is about 20 for about 2000Da-, 000Da.
45. the process of claim 1 wherein when when measuring down for 25 ℃, the viscosity of described enhancing oligomeric polyols be about 20Pas (20,000cps) or lower.
46. the process of claim 1 wherein that the number average hydroxy functionality (Fn) of described enhancing oligomeric polyols is about 1.0 or higher.
47. the enhancing oligomeric polyols of making by the method for one of claim 1-46.
48. make the method that strengthens oligomeric polyols for one kind, it comprises:
(a) provide a kind of anaerobic to hang down the dimerization fatty acid ester, this ester comprises the fatty acid glycerine ester bond; With
(b) disconnect the described fatty acid glycerine ester bond of at least a portion to form described enhancing oligomeric polyols.
49. the method for claim 48, wherein said method comprises the steps:
(a) provide natural oil;
(b) anaerobic heats described natural oil so that its low dimerization forms the low dimerization natural oil of anaerobic heat; With
(c) the low dimerization natural oil of the described anaerobic heat of amidation is to form described enhancing oligomeric polyols.
50. the method for claim 49, wherein said amidation is carried out with monoamine, diamine, polyamine, alkanolamine or its mixture.
51. the method for claim 50, wherein said amidation is carried out with polyamine.
52. the method for claim 51, wherein said polyamine has following formula:
H
2N-R-NH
2
Wherein R is fat group or aromatic group.
53. the method for claim 51, wherein said polyamine are the polyalkylene glycol diamines.
54. the method for claim 53, wherein said polyalkylene glycol diamines is polytetramethylene glycol diamines, polypropylene glycol diamine, polyethylene glycol diamines and composition thereof.
55. the method for claim 51, wherein said polyamine are the amine end groups polypropylene glycol diamine.
56. the method for claim 55, wherein said amine end groups polypropylene glycol diamine is expressed from the next:
H
2N-[-CH (CH
3)-CH
2-O-]
x-CH
2-CH (CH
3)-NH
2Wherein x is about 2-about 70.
57. the method for claim 56, the molecular weight of wherein said amine end groups polypropylene glycol diamine is the about 4000Da of about 200Da-.
58. the method for claim 51, wherein said polyamine is a polyethylene glycol diamines.
59. the method for claim 53, wherein said polyalkylene glycol diamines is expressed from the next:
H
2N-CH(-CH
3)-CH
2-[-O-CH
2-CH(-CH
3)-]
x-[O-CH
2-CH
2-]
y-[-O-CH
2-CH(-CH
3)-]
z-NH
2
Wherein y is about 2-about 40; (x+z) be about 1-about 6; And the molecular weight of this diamines is the about 2000Da of about 200-.
60. the method for claim 51, wherein said polyamine is expressed from the next:
H
2N-(CH
2)
x-O-CH
2-CH
2-O-(CH
2)
x-NH
2
Wherein x is about 2-3; And molecular weight is the about 180Da of about 140-.
61. the method for claim 48, wherein said enhancing oligomeric polyols comprises primary hydroxyl.
62. the method for claim 48, wherein said method comprises the steps:
(a) provide natural oil;
(b) anaerobic heats described natural oil so that its low dimerization forms the low dimerization natural oil of anaerobic heat; With
(c) the low dimerization natural oil of the described anaerobic heat of transesterify is to form described enhancing oligomeric polyols.
63. the method for claim 62, the peroxide value (PV) of the low dimerization fatty acid ester of wherein said anaerobic is lower than about 50.
64. the method for claim 62, wherein said transesterify is carried out with monohydroxy-alcohol, dibasic alcohol, polyvalent alcohol, sugar alcohol, ethylene glycol, polyalkylene glycol or its mixture.
65. the method for claim 48, the low dimerization fatty acid ester of wherein said anaerobic comprises the glycerin fatty acid ester with fatty acid glycerine ester bond; Wherein in described glycerin fatty acid ester, at least about 5% or more ethylidene (
*C=C
*-) during low dimerization reaction form and be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and composition thereof.
66. make the method that strengthens oligomeric polyols for one kind, it comprises:
(a) provide a kind of chemistry to hang down the dimerization fatty acid ester, this ester has the fatty acid glycerine ester bond; With
(b) disconnect the described fatty acid glycerine ester bond of at least a portion to form described enhancing oligomeric polyols.
67. the method for claim 66, wherein said method comprises the steps:
(a) provide natural oil;
(b) the low described natural oil of dimerization of chemistry is so that its low dimerization forms the low dimerization natural oil of chemistry; With
(c) the low dimerization natural oil of the described chemistry of amidation is to form described enhancing oligomeric polyols.
68. the method for claim 67, wherein said amidation is carried out with monoamine, diamine, polyamine, alkanolamine or its mixture.
69. the method for claim 67, wherein said amidation is carried out with polyamine.
70. the method for claim 69, wherein said polyamine has following formula:
H
2N-R-NH
2
Wherein R is fat group or aromatic group.
71. the method for claim 69, wherein said polyamine are the polyalkylene glycol diamines.
72. the method for claim 71, wherein said polyalkylene glycol diamines is polytetramethylene glycol diamines, polypropylene glycol diamine, polyethylene glycol diamines and composition thereof.
73. the method for claim 69, wherein said polyamine are the amine end groups polypropylene glycol diamine.
74. the method for claim 73, wherein said amine end groups polypropylene glycol diamine is expressed from the next:
H
2N-[-CH(-CH
3)-CH
2-O-]
x-CH
2-CH(-CH
3)-NH
2
Wherein x is about 2-about 70.
75. the method for claim 74, the molecular weight of wherein said amine end groups polypropylene glycol diamine is the about 4000Da of about 200Da-.
76. the method for claim 69, wherein said polyamine is a polyethylene glycol diamines.
77. the method for claim 71, wherein said polyalkylene glycol diamines is expressed from the next:
H
2N-CH(-CH
3)-CH
2-[-O-CH
2-CH(-CH
3)-]
x-[O-CH
2-CH
2-]
y-[-O-CH
2-CH(-CH
3)-]
z-NH
2
Wherein y is about 2-about 40; (x+z) be about 1-about 6; And the molecular weight of this diamines is the about 2000Da of about 200-.
78. the method for claim 69, wherein said polyamine is expressed from the next:
H
2N-(CH
2)
x-O-CH
2-CH
2-O-(CH
2)
x-NH
2
Wherein x is about 2-3; And molecular weight is the about 180Da of about 140-.
79. the method for claim 66, wherein said enhancing oligomeric polyols comprises primary hydroxyl.
80. the method for claim 66, wherein said method comprises the steps:
(a) provide natural oil;
(b) the low described natural oil of dimerization of chemistry is so that its low dimerization forms the low dimerization natural oil of chemistry; With
(c) the low dimerization natural oil of the described chemistry of transesterify is to form described enhancing oligomeric polyols.
81. the method for claim 80, wherein said transesterify is carried out with monohydroxy-alcohol, dibasic alcohol, polyvalent alcohol, sugar alcohol, ethylene glycol, polyalkylene glycol or its mixture.
82. the method for claim 66, the low dimerization fatty acid ester of wherein said chemistry comprises the glycerin fatty acid ester with fatty acid glycerine ester bond; Wherein in described glycerin fatty acid ester, at least about 5% or more ethylidene (
*C=C
*-) during low dimerization reaction form and be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and composition thereof.
83. a method of making polymkeric substance, it comprises the steps:
(a) provide the oligomeric fatty acids ester; Wherein said oligomeric fatty acids ester comprises at least a glycerin fatty acid ester with at least one lipid acid ester bond; Wherein in described glycerin fatty acid ester, at least about 5% or more ethylidene (
*C=C
*-) during low dimerization reaction form and be selected from C-
*C-C
*-C, O-
*C-C
*-O, C=
*C-C
*The bonding structure of-C and composition thereof;
(b) disconnect the described fatty acid glycerine ester bond of at least a portion and strengthen oligomeric polyols to form; With
(c) with the reactant reaction of described enhancing oligomeric polyols and at least a mixture that is selected from vulcabond, polymeric polyisocyanate, diacid, polyacid, formation carbonate, carbonyl dimidazoles, dialkyl carbonate and composition thereof, to make described polymkeric substance.
84. the polymkeric substance of making by the method for claim 83.
85. the polymkeric substance of claim 84, wherein said polymkeric substance comprises urethane.
86. the polymkeric substance of claim 85, wherein said urethane comprises foam, coating, tackiness agent, elastomerics or sealing agent.
87. the polymkeric substance of claim 86, wherein said urethane are block foam or molded foam.
88. the polymkeric substance of claim 87, wherein said urethane is soft.
89. the polymkeric substance of claim 85, wherein said urethane is hard.
90. the polymkeric substance of claim 83, wherein said polymeric polyisocyanate comprise 2,4 toluene diisocyanate (TDI), 2,6-tolylene diisocyanate (TD1), 4,4 '-'-diphenylmethane diisocyanate (MD1) and composition thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79532706P | 2006-04-27 | 2006-04-27 | |
| US60/795,327 | 2006-04-27 | ||
| US60/859,337 | 2006-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101437864A true CN101437864A (en) | 2009-05-20 |
Family
ID=40711606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800151599A Pending CN101437864A (en) | 2006-04-27 | 2007-04-27 | Enhanced oligomeric polyols and polymers made therefrom |
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| Country | Link |
|---|---|
| CN (1) | CN101437864A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122196A (en) * | 2013-01-31 | 2013-05-29 | 北京化工大学常州先进材料研究院 | Preparation of thermoset coating prepolymer based on vegetable oil epoxidation modification |
| CN107778630A (en) * | 2017-11-02 | 2018-03-09 | 浙江万里新材料科技有限公司 | A kind of crosslinked polyethylene foam material and preparation method thereof |
| CN108165214A (en) * | 2018-01-03 | 2018-06-15 | 浙江恒劲树脂有限公司 | A kind of reflective preparation process for taking polyurethane resin composite glue |
| CN111087591A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Process for reducing the content of cyclic oligomers in polyesters |
| CN111253995A (en) * | 2020-02-28 | 2020-06-09 | 上海壹萨化学科技有限公司 | Animal and vegetable oil high-pressure hydrolysis epoxidation modified additive for metal working fluid |
-
2007
- 2007-04-27 CN CNA2007800151599A patent/CN101437864A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122196A (en) * | 2013-01-31 | 2013-05-29 | 北京化工大学常州先进材料研究院 | Preparation of thermoset coating prepolymer based on vegetable oil epoxidation modification |
| CN107778630A (en) * | 2017-11-02 | 2018-03-09 | 浙江万里新材料科技有限公司 | A kind of crosslinked polyethylene foam material and preparation method thereof |
| CN108165214A (en) * | 2018-01-03 | 2018-06-15 | 浙江恒劲树脂有限公司 | A kind of reflective preparation process for taking polyurethane resin composite glue |
| CN111087591A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Process for reducing the content of cyclic oligomers in polyesters |
| CN111253995A (en) * | 2020-02-28 | 2020-06-09 | 上海壹萨化学科技有限公司 | Animal and vegetable oil high-pressure hydrolysis epoxidation modified additive for metal working fluid |
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