WO2011018161A1

WO2011018161A1 - Compounds for quenching reactive metal catalytic species remained in polyester polyol resins, quenching process and its application in polyurethane production therein

Info

Publication number: WO2011018161A1
Application number: PCT/EP2010/004613
Authority: WO
Inventors: Amin Cao; Yanchun Liu; Xinsuo Fan; Sharong Xudong Feng; Peter Schmitt; Zhiping Zhou
Original assignee: Bayer Materialscience Ag
Priority date: 2009-08-11
Filing date: 2010-07-28
Publication date: 2011-02-17
Also published as: CN101993529A

Abstract

A method to produce polyester polyol resin with quenched or deactivated residual catalytic metal ion species therein is disclosed. Feature organic compounds of macrocyclic ethers, alkyl and/or aryl substituted phoshine, alkyl and/or aryl substituted phosphine oxides, alkyl and/or aryl substituted phosphine sulfides, alkyl and/or aryl substituted quaternary ammonium halide salts are used as effective deactivation compounds to quench the unfavorable activities of residual metal ion species originated from the metal Lewis acid catalyst(s) during a continuous two-step process of polyester polyol production. Two deactivation processes denoted as the pre-deactivation process and the post-deactivation process are also disclosed. The polyester polyol resin product of present invention may be used as active-hydrogen atoms containing raw material for successive production of diverse two-component based polyurethane with decreased -OH/-NCO adduction rates, better color appearances and improved product qualities.

Description

Compounds for Quenching Reactive Metal Catalytic Species Remained in Polyester Polyol Resins, Quenching Process and Its Application in Polyurethane Production Therein

Field of the Invention

This invention relates to functional organic compounds of macrocyclic ethers, alkyl and/or aryl substituted phoshine, alkyl and/or aryl substituted phosphine oxides, alkyl and/or aryl substituted phosphine sulfides, alkyl and/or aryl substituted quaternary ammonium halide salts, aiming at efficient deactivation of reactive metal catalytic species remained in the polyester polyol resins. This invention also relates to quenching processes to deactivate the residual catalytic metal species in polyester polyol resins for subsequent conventional two-component polyurethane production with favorable color appearance and cross-linking rates. The above-said polyester polyol resins including deactivated catalytic metal species may be useful as active-hydrogen containing raw materials for fabricating a variety of ultimate polyurethane products in the areas of organic coatings, paints, polymer forms, thermal plastics, adhesives and sealants with improved properties.

Background and Description of the Related Art

Since polyurethane has been known to have excellent oil or solvent resistance, friction resistance, chemical corrosion resistance properties and long-term weather durability as well as favorable mechanical performance, it has nowadays been becoming one of the most important category of conventional synthetic polymer materials which can be applied for a broad area as functional organic coatings, paints, rigid and/or soft porous forms, thermal plastics, flexible synthetic fibers, adhesives and sealants and so forth. In general, conventional polyurethane resins were produced with simply mixing two necessary kinds of reactive starting raw components: (a) difunctional and/or polyfunctional active hydrogen atoms(-OH, -NH₂, -NH- groups etc) containing organics such as small molecular polyols or oligomeric polyols like polyester or polyether or polycarbonate polyols bearing appropriate molecular weights, and multifunctional organic amines and so forth; (b)difunctional and/or multifunctional isocyanates with functional -NCO groups which can react with active hydrogen atoms of the former component, thus to form urethane or urea linkages of the adducts and final chain-extended polymeric chain structures.

With regard to the active-hydrogen atoms containing components of multifunctional polyols or polyamines, diverse categories and grades of active-hydrogen atoms containing polyester polyols have been recognized as the important kinds of isocyanate-reactive polyol resins for two-component based polyurethane production. On one hand, it has been well-known that during the production of polyester polyol resins via condensation polymerization process, a large number of esterification and transesterification catalysts have been developed and thereby applied to accelerate the industrial polyester polyol resin synthetic process under high conduction temperatures for better efficiencies, and catalysts such as metals, metal alkoxides, metal oxides and organic Lewis acids and so forth were widely employed for the above-condensation polymerization of mixed raw materials comprising an aliphatic diol and at least an aliphatic dicarboxylic acid derivative compounds from an aliphatic dicarboxylic acid, a diester of aliphatic dicarboxylic acid, an aliphatic anhydride, and an auxiliary aliphatic hydroxyl carboxylic acid or an optional polyol. On the other hand, after the industrial production of polyester polyol resins, the employed catalysts as remained species will however be spontaneously present with various concentrations, strongly depending on their catalytic activities and necessary feeding amounts. These residual catalytic species, particularly the metal Lewis catalytic species like Ca(II), Mg(II)₅Sn(H), Sn(IV), Iron(II), Iron(III), Ti(rV),Ge(IV) Al(III) and other transition and rare-earth metal ions etc, will again catalyze unfavorable thermal depolymerization and coloration via reaction with other functional additives during thermal processing of the polyester and in-situ production of polyurethane resins, and accelerate -OH/-NCO adduction rates in an uncontrollable manner, and this will lead to easy cross-linking, gelation and much shortened pot-life and difficulties in handling the application systems like organic coatings, paints, forms. Therefore, it becomes important to find possible compounds and process to efficiently deactivate the remained catalytic species in the as-synthesized polyester polyol resins after the industrial polyester polyol production for successive higher quality polyurethane products. In order to quench or deactivate catalytic species remained in the catalyzed polycondensation products of either high molecular weight polyesters or oligomeric polyester polyols, for instance, Japanese patent (publication no. H6-256492) disclosed a method to purify the poly(hydroxy carboxylic acid)s like poly(l-lactic acid) and its copolymers with first introducing hydrogen chloride gas into the their polymer solution employing organic solvent, and successive separating the polymers with additional precipitating reagents, and most of the remained metal catalytic species of Sn²⁺ ions as toxic impurities were separated. In addition, patents JP Publication Nos. H9-40766, H9-110967, P2005-65771, P2006-182999, P2006-16322 and patent EP0644219A1 separately disclosed new similar physical processes to deactivate the residual metal catalytic ion species in the high molecular weight aliphatic polyester resins with a combination of different organic solvents and organic acids like phosphoric acid, however either preliminary dissolving the polyester resins in their good solvents or preparation of their microparticle solids was necessary, and this would lead to high practical cost of industrial production process, particularly this will become more complicated when these deactivation processes via separation purification were employed for low molecular weight polyester polyol resins with high polarities. With regard to industrial polyester synthesis, PCT patent WO 97/44376 disclosed a method for catalyst deactivation in continuous poly(ethylene terephthalate) PET production with phosphorus stabilizers for less acetaldehyde byproducts and enhanced thermal stability and color. Most recently, US patent(application no.20070066791Al) revealed some phosphorus compounds of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, carboxy phosphonic acid and their salts and ester derivatives, could deactivate the metal catalytic species to decrease the level of acetaldehyde byproduct through adding into the polyester melt either late in the polycondensation or upon remelting a solid polyester product. Patent US4401804 disclosed a deactivation process to quench residual catalytic species of Ti and Mn metal ions in aromatic polyester products by the use of a combination of the phosphonate or phosphate derivatives. Alternatively, for a polycarbonate polyol based two-component polyurethane production system, Kashiwaki et al (Patent JP publication no. P2003-206331A) suggested a simple process to in-situ deactivate the catalytic metal Ti(FV) ion species remained in the polycarbonate polyols via a combination of triester phosphite such as tributyl phosphite, trimethyl phophite and triphenyl phosphite and so forth as quenching compounds, and an appropriate conduction temperature of 70-145Q. Moreover, Doshi et al (Patent US4341689) disclosed a two-component polyurethane system with favorable extended pot-life and rapid curing, and its second polyisocyanate component in solution containing organotin as the subsequent -OH/-NCO adduction accelerator which was first quenched by the deactivator of acetic acid or formic acid. Additionally, PCT patent WO96/23826 suggested a characteristic deactivator of hindered hydrazine or hindered phenolic oxamide to quench the residual catalytic species of Sn²⁺or Sn⁴⁺ metal ions for rigid thermal plastic polyurethane resins with improve melt strength. In a view of above disclosures, more efficient state-of- art deactivator and easier handling low-cost process are however practically demanded for industrial production of the isocyanate-reactive polyester polyol resins with improved polyurethane product qualities.

Object and Summary of the Invention

To overcome the above problems, it is, therefore, an object of this invention to provide a series of functional organic compounds and their possible combination mixtures which are capable of efficiently quenching or deactivating unfavorable catalytic metal ion species remained the polyester polyol resins as one component of the necessary raw materials for conventional two-component polyurethane production.

It is further an object of present invention to provide related chemical processes and methods to quench or deactivate the catalytic metal ion species remained in the obtained polyester polyol resins during their production.

It is further another object of present invention to provide possible application of the above active deactivators and related chemical quenching processes for two-component polyurethane resin production with decreased cross-linking speeds and controllable gelation rates.

It is further an object of present invention to provide the efficient quenching compounds and their combinations and related chemical deactivating processes without adversely affecting the color of the polyester polyol and successive two-component polyurethane resin products which can be further applied for final production such as coatings, thermoplastic moldings, adhesives, sealants and so forth.

It is further an object of present invention to provide a method to produce active-hydrogen atoms containing difunctional and/or multifunctional polyester polyol resins with preferred molecular weights of 1000-5000, and irreversibly quenched or deactivated catalytic metal ion species therein. To accomplish the above objects, the present invention provides deactivators for residual catalytic metal ion species and related chemical quenching processes to produce polyester polyol resins through polycondensation under high carrying-out temperatures from starting raw materials which can be selected from the compound group consisting of

(Al)Mixtures of an aliphatic diol and/or an aliphatic polyol and at least an aliphatic dicarboxylic acid derivative which can further be selected from an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid anhydride, a diester of an aliphatic dicarboxylic acid,

(A2)Aliphatic hydroxyl carboxylic acid and its cyclized condensation product of aliphatic cyclic lactone compound,

(A3)Optional or auxiliary aromatic dicarboxylic acids and their anhydrides and diester derivatives with at least two reactive functional groups,

(A4)Mixtures of Al and A2,

(A5)Mixtures of Al and A3,

(Aό)Mixtures of Al and A2 and A3,

(A7)Prepolymers of mixture Al,

(A8)Prepolymers of mixture A2,

(A9)Prepolymers of mixture Al and A2,

(AlO)Prepolymers of mixture Al and A3,

(All)Prepolymers of mixture Al and A2 and A3.

These and other objects, features and merits of this invention will become more apparent upon taking detailed description of the preferred embodiments as following into consideration. - -

Detailed Description of the Preferred Embodiments of the Invention

The low molecular polyester polyol or polyester polyol prepolymer resins of the present invention is generally produced by condensation polymerization from the mixture of starting raw chemical compounds selected candidate compounds from Al through All,and the illustrative of molecular structures for the obtained polyester polyols may be represented by formula (1) or (2)

( 2 )

wherein the Ri represents a divalent saturated aliphatic group, or a divalent unsaturated aliphatic group, or a divalent cyclic aliphatic group, which comprises 0~l2 carbon atoms, preferably comprises O—IO carbon atoms, most preferably comprises 0~8 carbon atoms, and Ri may also optionally be a divalent aryl group consisting of 6~lO carbon atoms, most preferably 6~8 carbon atoms such as phenyl, tolyl. R₂ represents a divalent saturated or unsaturated aliphatic group, or a divalent cyclic aliphatic group, which is consisted of 2-12 carbon atoms, more preferably consisted of 2-10 carbon atoms, and most preferably consisted of 2-8 carbon atoms, or an optional aliphatic oxyalkylene group containing ether linkage which may be CH₂CH₂OCH₂CH₂, CH₂CH₂OCH₂CH₂OCH₂CH₂. R₃ represents a divalent aliphatic group which may be aliphatic alkylene group comprising 2-5 carbon atoms, or a divalent oxyalkylene group like CH₂CH₂OCH₂.

The polyester polyols obtained in accordance with the method of present invention may be produced from starting materials selected from following organic compounds.

Starting raw materials Al is a mixture of an aliphatic alcohol bearing at least two functional hydroxyl groups, and at least an aliphatic dicarboxylic acid derivative which can further be selected from an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid anhydride, or a diester derivative of an aliphatic dicarboxylic acid, and the related molecular structures can be represented by the following formula (3) and (4)

(3) (4)

Wherein the R₄ and R₅ express divalent saturated or unsaturated aliphatic groups, or divalent cyclic aliphatic groups, which comprises 0-12 carbon atoms, preferably comprises 0-10 carbon atoms, most preferably comprises 0-8 carbon atoms, and the R₄ and R₅ may also optionally be a divalent aryl group consisting of 6~10 carbon atoms, most preferably 6—8 carbon atoms such as phenyl, tolyl like terephthalic acid. R_4I represents hydrogen atom, lower alkyl functional group preferably consisting of 1-6 carbon atoms, an aryl functional group like phenyl.

Illustrative of aliphatic dicarboxylic acids are oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, their diester derivatives like dimethyl ester, diethyl ester, dibutyl ester, diphenyl ester, or their anhydrides thereof.

As the necessary combination of the condensation polymerization mixture, an aliphatic alcohol having at least two reactive hydroxyl groups may be represented by the following molecular formula (5)

HO OH

(5)

wherein R₆ represents a divalent saturated or unsaturated aliphatic group, or a divalent cyclic aliphatic group, which is consisted of 2-12 carbon atoms, more preferably consisted of 2— 10 carbon atoms, and most preferably consisted of 2-8 carbon atoms, or an optional aliphatic oxyalkylene group containing feature ether linkage such as CH₂CH₂OCH₂CH₂, CH₂CH₂OCH₂CH₂OCH₂CH₂. Specific examples of the said aliphatic alcohol having at least two reactive hydroxyl groups may be ethylene glycol, 1,3-propane diol, 1,2-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, dihydroxyl methyl cyclohexane, 1,7-hepatne diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, 1,12-dodecane diol, glycerin, neopentyl glycol, pentaerythritol, l,r,l "-tris(hydroxymethyl)propane, sorbitol, aliphatic diol with two reactive hydroxyl groups such as dihydroxyethyl disulfide HOCH₂CH₂SSCH₂CH₂OH, HOCH₂CH₂OCH₂CH₂OH, HOCH₂CH₂OCH₂CH₂OCH₂CH₂OH,

HOCH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂OH. AS for the aliphatic alcohol having more than two hydroxyl groups is generally used with a feeding molar ratio to preferably be 0.001-0.5mol% of total alcohol reactants in the condensation mixture from Al through A3, to more preferably be 0.01-0.3 mol% to avoid cross-linking and earlier gelation during the polyester polyol production.

Another starting material A2 may be a two functional aliphatic hydroxyl carboxylic acid and its cyclized product. Illustrative of two functional aliphatic hydroxyl carboxylic acids and their cyclized products are (Z-)-lactic acid, (J-)-lactic acid, racemic lactic acid, glycolic acid, glycolide, (Z-)-lactide, (J-)-lactide, racemic lactide, D-butyrolactone,D-butyrolactone, D-caprolactone, D-valerolactone, D-valerolactone^-l^-dioxan^-one.

Raw materials A3 of optional or auxiliary aromatic dicarboxylic acids and their anhydrides and diester derivatives with at least two functional groups may be a terephthalic acid, a 4-methyl phthalic acid, or their anhydride and diester derivatives. The optional or auxiliary aromatic dicarboxylic acids and their anhydrides and diester derivatives are generally used in such an amount that the aromatic comonomer content in the product polyester polyol resin is not greater than 50 mol%, and preferably no more than 40 mol%.

In one embodiment of present invention, the polyester polyol resin was produced through a two-step process. In the first stage, the selected raw material mixture was subjected to esterification and/or transesterifϊcation reaction under flowing dry nitrogen gas and an elevated temperature. The reaction of esterification and/or transesterification under a pressure of atmosphere is carried out at a step reaction temperature of 100-300D, more preferably at a step reaction temperature of 120-2500, and a reactor having distillation column and byproduct separation facility is preferably used. The feeding molar ratio of hydroxyl to dicarboxylic acid and its derivative in the starting raw materials is generally used as 0.8-4.0, more preferably as 0.9-2.5, and most preferably as 0.9-1.6. When the byproduct of water and/or volatile alcohol reaches 95% of its theoretically calculated amount, the as-said first step reaction proceeds to the second step of condensation polymerization to eliminate volatile alcohol byproduct(s) under reduced pressure and high temperature. The condensation polymerization is continuously performed preferably at a reaction temperature of 140-350D, more preferably at a reaction temperature of 160-280 D. The vacuum of condensation polymerization is generally used at 0.1~5^χ l0⁴ Pa, more preferably at l~5* 10⁴ Pa, and most preferably at 10-1.5*10³ Pa.

In another embodiment of the present invention, to accelerate the above ester exchanging and polycondensation reaction, a metal Lewis acid or a combinationary mixture is generally used as the catalyst. The metal catalyst may be an alkoxide, acetate, acetyl acetonate, alkyl, oxide, and chloride derivative of an alkaline metal, an alkaline earth metal, a main group IV metal, a transition metal, a rare earth metal. Illustrative of the above metal Lewis acids are titanium acetate, titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, Stannous oxide, tin(II) chloride, tin(FV) chloride, stannous oxalate, stannous octoate, dibutyl tin(IV) oxide, dibutyl tin laurate, antimony trioxide, germanium oxide, germanium tetrabutoxide, germanium tetraisopropoxide, diethyl zinc, lanthanum acetate, samarium acetate, europium acetate, zinc acetate, ytterbium acetate, zinc acetylacetonate, magnesium ethoxide, magnesium acetate, magnesium tert-butoxide, magnesium methoxide, magnesium chloride, calcium acetate, iron(II)oxalate, iron(II) acetate, zirconium acetate, zirconium acetylacetonate, trimethyl aluminum, trimethyl aluminum, aluminum triisopropoxide. In accordance with the present invention, the use of organometallic tin and titanium Lewis acids is particularly more preferred.

The as-said catalyst or a combination mixture may be used during the first process step of esterification and/or transesterification or at the beginning of the second process step of condensation polymerization after the removal of water and/or volatile alcohol byproduct with a feeding molar ratio of as-said metal Lewis acid catalyst to total carboxylic functional groups in raw material mixture equal to be 0.001%~10%, more preferably be O.OO5%~5%, and most preferably be 0.01%~2.0%. The use of above metal Lewis acid catalyst at the beginning of the second condensation reaction is more preferred for the reasons to keep its high catalytic activity and good color and transparency of the obtained polyester polyol products

hi a further embodiment, the as-obtained polyester polyol resin for subsequent two-component polyurethane production generally appears as milky color wax-state solids with acid value less than 5 mgKOH/g, and molecular weight of the as-said polyester polyol may be 500-50000, more preferably be 1000-10000, and particularly most preferably be 1000-5000 for the reasons of appropriate viscosity of its melt and easy handling during the successive production of two-component polyurethane.

Illustrative of the polyester polyol products in accordance with the present invention may be poly(ethylene oxalate), poly(propylene oxalate), poly(butylene oxalate), poly(hexamethylene oxalate), poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), poly(hexamethylene succinate), poly(octylene succinate), poly(ethylene adipate), poly(propylene adipate), poly(butylene aipate), poly(hexamethylene adipate), poly(octylene adipate), poly(ethylene azelaate), poly(butylene azelaate), poly(hexamethylene azelaate), poly(ethylene sebacate), poly(butylene sebacate), poly(hexamethylene sebacate), poly(octylene sebacate), poly(l-lactic acid), poly(d-lactic acid), poly(l/d-lactic acid), poly(glycolic acid), poly(D-caprolactone), poly(D-varelactone), poly(dimethylene glycol oxalate), poly(dimthylene glycol succinate), poly(trimethylene glycol succinate) and their polyester copolymers. For the reason of as-said polyester polyol resin as raw material for successive two-component polyurethane production, and poly(ethylene adipate), poly(ethylene succinate) and poly(butylene succinate) may be more particularly preferred.

In accordance with the present invention, the metal ion catalytic species remained in as-produced polyester polyol resin are quenched or deactivated by a process of adding quenching organic compounds into the polyester polyol melt just after the end of the as-said condensation polymerization step and mixing them therein, or by a process of adding quenching organic compounds into the remelting polyester polyol resin and mixing them therein. The effective quenching compound or active deactivator may be a substituted phosphine which can be represented by formula (6)

R₇ R₉

( 6 )

wherein R₇, R₈, R₉ represent hydrogen atoms, alkyl functional groups consisting of 1-12 carbon atoms, cyclic aliphatic functional groups consisting of 6~8 carbon atoms, aryl functional groups of consisting of 6-8 carbon atoms. The as-said substituted phosphine compounds may be a mono-hydrogen phoshine, a di-hydrogen phosphine, trimethyl phosphine, triethyl phosphine, triisopropyl phosphine, triterf-butyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tritolyl phosphine, and triphenyl phosphine and tritolyl phosphine are particularly preferred for the reason of an apparent better quenching or deactivating effect.

In a further embodiment of present invention, quenching compound or deactivator may be a substituted phosphine oxide which can be represented by a formula (7)

( 7 )

wherein Rio, Rn, Rn represent hydrogen atoms, alkyl functional groups consisting of 1-12 carbon atoms, cyclic aliphatic functional groups consisting of 6-8 carbon atoms, aryl functional groups of consisting of 6-8 carbon atoms. The as-said substituted phosphine oxide may be a mono-hydrogen phoshine oxide, a di-hydrogen phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triisopropyl phosphine oxide, triter/-butyl phosphine oxide, tricyclohexyl phosphine oxide, triphenyl phosphine oxide, tritolyl phosphine oxide, and triaryl phosphine oxide such as triphenyl phosphine oxide, tritolyl phosphine oxide are more preferred for the reason of an apparent better quenching or deactivating effect. - -

In a yet further embodiment of present invention, quenching compound or deactivator may be a substituted phosphine sulfide which can be represented by a formula (8)

S

( 8 )

wherein R₁₃, Ri₄, Ri₅ represent hydrogen atoms, alkyl functional groups consisting of 1— 12 carbon atoms, cyclic aliphatic functional groups consisting of 6~8 carbon atoms, aryl functional groups of consisting of 6~8 carbon atoms. The as-said substituted phosphine sulfide may be a mono-hydrogen phoshine sulfide, a di-hydrogen phosphine sulfide, trimethyl phosphine sulfide, triethyl phosphine sulfide, triisopropyl phosphine sulfide, tήtert-buty\ phosphine sulfide, tricyclohexyl phosphine sulfide, triphenyl phosphine sulfide, tritolyl phosphine sulfide, and triaryl phosphine sulfide such as triphenyl phosphine sulfide, tritolyl phosphine sulfide are more preferred for the reason of an apparent better quenching or deactivating effect and quality of the deactivated polyester polyol resin product.

In a further embodiment of present invention, quenching compound or deactivator may be a crown ether compound which can be represented by following formula (9).

12-crown-4 15-crown-5

18-crown-6 Dibenzo 18-crown-6 (9) - -

Illustrative of the effective cyclic crown ether deactivators are 12-crown-4, 15-crown-5, 18-crown-6 and dibenzo 18-crown-6.

In a yet further embodiment of present invention, functional compound capable of quenching the residual catalytic metal ion species in the obtained polyester polyol resin may be an alkyl and/or aryl substituted quaternary ammonium halide salt with the molecular structure represented by a formula

(10),

( 10 )

wherein Ri₆, Rn, Ris and R₁₉ represent hydrogen atoms, alkyl functional groups consisting of 1-16 carbon atoms, cyclic aliphatic functional groups consisting of 6-8 carbon atoms, aryl functional groups of consisting of 6—8 carbon atoms, and X represents a halogen atom such as Cl, Br, and I. The as-said substituted quaternary ammonium halide salt may be particularly preferred to be an alkyl and/or aryl substituted quaternary ammonium bromide salt such as tetraisopropyl ammonium bromide, tetra n-butyl ammonium bromide, hexadecyl trimethyl ammonium bromide for the reason of apparent deactivating effects, and color and quality of products.

In accordance of present invention, the amount of as-selected quenching compound or active deactivator is generally used with a molar ratio of the deactivator to catalytic metal ion species remained in the obtained polyester polyol resin equal to a value of 0.01-20, more preferably equal to a value of 0.05-10, and most preferably equal to a value of 0.1-5.0 for both effective quenching the remained catalytic metal ion species and reasonable product cost.

In a further embodiment, employing the quenching compounds in accordance of present invention, deactivation of catalytic metal ion species in as-produced polyester polyol may be selectively performed by two possible processes denoted as the pre-deactivation process and the post-deactivation process. With regard to the pre-deactivation process, the deactivator is added to the melt of polyester _ _

polyol condensation product, and continuously in-situ mixed for effectively quenching the remained catalytic metal ion species. On the other hand, for the post-deactivation process, the as-obtained polyester polyol resin is first dehydrated, and is then remelt to mix together with quenching compound to deactivate the remained catalytic metal ion species under a quenching temperature above melting point of therein applied deactivator prior to further addition of reactive isocyanate for successive polyurethane production.

During the above feature deactivation process, the mixing and in-situ quenching temperature may be 40~200°C, more preferably be 60~180°C, and most preferably be 60~150°C for avoiding unfavorable thermal degradation of polyester polyol and occurrence of coloration, and the deactivation is particularly preferred to be carried out under inert atmosphere like dry nitrogen, argon. For either a pre-deactivation process or a post-deactivation process, a mixing and quenching period may be preferred as 0.1— 10 hours, and is particularly preferred as 0.5-4 hours.

In accordance with quenching compounds and related deactivating process, the obtained polyester polyol product after deactivating the remained catalytic metal ion species may be further used for subsequent production of two-component based polyurethane with the active-hydrogen reactive isocyanate raw materials which can be selected from the group containing at least two isocyanate groups. Illustrative of the as-said active hydrogen reactive isocyanate are 2,4-toluene diisocyanate (TDI), 2,6-tuluene diisocyanate (TDI), diphenyl methane 4,4'-diisocyanate (MDI), />-phenylene diisocyanate, hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocynate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diisocyanto dicyclohexyl methane, isophorone diisocyanate (IPDI) and their possible isocyanate dimers, isocyanate trimers, isocyanate pentamers, and their combination mixtures thereof. The diisocyanate compounds of TDI, MDI, HDI and IPDI are more preferred for the reason of better final deactivation effect, feature color and improved qualities of the polyurethane products.

The present invention will now be illustrated in detail in a way of experimental samples. However, these samples may not be construed to limit the scope of this invention. The physical properties of the as-obtained polyester polyol products were characterized in the ways as illustrated below: Acid value was thereby analyzed in accordance with conventional titration strategy. A predetermined amount of dehydrated polyester polyol resin was first weighted into a 150 ml flask, and then 30 ml of toluene-ethanol mixture solution (toluene/ethanol=2:l) was added and mixed with gentle shaking. After well dissolving of the polyester polyol sample, a few drops of 1% phenolphalein indicator solution were further placed, and then KOH in methanol (0.1 mol/L) was employed for repeated titration until the above mixture solution turned into stable reddish color. At the mean time, the blank control was also done. Therefore, acid value of the obtained sample was thus calculated by a formula

Acid value(AV in mg KOH/g)=(V_s-V_b)^χC^χ56.1/M

where V₅ and V_b in ml represent volumes of KOH-methanol solution used for titrating the polyester polyol and the blank control, C is the concentration of KOH-methanol solution, M is the mass weight of sample in gram.

Hydroxyl value of the as-obtained polyester polyol product was analyzed with an improved acetic anhydride-pyridine method. First, a predetermined amount (1-2 gram) of as-obtained polyester polyol was weighted into a 150 ml flask with 5.0 ml of routinely prepared acetylation reagent, and kept refluxing the mixture solution in water bath, and then kept at ambient temperature for 5—10 minutes. Then, 2 ml of distilled water and 10 ml of pyridine aqueous solution (pyridine/water=3: l) were in turn added and mixed, subsequently kept for more than 5 minutes after stirring. KOH aqueous solution (0.5 mol/L) was employed for repeatedly titrating the mixture solution with phenolphalein indicator until the above mixture solution turned from colorless into stable reddish color. At the mean time, the blank control was also done. Therefore, an averaged hydoxyl value of the obtained sample was thus calculated by following formula

Hydroxyl value (HV in mg KOH/g)=(V_b-V_s)^χC^χ56.1/M

where V_s and V_b in ml represent volumes of KOH aqueous solution used for titrating the polyester polyol and the blank control, C is the concentration of KOH-methanol solution, M is the mass weight of sample in gram.

Molecular weigh of the difunctional polyester polyol was evaluated by a formula

Molecular weight (Mn)=2^χ56.1^χ l000/(acid value + hydroxyl value) Measurement of exact residual metal specie mass concentration was quantitatively analyzed in a Prodigy inductive coupled plasma atom emission spectrometer (ICP-AES).

Method to assay quenching or deactivation effect was performed with a simple building up system comprising an IKA Eurostar mixing facility under a fixed mixing rate and similar mass weight of two-component polyurethane reaction mixture, and real-time torque values in N.cm of the reacting two-component polyurethane mixture were recorded via an attached cable, and controlled by a commercial software of labworldsoft, and the polyester-polyol produced without any catalyst was simultaneously used as the blank control. In addition, to shorten the practical assay process, a three functional alcohol of trihydroxymethyl propane (TMP) with an initial feeding molar ratio of 1.5 (hydroxyl of TMP): 1 (hydroxyl of the as-obtained polyester polyol):2.5 (isocyanate of the isocyanate component), and a total -OH/-NCO molar ratio equal to 1.0 were used. As a result, times for torque values under a stirring speed of 300 rpm of the two-component polyurethane reaction mixture reaching 5 N.cm were used to compare and assay apparent effectiveness of deactivation. EXAMPLE 1

In a 500 ml three-necked round-bottom flask with a mechanical stirrer, a dry nitrogen purge inlet, a vapor outlet, 2.00 mole of adipic acid and 2.60 mole of ethylene glycol were in turn charged under flowing nitrogen atmosphere, and the mixture of raw materials was heated up for esterification to eliminate the water byproduct. After melting the mixture of starting materials, the reaction mixture was stirred, and the water byproduct began to be removed at 140°C with an iced trap. When 80% of theoretical water byproduct was removed, temperature of the reaction system were gradually increased to 220 °C , and kept the step of esterification till 95% of theoretical water byproduct was removed, and acid value of the polyester polyol approached less than 15 mgKOH/g. Subsequently, the step of condensation polymerization was performed at 230°C under gradually reduce pressure with a final pressure of about 1.0 mmHg. When the acid value and hydroxyl value of the reacting polyester polyol reached values of less than 3 mgKOH/g and 55 mgKOH/g, respectively, the polycondensation reaction was terminated, and white-color waxy solids of residual catalytic metal ion specie free poly(ethylene adipate) polyol resin was thus produced with an acid value of 0.57 mgKOH/g, a hydroxyl value of 46.30 mgKOH/g and a number average molecular weight of 2394.

EXAMPLE 2

Example 1 was repeated in the same way except that 2.00 mmol of tin(II) oxide was used as the metal Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic tin(II) ion species was thus produced with an acid value of 0.83 mgKOH/g, a hydroxyl value of 36.60 mgKOH/g and a number average molecular weight of 2998.

EXAMPLE 3

Example 1 was repeated in the same way except that 2.00 mmol of tin(II) oxalate was used as the metal Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic tin(II) ion species was thus produced with an acid value of 0.83 mgKOH/g, a hydroxyl value of 43.91 mgKOH/g and a number average molecular weight of 2508.

COMPARATIVE EXAMPLE 1

Example 1 was repeated in the same way except that 2.00 mmol of /?-toluene sulfonic acid was used as the Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin without residual catalytic metal ion species was thus produced with an acid value of 3.43 mgKOH/g, a hydroxyl value of 55.17 mgKOH/g and a number average molecular weight of 1915. EXAMPLE 4

Example 1 was repeated in the same way except that 2.00 mmol of tetra n-butoxy titanate was used as the metal Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic Ti(IV) ion species was thus produced with an acid value of 3.60 mgKOH/g, a hydroxyl value of 53.12 mgKOH/g and a number average molecular weight of 1978. EXAMPLE 5

Example 1 was repeated in the same way except that 2.00 mmol of magnesium acetate was used as the metal Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic Mg(II) ion species was thus produced with an acid value of 1.83 mgKOH/g, a hydroxyl value of 56.60 mgKOH/g and a number average molecular weight of 1920.

EXAMPLE 6

Example 1 was repeated in the same way except that 2.00 mmol of germanium tetraisopropoxide was used as the metal Lewis acid catalyst to accelerate the condensation polymerization process, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic Ge(IV) ion species was thus produced with an acid value of 1.35 mgKOH/g, a hydroxyl value of 56.48 mgKOH/g and a number average molecular weight of 1956.

EXAMPLE 7

Example 1 was repeated in the same way except that 2.50 mole of adipic acid, 3.38 mole of ethylene glycol and 2.50 mmol of tin(II) oxalate as the metal Lewis acid catalyst to accelerate the condensation polymerization process were used to polyester polyol, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic tin(II) ion species was thus produced with an acid value of 1.48 mgKOH/g, a hydroxyl value of 53.24 mgKOH/g and a number average molecular weight of 2050.

EXAMPLE 8 Example 1 was repeated in the same way except that 2.00 mole of adipic acid, 2.40 mole of ethylene glycol and 2.00 mmol of tin(II) oxalate as the metal Lewis acid catalyst to accelerate the condensation polymerization process were used to polyester polyol, and finally white-color waxy solids of poly(ethylene adipate) polyol resin containing residual catalytic tin(II) ion species was thus produced with an acid value of 2.16 mgKOH/g, a hydroxyl value of 52.52 mgKOH/g and a number average molecular weight of 2052.

EXAMPLE 9

40.40 gram of the polyester polyol product of Example 1 was first placed into a 250 ml three-necked round-bottom flask equipped with a mechanical stirrer, a dry nitrogen gas inlet and an outlet connected with vacuum line, the polyester polyol was first heated up to 90-100 °C for remelting the resin, and was then kept under reduced pressure to remove moisture for 1 hour. Then, 2.30 gram of trihydroxylmethyl propane TMP was added into the above polyester polyol melt, and simultaneously decreased the system temperature to 50~60^°C under vacuum for 0.5 hour. Finally, 6.0 ml of toluene diisocyanate TDI was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time of 320 minutes for the torque value to reach 5.0 N.cm was obtained with a clear and thin yellow appearance of the polyurethane product.

EXAMPLE 10

Example 9 was repeated in the same manner except that 40.80 gram of the produced polyester polyol resin of Example 3 and 2.20 gram of trihydroxymethyl propane (TMP) were used. Finally, 5.80 ml of toluene diisocyanate (TDI) was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time within 2 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow gel appearance of the polyurethane product. EXAMPLE 11

Example 9 was repeated in the same manner except that 40.80 gram of the produced polyester polyol resin of Example 3 and 0.039 gram of 18-crown-6 ether as a deactivator were used to mixed under a temperature of 120 "C, and the residual catalytic metal tin(II) ion specie was continuously quenched under 120 °C for 2 hours, and then decreased the temperature to 90-100 "C and kept under vacuum for

1 hour. Subsequently, 2.20 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 50~60^°C under vacuum and kept for 0.5 hour. Finally, 5.80 ml of toluene diisocyanate (TDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and a remarkably extended time of 150 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product.

EXAMPLE 12

Example 9 was repeated in the same manner except that 40.80 gram of the produced polyester polyol resin of Example 2 and 0.097 gram of tetraisopropyl ammonium bromide as a deactivator were used to mixed under a temperature of 160 °C, and the residual catalytic metal tin(II) ion specie was continuously quenched under 160 °C for 2 hours, and then decreased the temperature to 90~100^°C and kept under vacuum for 1 hour. Subsequently, 2.20 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 50~60°C under vacuum and kept for 0.5 hour. Finally, 5.80 ml of toluene diisocyanate (TDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and a remarkably extended time of 290 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product.

EXAMPLE 13

Example 9 was repeated in the same manner except that 39.16 gram of the produced polyester polyol resin of Example 7 and 0.067 gram of triphenyl phosphine oxide as a deactivator were used to mixed under a temperature of 120 "C, and the residual catalytic metal tin(II) ion specie was continuously quenched under 120 "C for 2 hours, and then decreased the temperature to 80-90 °C and kept under vacuum for 1 hour. Subsequently, 2.56 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 50~60°C under vacuum and kept for 0.5 hour. Finally, 6.80 ml of toluene diisocyanate (TDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and a remarkably extended time of 300 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product. Further, the deactivator/metal ion specie molar ratio dependence of quenching effect is illustrated in table 1.

Table 1 the triphenyl phosphine oxide deactivator/metal ion specie molar ratio dependence of quenching effect (TDI based PU)

Time for

Entry Deactivator/i torque to Appearance

Quenching process

no. on molar ratio reach 5 N.cm color

(minutes )

thin yellow

1 No deactivation 0 2

gel

2 Pre-deactivation 0.5 140 thin yellow

3 Pre-deactivation 1.0 300 thin yellow

4 Pre-deactivation 1.5 120 thin yellow

5 Pre-deactivation 2.5 130 thin yellow

6 Pre-deactivation 3.0 145 thin yellow

7 Post deactivation 0.5 220 thin yellow

8 Post deactivation 1.0 170 thin yellow

9 Post deactivation 1.5 55 thin yellow

10 Post deactivation 2.5 60 thin yellow

11 Post deactivation 3.0 225 thin yellow

Notes: the exact residual metal ion mass concentration was measured by ICP-AES EXAMPLE 14

Example 9 was repeated in the same manner except that 39.14 gram of the produced polyester polyol resin of Example 8 and 0.102 gram of triphenyl phosphine sulfide as a deactivator were used to mixed under a temperature of 160 °C, and the residual catalytic metal tin(II) ion specie was continuously quenched under 160 °C for 2 hours, and then decreased the temperature to 90-100 °C and kept under vacuum for 1 hour. Subsequently, 2.20 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 70 ^°C under vacuum and kept for 0.5 hour. Finally, 5.80 ml of toluene diisocyanate (TDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and a remarkably extended time of 120 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product. Further, the deactivator/metal ion specie molar ratio dependence of quenching effect is illustrated in table 2.

Table 2 the triphenyl phosphine sulfide deactivator/metal ion specie molar ratio dependence of quenching effect (TDI based PU)

Time for

Entry Deactivator/ion torque to Appearance

Quenching process

no. molar ratio reach 5 N.cm color

(minutes)

1 Pre-deactivation 0.5 300 thin yellow

2 Pre-deactivation 1.0 315 thin yellow

3 Pre-deactivation 1.5 256 thin yellow

4 Pre-deactivation 2.5 55 thin yellow

5 Pre-deactivation 3.0 10 thin yellow

6 Post-deactivation 0.5 40 thin yellow

7 Post-deactivation 1.0 50 thin yellow

8 Post-deactivation 1.5 120 thin yellow

9 Post-deactivation 2.5 110 thin yellow 10 Post-deactivation 3 . 0 120 thin yellow

Notes: the exact residual metal ion mass concentration was measured by ICP-AES

COMPARATIVE EXAMPLE 2

Example 9 was repeated in the same manner except that 38.00 gram of the produced polyester polyol resin of Example 1 and 2.15 gram of trihydroxymethyl propane (TMP) were used. Finally, 9.95 gram of diphenyl methane 4,4'-diisocyanate (MDI) was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time within 55 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow gel appearance of the polyurethane product. COMPARATIVE EXAMPLE 3

Example 9 was repeated in the same manner except that 38.40 gram of the produced polyester polyol resin of Example 3 and 2.05 gram of trihydroxymethyl propane (TMP) were used. Finally, 9.60 gram of diphenyl methane 4,4'-diisocyanate (MDI) was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time within 5 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow gel appearance of the polyurethane product.

EXAMPLE 15

Example 9 was repeated in the same manner except that 38.40 gram of the produced polyester polyol resin of Example 3 and 0.063 gram of triphenyl phosphine oxide as a deactivator were used to mixed under a temperature of 160 D, and the residual catalytic metal tin(II) ion specie was continuously quenched under 160 D for 2 hours, and then decreased the temperature to 90-100D and kept under vacuum for 1 hour. Subsequently, 2.05 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 50-60 D under vacuum and kept for 0.5 hour. Finally, 9.60 gram of diphenyl methane 4,4'-diisocyanate (MDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and a time of 40 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product. COMPARATIVE EXAMPLE 4

Example 9 was repeated in the same manner except that 40.60 gram of the produced polyester polyol resin of Example 1 and 2.30 gram of trihydroxymethyl propane (TMP) were used. Finally, 6.90 ml of hexamethylene diisocyanate (HDI) was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time of 250 minutes for the torque value to reach 5.0 N.cm was obtained with a clear thin yellow appearance of the polyurethane product.

COMPARATIVE EXAMPLE 5

Example 9 was repeated in the same manner except that 40.90 gram of the produced polyester polyol resin of Example 3 and 2.20 gram of trihydroxymethyl propane (TMP) were used. Finally, 6.60 ml of hexamethylene diisocyanate (HDI) was added into the resin mixture, and continuously stirred the mixture at 300 rpm, and a time of 55 minutes for the torque value to reach 5.0 N.cm was obtained with a clear thin yellow appearance of the polyurethane product. EXAMPLE 16

Example 9 was repeated in the same manner except that 40.90 gram of the produced polyester polyol resin of Example 3 and 0.068 gram of triphenyl phosphine oxide as a deactivator were used to mixed under a temperature of 160 D, and the residual catalytic metal tin(II) ion specie was continuously quenched under 160 D for 2 hours, and then decreased the temperature to 90—100 D and kept under vacuum for 1 hour. Subsequently, 2.20 gram of trihydroxymethyl propane (TMP) were added and mixed, and then decreased the system temperature to 50-60D under vacuum and kept for 0.5 hour. Finally, 6.60 ml of hexamethylene diisocyanate (HDI) was again placed into the above resin mixture, and continuously stirred the mixture at 300 rpm, and an extended time of 80 minutes for the torque value to reach 5.0 N.cm was obtained with a thin yellow appearance of the polyurethane product.

Claims

- - Claims:

1. A quenching agent for quenching an active impurity in a polyester polyol, the quenching agent comprising one or more components selected from the group consisting of organic phosphine compound having a general formula (1), organic phosphine oxide compound having a general formula (2), organic phosphine sulfide compound having a general formula (3), organic ammonium salt having a general formula (4) and organic crown ether compound having a general formula (5), (6), (7) or (8),

R₁

(6)

(8)

wherein,

Rl, R2, R3, R4, R5, R6, R7, R8 and R9 independently represent hydrogen atom, alkyl substituent group consisting 1-12 carbon atoms, cyclic aliphatic group consisting of 6-8 carbon atoms or aryl substituent group consisting of 6-8 carbon atoms;

Rl(K Rl K R12 and Rl 3 independently represent hydrogen atom, alkyl substituent group consisting 1-16 carbon atoms, cyclic aliphatic group consisting of 6-8 carbon atoms or aryl substituent group consisting of 6-8 carbon atoms; and

X represents a halogen atom.

2. The quenching agent as claimed in Claim 1, wherein, the organic phosphine compound is selected from the group consisting of mono-hydrogen phoshine, di-hydrogen phosphine, trimethyl phosphine, triethyl phosphine, triisopropyl phosphine, tritert-butyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tritolyl phosphine and diphenyl phosphine.

3. The quenching agent as claimed in Claim 1, wherein, the organic phosphine oxide compound is selected from the group consisting of mono-hydrogen phoshine oxide, di-hydrogen phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triisopropyl phosphine oxide, tritert-butyl phosphine oxide, tricyclohexyl phosphine oxide, triphenyl phosphine oxide, tritolyl phosphine oxide and diphenyl phosphine oxide.

4. The quenching agent as claimed in Claim 1, wherein, the organic phosphine sulfide compound is selected from the group consisting of mono-hydrogen phoshine sulfide, di-hydrogen phosphine sulfide, trimethyl phosphine sulfide, triethyl phosphine sulfide, triisopropyl phosphine sulfide, tritert-butyl phosphine sulfide, tricyclohexyl phosphine sulfide, triphenyl phosphine sulfide, tritolyl phosphine sulfide and diphenyl phosphine sulfide.

5. The quenching agent as claimed in Claim 1, wherein, the organic ammonium salt is selected from the group consisting of tetraisopropyl ammonium bromide, tetra n-butyl ammonium bromide and hexadecyl trimethyl ammonium bromide.

6. The quenching agent as claimed in Claim 1-5, wherein, the quenching temperature of the quenching agent is 40-200 O.

7. The quenching agent as claimed in Claim 1-5, wherein, the mole ratio between the quenching agent and the active impurity in the polyester polyolis 0.01-20.

8. A polyester polyol having a general formula (9) or (10), wherein, the active impurity in the polyester polyol is quenched by the quenching agent as claimed in Claim 1 -5

H — H

(9)

(10),

wherein,

the molecular weight of the polyester polyol is 500-50000;

Rl 4 is selected from the group consisting of hydrogen atom, divalent saturated or unsaturated aliphatic group consisting of 1-12 carbon atoms, divalent cyclic aliphatic group consisting of 1-12 carbon atoms and divalent aryl group consisting of 6-10 carbon atoms; Rl 5 is selected from the group consisting of hydrogen atom, divalent saturated or unsaturated aliphatic group consisting of 2-12 carbon atoms, divalent cyclic aliphatic group consisting of 2-12 carbon atoms and divalent aryl group consisting of 6-10 carbon atoms;

Rl 6 is a divalent saturated or unsaturated aliphatic group; and

m and n in the general formula (9) or (10) is independently fixed according to the molecular weight of the polyester polyol.

9. The polyester polyol as claimed in Claim 8, wherein, the quenching temperature is 40-200 D .

10. The polyester polyol as claimed in Claim 8, wherein, the mole ratio between the quenching agent and the active impurity in the polyester polyol is 0.01-20.

11. A method for preparing polyester polyol having a general formula (9) or (10) , comprising the steps of:

quenching active impurity in the polyester polyol by using the quenching agent as claimed in Claim 1-5

(9)

(10), wherein,

the molecular weight of the polyester polyol is 500-50000;

Rl 4 is selected from the group consisting of hydrogen atom, divalent saturated or unsaturated aliphatic group consisting of 1-12 carbon atoms, divalent cyclic aliphatic group consisting of 1-12 carbon atoms and divalent aryl group consisting of 6-10 carbon atoms;

Rl 5 is selected from the group consisting of hydrogen atom, divalent saturated or unsaturated aliphatic group consisting of 2-12 carbon atoms, divalent cyclic aliphatic group consisting of 2-12 carbon atoms and divalent aryl group consisting of 6-10 carbon atoms;

Rl 6 is a divalent saturated or unsaturated aliphatic group; and

12. The method as claimed in Claim 11, wherein, the quenching temperature is 40-200 D .

13. The method as claimed in Claim 11 or 12, wherein, the mole ratio between the quenching agent and the active impurity in the polyester polyol is 0.01-20.

14. A use of the polyester polyol as claimed in Claim 8, 9 or 10 in preparing polyurethane.

15. A polyurethane, wherein, the polyurethane comprises the reaction product of the reaction components of isocyanate and the polyester polyol as claimed in Claim 8, 9 or 10.

16. A use of the polyurethane as claimed in Claim 15 in preparing coating, adhesive, sealant or foam.