CN103080186A - Method for producing polyester alcohols - Google Patents
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- CN103080186A CN103080186A CN2011800427054A CN201180042705A CN103080186A CN 103080186 A CN103080186 A CN 103080186A CN 2011800427054 A CN2011800427054 A CN 2011800427054A CN 201180042705 A CN201180042705 A CN 201180042705A CN 103080186 A CN103080186 A CN 103080186A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a method for producing polyester alcohols by condensing polytetrahydrofuran with aromatic dicarboxylic acids and/or the anhydrides thereof and/or the esters thereof, preferably isophthalic acid, pthalic acid, and terephthalic acid, particularly preferably isophthalic acid, in the presence of a transesterification catalyst in a multistage operation at different pressure levels with at least one reaction stage at normal pressure and at least one reaction stage in a vacuum, wherein distillate is discharged from the reaction system. The method is characterized in that phosphoric acid is introduced in a molar ratio of the catalyst to the phosphoric acid of 1:1 to 1:3.5 after the polycondensation in order to deactivate the catalyst.
Description
Describe
The rights and interests of the pending trial US temporary patent application series number 61/380338 of claimed 09/07/2010 application of the application are incorporated herein its full content for reference.
The present invention relates to a kind of method for preparing based on the polyesterols of polytetrahydrofuran and dicarboxylic acid, and these polyesterols are for the preparation of the purposes (spandex based on the spandex fiber of polyurethane-urea, or spandex fibre), the hysteresis curve that it has especially flat is called " soft spandex " or " soft polyurethane fiber " in the literature.Spandex fibre for example is described in H.J.Koslowski, " the regenerated fiber dictionary (Dictionary of Man-Made Fibers ", the 1st edition 1998, International Business Press Publishers GmbH, Frankfurt am Main, the 69th page is risen.
The method that condensation reaction by poly carboxylic acid and polyvalent alcohol (or polyhydroxy-alcohol) prepares polyesterols (being also referred to as polyester polyol) has had many descriptions.For example, can be referring to Kunststoffhandbuch, the VII volume, urethane, Carl-Hanser-Verlag, Munich the 1st edition 1966 is by Dr.R.Vieweg and Dr.A.
Editor, and the 2nd edition the 1983 and the 3rd revised edition 1993 are edited by Dr.G.Oertel.
These polyesterols are especially being produced urethane (PU) product, are more especially being selected carefully used material and used polycondensation technology based on the application requiring in the spandex fiber (it has flat hysteresis curve) of polyurethane-urea.Dicarboxylic acid/the acid anhydrides and difunctionality, trifunctional and/or the polyfunctional alcohol that use aromatics and/or aliphatic series have been known, glycol more especially, they are being reacted in the presence of catalyzer under normal atmosphere and/or decompression under the temperature of 150-250 ° of C particularly, and remove reaction water simultaneously.Routine techniques for example referring to DE-A-2904184, is that reactive component is added with suitable catalyzer when the synthetic beginning, and raise simultaneously temperature and reduction pressure.Then in building-up process, further change temperature and vacuum.
When polycondensation related to multiple acid and/or alcohol, various reactive material also can only add in reaction process.Usually, condensation reaction under atmospheric pressure or under the pressure of slight reduction is carried out, until remove low boiling component (water, methyl alcohol).After the release of low boilers has finished, then add when appropriate other reactive component, change temperature, and begin to make vacuum stages to shift to high vacuum stage of Fig.
Polyurethane fiber is to produce by forming isocyanate-terminated prepolymer with di-isocyanate reaction from the polyesterols of acquisition like this, the reaction of described prepolymer and chainextender, randomly with end-capping reagent and optional other additive further reaction in suitable solvent, be converted to polyurethane elastomer.In the in the end step, polyurethane elastomer is spun to fiber by desolventizing, and described solvent is widely used in the dry-spinning, can be for example N,N-DIMETHYLACETAMIDE, dimethyl formamide or N-Methyl pyrrolidone.
When catalyzer be used for dicarboxylic acid and polyvalent alcohol, more especially during the polycondensation of polytetrahydrofuran, thereby it adds the processing step that can not disturb subsequently usually under lower concentration, perhaps in case reach the number-average molecular weight Mn of required polyesterols, then come passivation by adding passivator, for example phosphoric acid, thereby can not damage the reaction that forms subsequently prepolymer with vulcabond.
The passivation of catalyzer is completely ideally, because the reactive behavior of polyester has a direct impact the performance of the isocyanate-terminated prepolymer for preparing in next step of fiber production operation, and viscosity more especially.When the reactive behavior of the polyesterols in the prepolymer reaction was too high, the reaction heat of gained can not be removed fast enough, caused the reaction mixture heating to surpass maximum permissible temperature.On this temperature, side reaction increases, and particularly crosslinked, this can increase the viscosity of elastic polyurethane liquid solution, so that batch of material no longer can spinning.
The objective of the invention is to develop a kind of method for preparing based on the polyester polyol of polytetrahydrofuran and aromatic dicarboxylic acid and/or its acid anhydrides and/or its ester, thereby can prepare the polyester polyol based on polytetrahydrofuran and aromatic dicarboxylic acid with high functionality simple and economically.Therefore this purpose is to prepare the polyester polyol that has simultaneously high functionality and low reactivity.Must be noted that increase catalyst concn with realize Reaction time shorten and and then increase functionality, can cause reactive increasing.
Therefore, the invention provides a kind of method for preparing polyesterols, wherein polytetrahydrofuran and aromatic dicarboxylic acid and/or its acid anhydrides and/or its ester carry out condensation according to the multistage operation under the different pressures level in the presence of transesterification catalyst, wherein at least one step of reaction is in normal atmosphere and is in decompression with at least one step of reaction, aromatic dicarboxylic acid and/or its acid anhydrides and/or its ester m-phthalic acid preferably wherein, phthalic acid and terephthalic acid, more preferably m-phthalic acid, wherein remove overhead product from reaction system, described method is included in uses after the polycondensation phosphoric acid according to catalyzer: the mol ratio of phosphoric acid is come catalyst deactivation as 1:1 to 1:3.5.
Be surprised to find catalyzer: the molar ratio range of phosphoric acid causes passivation very narrow.Neither can or not realize required effect by phosphoric acid very little too much yet.Catalyzer: the mol ratio of phosphoric acid is preferably in the scope of 1:1.1 to 1:2.4, more preferably in the scope of 1:1 to 1:1.4.
The transesterification catalyst that adds can for example be tetrabutyl orthotitanate, tetra isopropyl orthotitanate, dibutyl tin laurate, dibutyltin oxide, stannous octoate, tin chloride, stannic oxide, potassium hydroxide, sodium methylate, titanium zeolite, lipase or be fixed on lytic enzyme on the carrier, preferred concentration is 3-100ppm, more preferably concentration is 20-60ppm, even more preferably concentration is 40-50ppm.Preferred catalyzer is tetrabutyl orthotitanate.
Preferably, tetrabutyl orthotitanate being added molecular-weight average is in the daltonian polytetrahydrofuran of 250-1000 and/or the BDO as solvent.The concentration of tetrabutyl orthotitanate in solvent is the 0.1-15 % by weight, preferred 2-10 % by weight.But the use of solvent not necessarily.
Polyesterols is 1:0.9 to 1:0.5, preferred 1:0.8 to 1:0.7 and more preferably 1:0.75 polycondensation preparation according to mol ratio advantageously by m-phthalic acid and polytetrahydrofuran.
Usually in a conventional manner preparation in technique of polytetrahydrofuran (PTHF) is wherein with tetrahydrofuran (THF) (hereafter is THF) polymerization on suitable catalyzer.Can add suitable reagent with the chain length of control polymer chain and and then control molecular-weight average.These reagent are called end-capping reagent or " conditioning agent ".By selecting conditioning agent and consumption thereof can carry out described control.Suitable conditioning agent can be introduced functional group in the one or both ends of polymer chain in addition.Industrial, diacetyl oxide or water are typically used as conditioning agent.This method is for example referring to patent DE19801462.
The PTHF that uses in the methods of the invention preferably has the daltonian molecular-weight average of 250-3000, more preferably 250-2000 dalton, for example PTHF250, PTHF450, PTHF650, PTHF1800 and PTHF2000.Preferably, molecular-weight average is 400-1000 dalton, preferred 650 dalton." molecular-weight average " or " average molar mass " represents the number-average molecular weight M of polymkeric substance in this article
n, it is for example measured by wet-chemical hydroxyl value detection method.
Useful aromatic dicarboxylic acid especially has 2-12 carbon atom.Useful dicarboxylic acid for example comprises: hexanodioic acid, Succinic Acid, pentanedioic acid, suberic acid, nonane diacid, sebacic acid, decane dioctyl phthalate, toxilic acid, fumaric acid, the naphthalene dicarboxylic acids of preferred hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid and isomery.Dicarboxylic acid not only can use separately, and can be mixed with each other.Replace dicarboxylic acid, can use corresponding dicarboxylic acid derivatives, for example have the dicarboxylic ester of the alcohol of 1-6 carbon atom, or dicarboxylic anhydride.The preferred molar ratio of Succinic Acid, pentanedioic acid and hexanodioic acid that uses is as being the dicarboxylic acid mixture of 20 to 35:35 to 50:20 to 32 weight parts and hexanodioic acid, the mixture of phthalic acid and/or Tetra hydro Phthalic anhydride and hexanodioic acid more especially, the mixture of phthalic acids/anhydrides, m-phthalic acid and hexanodioic acid, or the dicarboxylic acid mixture of Succinic Acid, pentanedioic acid and hexanodioic acid, and the dicarboxylic acid mixture of terephthalic acid and Succinic Acid, pentanedioic acid and hexanodioic acid or the mixture of hexanodioic acid.The preferred mixture that uses the aromatic carboxylic acid or contain the aromatic carboxylic acid.Particularly preferably use m-phthalic acid.
Reaction between polytetrahydrofuran and aromatic dicarboxylic acid and/or the acid anhydrides is carried out under ester (exchange) change condition.Reaction mixture heats gradually, for example is heated to 150-250 ° of C, and apply＜1013 to 5hPa vacuum this moment, and removes the by product of gained by distillation.
In a particularly preferred embodiment of the inventive method, polytetrahydrofuran and m-phthalic acid react according to the multistage operation under the different pressures level in the presence of tetrabutyl orthotitanate, wherein at least one step of reaction is in normal atmosphere and is in decompression with at least one step of reaction, wherein remove overhead product from reaction system, and reaction mixture is heated in two or more steps in the normal atmosphere step of reaction, and wherein heating steps is wherein kept the step institute interval of homo(io)thermism by at least one.
Reaction mixture is heated to temperature T in 0.1-15 hour process in first heating steps
1, T wherein
1=130-190 ° of C, preferred 180 ° of C.Can reach temperature T by laser heating (temperature rising)
1, or this temperature rising can be by at least one steady temperature △ T
1The step interval of (temperature platform), wherein △ T
1Preferably than T
1Low 1-10 ° of C.Second heating steps is heated to temperature T in 1-20 hour process
Finally=200-230 ° of C, preferred 220 ° of C.Equally, this second step can be by the outlet temperature T of laser heating to the normal atmosphere step of reaction
FinallyRealize, or can be by at least one steady temperature △ T
2The step interval of (temperature platform), wherein △ T
2Preferably than T
FinallyLow 1-20 ° of C.
Preferably, it is constant twice that the temperature between the outlet temperature (temperature up step) of heating steps and normal atmosphere step of reaction keeps, and this is corresponding to two temperature platforms.Temperature preferably twice between a plurality of heating stepses kept constant 0.5-10 hour, and preferred 1-5 hour, more preferably 1-4 hour.
Be heated to T
eNormal atmosphere step of reaction corresponding to time preferably carry out altogether 2-15 hour time, more preferably 2.5-8 hour.
The synthetic of polyesterols is to carry out under esterification (exchange) condition, and can carry out in solvent.Preferably, when polytetrahydrofuran and aromatic dicarboxylic acid reaction, do not use solvent.
For fear of oxidation and loss functionality, polytetrahydrofuran and aromatic dicarboxylic acid, preferably m-phthalic acid, phthalic acid and terephthalic acid and more preferably the condensation reaction between the m-phthalic acid advantageously under inert gas atmosphere, carry out.Useful rare gas element comprises nitrogen, carbonic acid gas or rare gas for example, preferred nitrogen.Inert gas atmosphere is reduced to for the oxygen level with conversion unit and is lower than 0.1 volume %.
Transesterification catalyst, for example tetrabutyl orthotitanate, tetra isopropyl orthotitanate, dibutyl tin laurate, dibutyltin oxide, stannous octoate, tin chloride, stannic oxide, potassium hydroxide, sodium methylate, titanium zeolite, lipase or lytic enzyme, be fixed on the carrier, preferred tetrabutyl orthotitanate is preferably reaching temperature T
FinallyAfterwards and added in the 2-4 before applying vacuum hour.Preferably, tetrabutyl orthotitanate being added molecular-weight average is in the daltonian polytetrahydrofuran of 250-1000 and/or the BDO as solvent.The concentration of tetrabutyl orthotitanate in solvent is the 1-15 % by weight, preferred 2-10 % by weight, more preferably 5-10 % by weight.But the use of solvent not necessarily.
The Depressor response stage preferably carries out under＜1013 to 2 millibars pressure, preferred 2-100 millibar, more preferably 2-50 millibar.
The Depressor response stage is preferably carried out altogether 2-15 hour time, more preferably 2.5-8 hour.
The inventive method has significantly been improved the production of polyesterols, shows as to have high functionality and low reactivity.
Further specify the present invention below by embodiment.
Embodiment
The detection of molecular weight
Average molecular mass Mn is the form of number-average molecular weight, is defined as the quality of all PTHF molecules divided by their molar weight, and number-average molecular weight Mn is by detecting hydroxy value measuring in polytetrahydrofuran.Hydroxyl value is the mg amount of potassium hydroxide, and it is equal to the acetic acid amount of combination in the ethanoyl process of 1g material.Hydroxyl value is carried out esterification by existing hydroxyl with the excessive acetic acid acid anhydride and is detected.
H-[O(CH
2)
4]n-OH+(CH3CO)
2→CH
3CO-[O(CH
2)
4]n-O-COCH
3+H
2O
After reaction, excessive diacetyl oxide is hydrolyzed according to following reaction formula water:
(CH
3CO)
2O+H2O→2CH
3COOH
And with potassium hydroxide acetic acid is carried out back titration.
The detection of viscosity
Viscosity is to use Physica MCR101 viscometer (being installed in entrained air) from Anton Paar (milli pascal second=mPas) detect according to DIN53019-1 under 60 ° of C.This instrument has Anton Paar Drypoint film moisture eliminator, Haake DC10 thermostatted (water temp is controlled to be 30 ° of C), with PC (connecting via serial interface), the pressurized air supply (3 hand shaft line) of Rheoplus/32V3.10 software.Liquid to be detected is placed on cone angle: Anton Paar CP50-1 and plate: in the viscometer detector gap between the Anton Paar Peltier P-PTD200 (the cone-plate distance is 0.05mm), one of them is according to circular frequency U rotation (rotor), another static (stator).(time is set: 15 data points, (this appliance requires was adjusted to corresponding shearing rate in 2.5 seconds in the detection that relates to separately 5 seconds.In next 2.5 seconds, torque sensor is by per 2 seconds detection raw data (i.e. 250 values), shearing rate: rising 10-1001/s logarithm, detected temperatures: 60 ° of C, angular position: 0.06mm, detection position: 0.05mm).
15 data points are 10,11.8,13.9,16.4,19.3,22.8,26.8,31.6,37.3,43.9,51.8,61.1,72,84.8,100[1/s in shearing rate] the lower detection, the value of wherein reporting is at 100[1/s] shearing rate under obtain.
The detection of iodine number
Iodine number is to pass through (the DGF standard method C-V11b) that Kaufmann ' s method detects.Iodine number is to weigh the means of the level of unsaturated carbon-to-carbon double bond.This detection is based on halogen (being bromine in this case) and adds to ability on two keys.This is to measure by the back titration of the not consumption of halogen.It is expressed as g iodine/100g material.
The 1g sample accurately is weighed to 0.001g, then adds 1:1 (v/v) hexanaphthene/glacial acetic acid of 10ml, and mix with the 25ml bromine solutions that 1000ml methyl alcohol and 5.20ml bromine, prepares from 120-150g Sodium Bromide (in advance dry under 130 ° of C).Then, add 20ml liquor kalii iodide (potassiumiodide of 100g/l) and 100ml distilled water, the iodine that discharges uses first the 0.1mol/l sodium thiosulfate solution titrated to yellow, adding some amidins (5g/l starch) afterwards, is titrated to the atropurpureus batch of material colourless.
The detection of hydroxyl value
Hydroxy radical content detects by measuring " hydroxyl value " according to DIN53240-2.For this reason, all hydroxyls and the reaction of excessive acetylation reagent (diacetyl oxide), and measure excessive acid equivalent by carrying out the volume titration with potassium hydroxide solution.Hydroxyl value is the mg amount of potassium hydroxide, and it is equal in acetylize by the acetic acid amount of 1g material combination.
Detect functionality from iodine number and hydroxyl value
The method that detects functionality from iodine number and hydroxyl value is referring to N.Barksby, G.L.Allen, urethane international conference (Polyurethane World Congress) 1993, the 445-450 pages or leaves.Polyesterols synthetic is accompanied by side reaction, causes forming the polymer chain with allyl ethers end group, is called monohydroxy-alcohol.The monohydroxy-alcohol fraction that exists with the difunctionality polyesterols causes functionality to reduce.
Monohydroxy-alcohol content is to detect by the allylic terminal double bond of potassium hydroxide titration with mercuric acetate/contain alcohol, namely by analyzing the degree of unsaturation level, is expressed as milliequivalent/gram polyvalent alcohol.From degree of unsaturation (" unsat "=iodine number, unit is meq/g) and hydroxyl value (" OH ", unit are mg KOH/g), can be according to formula 1) calculate functionality f:
F wherein
nBe for described polyesterols nominal functionality (for glycol, namely in situation of the present invention, f
n=2).For the normal polyester alcohol of molecular weight Mn=4000, f is in 1.7 scope.
Detect afterwards water-content (DIN EN60814) at Ka Er-Fischer (Karl Fischer)
Water-content detects by Ka Er-Karl Fischer titration.For this reason, the sample solution with the 1-3 milliliter injects the automatic instrument (Metrohm Karl Fischer Coulometer KF756) that detects water-content by Ka Er-Fischer method.This detection is to carry out according to the coulometric titration mode, and is based on Ka Er-fischer reaction, i.e. the water conditioned reaction of iodine and sulfurous gas.
Detect chromatic number
Chromatic number detects according to ASTM D4890EN or DIN ISO6271.Not solvent-laden polymkeric substance detects in the LICO200 tintometer of (Precision cuvettes) model No.100-QS (path length 50mm is from Helma) that accurately lags behind from Dr.Lange. in untreated situation.
Detect acid number (DIN EN12634)
The ester of raw material and carboxylic acid content (carboxyl that exists in mixture) are by well known to a person skilled in the art that method detects " ester value " and " acid number " and measures.In order to detect acid number, the carboxylic acid of all existence neutralizes with excessive potassium hydroxide, and the potassium hydroxide of residual content is measured by carrying out the volume titration with hydrochloric acid.In order to detect saponification value, the ester of all existence is with excessive potassium hydroxide-ethanol solution saponification.The potassium hydroxide of residual content is measured by carrying out the volume titration with hydrochloric acid.Ester value is the difference between the saponification value that so detects and the acid number that had before detected.Ester value is the mg amount of potassium hydroxide, and it is equal in acetylize by the acetic acid amount of 1g material combination.
Isothermal prepares prepolymer
Prepolymer prepares under the temperature of 70 ° of C in the isothermal mode.Polyesterols and 4, the mol ratio of 4 '-diphenylmethanediisocyanate (MDI) is 1:2, the batch of material size is 350g.
First polyesterols is added in the reaction vessel in 70 ° of C, and stir.It is very important that the accurate temperature of 2 ° of C of+/-keeps.
With diphenylmethanediisocyanate (4,4-MDI) add in the polyesterols, and sample is taken out from reaction mixture in after adding MDI 5,10,15,20,25,30,35,40,50,60,70 and 80 minutes, and by titration detection NCO content.
NCO titration (detection isocyanate content)
The prepolymer sample is added in the mixture of the dibutylamine of 30ml and chlorobenzene, wherein dibutylamine concentration is 0.05mol/l.Before adding prepolymer, detect the blank value of mixture with 0.1 mole hydrochloride.The mixture that will comprise sample stirred 10-15 minute, mixed with 50ml ethanol subsequently.Unconverted dibutylamine detects with 0.1 mole hydrochloride.From consumption, can be by considering that blank value calculates NCO content.
NCO concentration is along with the reduction of time is faster, and the reactivity of polyesterols is higher.
Embodiment
Embodiment 1
A) preparation polyesterols Mn3000g/mol (the present invention)
In being equipped with the 4L flask of heating, stirring and water distilling apparatus, with the m-phthalic acid of 375.4g and the polytetrahydrofuran 650 of 1956.08g (the expression molecular-weight average is 650g/mol) in succession three times degassed, use nitrogen purging, then under atmospheric pressure be heated to 180 ° of C.Regulate heating rate, so that approximately reaching 180 ° of C after 2 hours.
Polycondensation under atmospheric pressure begins under the temperature of 180 ° of C.This temperature kept 3 hours.Then be heated to 205 ° of C, kept 2 hours, then be heated to 220 ° of C.After this temperature keeps 3 hours, the tetrabutyl orthotitanate of 11.25g (50ppm) form with 1 % by weight solution in PTHF650 was added before the beginning vacuum stages.Apply 20 millibars vacuum.Water was distilled in 8 hours and reaches acid number less than 1.
When reaching required acid number, system is cooled to 190 ° of C.For catalyst deactivation, add the 85 % by weight phosphoric acid of 0.045g (20ppm is 1:1.18 corresponding to mol ratio).With the batch of material cool to room temperature, and detect the quality of polyesterols via iodine number, chromatic number, hydroxyl value, acid number, viscosity and water-content.
B) the isocyanate-terminated prepolymer of preparation
Prepolymer prepares under isothermal condition under 70 ° of C.
The result of prepolymer test as shown in Figure 1.NCO concentration represents the good passivation of polyesterols along with the time reduces gradually.
Comparative example 1 (VB1) is with respect to the embodiment of the invention
(phosphoric acid not contains the catalyzer of 10ppm)
A) preparation polyesterols Mn3000g/mol
In being equipped with the 4L flask of heating, stirring and water distilling apparatus, with the m-phthalic acid of 375.4g and the polytetrahydrofuran 650 of 1956.08g (the expression molecular-weight average is 650g/mol) in succession three times degassed, use nitrogen purging, then under atmospheric pressure be heated to 180 ° of C.Regulate heating rate, so that approximately reaching 180 ° of C after 2 hours.
Polycondensation under atmospheric pressure begins under the temperature of 180 ° of C.This temperature kept 3 hours.Then be heated to 205 ° of C, kept 2 hours, then be heated to 220 ° of C.After this temperature keeps 3 hours, the tetrabutyl orthotitanate of 2.25g (10ppm) form with 1 % by weight solution in PTHF650 was added before the beginning vacuum stages.Apply 20 millibars vacuum.Water was distilled in 22 hours and reaches acid number less than 1.
When reaching required acid number, with the system cool to room temperature, and detect the quality of polyesterols via iodine number, chromatic number, hydroxyl value, acid number, viscosity and water-content.
B) the isocyanate-terminated prepolymer of preparation
Prepolymer prepares under isothermal condition under 70 ° of C.NCO concentration gradually along with the reduction of time as shown in Figure 1.The reduction of NCO concentration is obviously faster, and expression has significantly higher reactivity than the embodiment of the invention.
Comparative example 2 (VB2) is with respect to the embodiment of the invention
(using the catalyzer of 10ppm and the H3PO4 of 30ppm)
A) preparation polyesterols Mn3000g/mol
In being equipped with the 4L flask of heating, stirring and water distilling apparatus, with the m-phthalic acid of 375.4g and the polytetrahydrofuran 650 of 1956.08g (the expression molecular-weight average is 650g/mol) in succession three times degassed, use nitrogen purging, then under atmospheric pressure be heated to 180 ° of C.Regulate heating rate, so that approximately reaching 180 ° of C after 2 hours.
Polycondensation under atmospheric pressure begins under the temperature of 180 ° of C.This temperature kept 3 hours.Then be heated to 205 ° of C, kept 2 hours, then be heated to 220 ° of C.After this temperature keeps 3 hours, the tetrabutyl orthotitanate of 2.25g (10ppm) form with 1 % by weight solution in PTHF650 was added before the beginning vacuum stages.Apply 20 millibars vacuum.Water was distilled in 22 hours and reaches acid number less than 1.
When reaching required acid number, system is cooled to 190 ° of C.For catalyst deactivation, add the 85 % by weight phosphoric acid of 0.0675g (30ppm is 1:8.8 corresponding to mol ratio).With the batch of material cool to room temperature, and detect the quality of polyesterols via iodine number, chromatic number, hydroxyl value, acid number, viscosity and water-content.
B) the isocyanate-terminated prepolymer of preparation
Prepolymer prepares under isothermal condition under 70 ° of C.NCO concentration along with the reduction of time as shown in Figure 1.The reduction of NCO concentration is obviously faster, and expression has higher reactivity than the embodiment of the invention.
Comparative example 3 (VB3) is with respect to the embodiment of the invention
(using the catalyzer of 10ppm and the H3PO4 of 15ppm)
A) preparation polyesterols Mn3000g/mol (LJ843)
In being equipped with the 4L flask of heating, stirring and water distilling apparatus, with the m-phthalic acid of 375.4g and the polytetrahydrofuran 650 of 1956.08g (the expression molecular-weight average is 650g/mol) in succession three times degassed, use nitrogen purging, then under atmospheric pressure be heated to 180 ° of C.Regulate heating rate, so that approximately reaching 180 ° of C after 2 hours.
Polycondensation under atmospheric pressure begins under the temperature of 180 ° of C.This temperature kept 3 hours.Then be heated to 205 ° of C, kept 2 hours, then be heated to 220 ° of C.After this temperature keeps 3 hours, the tetrabutyl orthotitanate of 2.25g (10ppm) form with 1 % by weight solution in PTHF650 was added before the beginning vacuum stages.Apply 20 millibars vacuum.Water was distilled in 8 hours and reaches acid number less than 1.
When reaching required acid number, system is cooled to 190 ° of C.For catalyst deactivation, add the 85 % by weight phosphoric acid of 0.0338g (15ppm is 1:4.5 corresponding to mol ratio).With the batch of material cool to room temperature, and detect the quality of polyesterols via iodine number, chromatic number, hydroxyl value, acid number, viscosity and water-content.
B) the isocyanate-terminated prepolymer of preparation
Prepolymer prepares under isothermal condition under 70 ° of C.NCO concentration along with the reduction of time as shown in Figure 1.The reduction of NCO concentration is obviously faster, and expression has higher reactivity than the embodiment of the invention.
Comparative example 4 (VB4) is with respect to the embodiment of the invention
(using the catalyzer of 50ppm and the H3PO4 of 10ppm)
A) preparation polyesterols Mn3000g/mol
In being equipped with the 4L flask of heating, stirring and water distilling apparatus, with the m-phthalic acid of 375.4g and the polytetrahydrofuran 650 of 1956.08g (the expression molecular-weight average is 650g/mol) in succession three times degassed, use nitrogen purging, then under atmospheric pressure be heated to 180 ° of C.Regulate heating rate, so that approximately reaching 180 ° of C after 2 hours.
Polycondensation under atmospheric pressure begins under the temperature of 180 ° of C.This temperature kept 3 hours.Then be heated to 205 ° of C, kept 2 hours, then be heated to 220 ° of C.After this temperature keeps 3 hours, the tetrabutyl orthotitanate of 11.25g (50ppm) form with 1 % by weight solution in PTHF650 was added before the beginning vacuum stages.Apply 20 millibars vacuum.Water was distilled in 8 hours and reaches acid number less than 1.
When reaching required acid number, system is cooled to 190 ° of C.For catalyst deactivation, add the 85 % by weight phosphoric acid of 0.0225g (10ppm is 1:0.6 corresponding to mol ratio).With the batch of material cool to room temperature, and detect the quality of polyesterols via iodine number, chromatic number, hydroxyl value, acid number, viscosity and water-content.
B) the isocyanate-terminated prepolymer of preparation
Prepolymer prepares under isothermal condition under 70 ° of C.
NCO concentration along with the reduction of time as shown in Figure 1.The reduction of NCO concentration is obviously faster, and expression has higher reactivity than the embodiment of the invention.
Claims (10)
1. method for preparing polyesterols, wherein polytetrahydrofuran and aromatic dicarboxylic acid and/or its acid anhydrides and/or its ester carry out condensation according to the multistage operation under the different pressures level in the presence of transesterification catalyst, wherein at least one step of reaction is in normal atmosphere and is in decompression with at least one step of reaction, wherein remove overhead product from reaction system, described method is included in uses after the polycondensation phosphoric acid according to catalyzer: the mol ratio of phosphoric acid is come catalyst deactivation as 1:1 to 1:3.5.
2. according to claim 1 method, wherein phosphoric acid is according to catalyzer: the mol ratio of phosphoric acid is that 1:1 to 2:4 uses.
3. according to claim 1 and 2 method, wherein phosphoric acid is according to catalyzer: the mol ratio of phosphoric acid is that 1:1 to 1:4 uses.
4. each method according to claim 1-3, wherein used catalyzer is tetrabutyl orthotitanate, tetra isopropyl orthotitanate, dibutyl tin laurate, dibutyltin oxide, two stannous octoates, tin chloride, stannic oxide, potassium hydroxide, sodium methylate, titanium zeolite, lipase and/or lytic enzyme, and concentration is 3-100ppm.
5. each method according to claim 1-4, wherein used catalyzer is to be the daltonian polytetrahydrofuran of 250-1000 and/or as four butanols titaniums in the BDO of solvent at molecular-weight average.
6. each method according to claim 1-5, wherein polytetrahydrofuran and m-phthalic acid react in the presence of tetrabutyl orthotitanate, and reaction mixture is heated in two or more steps in the normal atmosphere step of reaction, and wherein said heating steps is wherein kept the step institute interval of homo(io)thermism by at least one.
7. each method according to claim 1-6, wherein reaction mixture is heated to temperature T in 0.1-15 hour process in first heating steps
1, T wherein
1=130-190 ° of C.
8. each method according to claim 1-7, wherein reaction mixture is heated to temperature T in 3-12 hour process in second heating steps
e=200-230 ° of C.
9. each method according to claim 1-8, wherein temperature keeps constant twice between described heating steps.
10. each method according to claim 1-9, wherein the Depressor response stage is carrying out under less than 1013 to 5hPa pressure.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38033810P | 2010-09-07 | 2010-09-07 | |
| US61/380,338 | 2010-09-07 | ||
| EP10175583 | 2010-09-07 | ||
| EP10175583.3 | 2010-09-07 | ||
| PCT/EP2011/065253 WO2012031997A1 (en) | 2010-09-07 | 2011-09-05 | Method for producing polyester alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103080186A true CN103080186A (en) | 2013-05-01 |
Family
ID=45810147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800427054A Pending CN103080186A (en) | 2010-09-07 | 2011-09-05 | Method for producing polyester alcohols |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2614100A1 (en) |
| KR (1) | KR20130114124A (en) |
| CN (1) | CN103080186A (en) |
| WO (1) | WO2012031997A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT3630869T (en) | 2017-05-31 | 2021-05-18 | Basf Se | Aliphatic-aromatic polyester having elevated whiteness index |
| WO2019076582A1 (en) * | 2017-10-20 | 2019-04-25 | Henkel Ag & Co. Kgaa | Polyester polyols based on phthalic acid having low viscosity |
| CN113788949B (en) * | 2021-09-16 | 2022-08-12 | 北京化工大学 | Preparation method of polyester plasticizer, product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663653A (en) * | 1968-07-09 | 1972-05-16 | Hoechst Ag | Polytetrahydrofuran modified block copolyester thermoplastic molding compositions |
| CN101432326A (en) * | 2006-04-25 | 2009-05-13 | 巴斯夫欧洲公司 | Segmented polyurethane elastomers with high elongation at tear |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2904184A1 (en) | 1978-03-17 | 1979-09-20 | Gaf Corp | MOLDING COMPOUNDS AND THE INJECTION MOLDED BODIES MADE FROM THEM |
| DE19801462A1 (en) | 1998-01-16 | 1999-07-22 | Basf Ag | Production of tetrahydrofuran polymers, useful e.g. as diol components for polymer production |
-
2011
- 2011-09-05 CN CN2011800427054A patent/CN103080186A/en active Pending
- 2011-09-05 KR KR1020137008712A patent/KR20130114124A/en not_active Application Discontinuation
- 2011-09-05 WO PCT/EP2011/065253 patent/WO2012031997A1/en active Application Filing
- 2011-09-05 EP EP11751906.6A patent/EP2614100A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663653A (en) * | 1968-07-09 | 1972-05-16 | Hoechst Ag | Polytetrahydrofuran modified block copolyester thermoplastic molding compositions |
| CN101432326A (en) * | 2006-04-25 | 2009-05-13 | 巴斯夫欧洲公司 | Segmented polyurethane elastomers with high elongation at tear |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130114124A (en) | 2013-10-16 |
| EP2614100A1 (en) | 2013-07-17 |
| WO2012031997A1 (en) | 2012-03-15 |
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