CN103073712A - Preparation method for polyester by using liquid titanium catalyst - Google Patents
Preparation method for polyester by using liquid titanium catalyst Download PDFInfo
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- CN103073712A CN103073712A CN201110327457XA CN201110327457A CN103073712A CN 103073712 A CN103073712 A CN 103073712A CN 201110327457X A CN201110327457X A CN 201110327457XA CN 201110327457 A CN201110327457 A CN 201110327457A CN 103073712 A CN103073712 A CN 103073712A
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Abstract
The invention provides a preparation method for polyester by using a liquid titanium catalyst. According to the method, one dicarboxylic acid and at least one dihydric alcohol are used as basic raw materials to prepare slurry, and the slurry is added into a reaction vessel for esterification after uniform stirring to obtain an esterification product under the conditions of a reaction temperature of 220 to 280 DEG C, a pressure of normal pressure to 0.3 MPa and reaction time of 1 to 4 h; then pre-polycondensation is carried out under the conditions of a reaction temperature of 240 to 280 DEG C, a reaction pressure of 101 kPa to 600 Pa and pre-polycondensation time of 0.5 to 1.5 h so as to obtain a prepolymer; and finally condensation polymerization is carried out under the conditions of a reaction temperature of 270 to 295 DEG C, an absolute pressure of 150 to 50 Pa and final polycondensation time of 0.5 to 2 h so as to prepare a polyester product. With the method provided by the invention, the disadvantage that a powdery titanium catalyst cannot be dissolved in glycol and can only form fluid suspension is overcome, continuous stability of addition concentration of the catalyst is guaranteed, and requirements for concentration stability and production stability of the catalyst are met.
Description
Technical field
The present invention relates to a kind of method of using liquid condition titanium series catalyst to prepare polyester, particularly relating to the method that a kind of antimony-based catalyst that uses liquid condition titanium series catalyst and certain usage ratio prepares polyester is a kind of method of using liquid condition titanium series catalyst to prepare polyester.
Background technology
Being widely used in the daily life of the goods of synthesizing polyester, such as trevira, polyester bottles, polyester film etc.Common polyester has polyethylene terephthalate (being called for short PET), Poly(Trimethylene Terephthalate) (being called for short PPT), polybutylene terephthalate (being called for short PBT), PEN (being called for short PEN) etc., and is wherein general with PET.
Catalyzer is very important link in the polyester production process, and the catalyzer that can be used for polycondensation of polyester mainly contains antimony system, germanium system, titanium system, aluminium system etc.Because the antimony-based catalyst activity is moderate, and the degree that affects thermal degradation reaction is less, almost the polyester of each kind grade all can use antimony-based catalyst to be prepared, therefore commercially producing of polyester all is to use with the antimony-based catalyst of heavy metal antimony as main component in decades, comprises antimonous oxide, antimony acetate and antimony glycol etc.Yet, there is successively in recent years research to point out that antimony metal can be detrimental to health, the recent regulations in Europe also begins to limit the antimony content of weaving textiles.In addition, the environmental protection aspect, the ethylene glycol residue that contains antimony must be processed, and antimony can immersedly take out the pollution that causes process water in the textile dyeing operation.Therefore do not contain the trend that antimony and heavy metal have become future development in the polyester.
The most possible environment-friendly type catalyzer that replaces antimony-based catalyst is Titanium series catalyst, the development work that tens of companies American-European and Japan have carried out Titanium series catalyst, the domestic research work that also has many companies and research institution to carry out Titanium series catalyst of China, annual have the patent of One's name is legion to come out, but the patent that the Titanium series catalyst application facet is seldom arranged, rarer Titanium series catalyst are applied to the report of production of polyester and relatively ripe application art.
Patent CN 101220142A discloses a kind of method of using liquid condition titanium series catalyst to prepare polyethylene terephthalate, step is: (1) with terephthalic acid and ethylene glycol in the presence of liquid condition titanium series catalyst, must temperature, carry out esterification under the pressure, (2) then fix on one and carry out prepolymerization reaction under temperature, the pressure, (3) then with the product of step (2), be that final minification is poly-under the condition of 60Pa～25Pa at 275～286 ℃ and pounds per square inch absolute (psia), obtain target product.But the application Titanium series catalyst is very high in the b value of the polyester that the intermittent type polyester production device prepares, and form and aspect are that polyester product is poor than antimony; The scale that is applied in the continous way polyester production device is less, only is 1 kiloton/grade, and making beating is that device is not the continous way polyester production device in the industrial application intermittently in batches.
Patent CN 101104678A discloses the preparation method of titanium catalyst polyester, mainly be to carry out the method that esterification and polycondensation prepare titanium catalyst polyester take dibasic alcohol and diprotic acid as basic raw material, it is characterized in that: add titanium catalyst, phosphorus thermo-stabilizer and toning agent in esterification or polycondensation phase, the titanium catalyst general formula is Ti (L)
n(OR)
m, wherein L is a kind of element among oxygen O, phosphorus P, the sulphur S, R is C
1-C
10Alkyl.Undeclared its state of matter of the described titanium catalyst of this preparation method also will be added the problem that phosphorus thermo-stabilizer and toning agent solve the hue of chip jaundice simultaneously; Embodiment among the preparation method only lists the standby process of polyester, and the scale of polyester preparation facilities is not described.
Patent CN 101121776B discloses a kind of method for making of using the polyester of non-antimony catalyst, key step is to make at least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, or after at least a dicarboxylic ester and at least a dibasic alcohol carry out transesterification reaction, make again the prepolymer that generates under the effect of a Zinc catalysts and a phosphorous acid ester of using as tranquilizer, carry out the condensation polymerization reaction and make polyester.It is characterized in that described Zinc catalysts is the oxide compound that is selected from zinc, the organic acid salt of zinc, halogenide and the combination thereof of zinc.This preparation method has enumerated and has used Zinc catalysts to prepare the method for polyester, only lists the embodiment that the laboratory bench scale prepares polyester.
The contriver notices, a kind of new catalyst can be applied at existing polyester production device, except the activity and selectivity that will consider catalyzer, also will consider the device characteristic of existing all kinds of production technique, can the mass transfer that satisfy new catalyst such as reactor types, stirring or film forming ability, the vacuum system etc. of installing require etc.
Existing production of polyester flow process generally can be divided into two kinds of intermittent type and continous ways, and the single line industrial scale is from several thousand ton/years to hundreds thousand of ton/years, and correspondingly, the processing parameter that different flow processs adopts and equipment are not identical yet.And, existing polyester production device, the larger device of production capacity particularly, the above continuous apparatus of 380 ton per days for example, all be that characteristics according to antimony-based catalyst design the technological process of production and lectotype selection, can not get the polyester of acceptable performance after the device that has can't use Titanium series catalyst or use Titanium series catalyst.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of method of using liquid condition titanium series catalyst to prepare polyester, particularly relate to a kind of method of using liquid condition titanium series catalyst and the antimony-based catalyst of certain usage ratio to prepare polyester, to overcome the following defective that exists in the prior art: because existing polyester production device, the larger device of production capacity particularly, the above continuous apparatus of 380 ton per days for example, all be that characteristics according to antimony-based catalyst design the technological process of production and lectotype selection, can not get the polyester of acceptable performance after the device that has can't use Titanium series catalyst or use Titanium series catalyst.Therefore use Titanium series catalyst at existing apparatus, solve the performance of Titanium series catalyst own and device to the problem of performance adaptability two aspects of Titanium series catalyst.
Particular content of the present invention:
A kind of method of using liquid condition titanium series catalyst to prepare polyester, this preparation method may further comprise the steps:
(A) take at least a dicarboxylic acid and at least a dibasic alcohol as basic raw material, be prepared into slurry, join after stirring and carry out esterification in the reactor, temperature of reaction is 220～280 ℃, reaction pressure is normal pressure～0.3MPa, and the time is 1～4 hour, obtains esterification products; (B) be 240～280 ℃ in temperature of reaction then, reaction pressure is to carry out prepolymerization reaction under the condition of pounds per square inch absolute (psia) 101kPa～600Pa, and the precondensation time is 0.5～1.5 hour, obtains prepolymer; (C) prepolymer that step (B) is obtained is 270～295 ℃ in temperature of reaction, and pounds per square inch absolute (psia) is to carry out the poly-reaction of final minification under the condition of 150Pa～50Pa, and the poly-time of final minification is 0.5～2 hour, makes polyester product.It is characterized in that the antimony-based catalyst with liquid condition titanium series catalyst and certain usage ratio before esterification or after the esterification adds in the reaction system.
Adopt the batch production mode or adopt the continous way mode of production.
The antimony-based catalyst of described certain usage ratio, its usage ratio are antimony-based catalyst consumption meters required when preparing polyester for independent use antimony-based catalyst, and proportional range is 0～80%.
Described prepolymerization reaction thermotonus temperature is 240～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～295 ℃, and pounds per square inch absolute (psia) is 150Pa～50Pa.
Described prepolymerization reaction temperature is 260～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～290 ℃, and pounds per square inch absolute (psia) is 150Pa～60Pa.
The consumption of described liquid condition titanium series catalyst is that Ti content is 5 * 10 during not composite use antimony-based catalyst with the content meter of titanium atom quality in made polyester gross weight
-6～60 * 10
-6
The consumption of described liquid condition titanium series catalyst is that Ti content is 2.5 * 10 during the composite use antimony-based catalyst of 50% ratio with the content meter of titanium atom quality in made polyester gross weight
-6～30 * 10
-6Ti content is 4 * 10 during the composite use antimony-based catalyst of 80% ratio
-6～48 * 10
-6
At least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, and described dicarboxylic acid is selected from terephthalic acid, m-phthalic acid, naphthalic acid, cyclohexane cyclohexanedimethanodibasic, Succinic Acid, pentanedioic acid, hexanodioic acid etc.; Described dibasic alcohol is selected from ethylene glycol, 1,3-PD, naphthalene glycol, 1,2-PD, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, Diethylene Glycol, 1,3-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, triethylene glycol etc.
Described dicarboxylic acid is terephthalic acid, and described dibasic alcohol is ethylene glycol.
Method of the present invention, can adopt the batch production mode, the device of this mode mainly adopts two still flow processs and three still flow processs etc., wherein two still flow process principal reaction equipment comprise an esterifying kettle and a polycondensation vessel, and three still flow processs then mainly comprise an esterifying kettle, a precondensation still and a whole polycondensation vessel.The principal feature of batch production device is the form that the poly-reactor of final minification adopts continuous stir reactor more, by stirring reaction mass is carried out Surface Renewal, with the micromolecular devolatilizations such as ethylene glycol that promote that reaction generates.Because not ideal enough by stirring the long-pending effect of increase reaction-ure surface, so the batch production device requires higher to the vacuum of whole polycondensation vessel, condition of high vacuum degree is conducive to micromolecular devolatilization equally, is one of reaction mass specific surface area deficiency in the terminal polymerization kettle is replenished.Aspect the catalyzer interpolation, the method that the intermittent type device mainly adopts intermittent type to add, to dispersed less demanding in ethylene glycol of catalyzer, do not need catalyzer is carried out pre-treatment, and as long as catalyzer and ethylene glycol are mixed (be mixed into suspension or mix become solution all can).
Method of the present invention, also can adopt the continous way mode of production, the flow process of employing mainly comprises three still flow processs (containing an esterifying kettle, a precondensation still, a whole polycondensation vessel), four still flow processs (containing two esterifying kettles, a precondensation still, a whole polycondensation vessel) and five autoclaves process (containing two esterifying kettles, two precondensation stills, a whole polycondensation vessel) etc.Compare with the reaction unit of intermittent type flow process, the main characteristics of continous way device are that whole polycondensation vessel adopts horizontal reactor more, mainly comprise the types such as disc type reactor and squirrel-cage reactor, improve the specific surface area of material by the reaction mass pull-up being become liquid film and by gravity and scraper plate the liquid film surface being constantly updated, and then improve micromolecular devolatilization speed.Can say that compare with the continuous stir reactor of intermittent type device, the mass transfer effect of the horizontal reactor of continous way device is better.Aspect the catalyzer interpolation, the interpolation of continous way device mainly also is to adopt continuous mode, most devices add after all needing antimony-based catalyst is dissolved in the solution that becomes homogeneous phase in the ethylene glycol fully again, therefore, require very high to the solubility property of catalyzer in ethylene glycol.
The inventor finds that the processing condition of polycondensation and the mode of production have certain relation, and the different modes of production adopts different reaction conditionss, and the contriver selects as follows through a large amount of experiment screenings:
For the batch production device, described prepolymerization reaction temperature is 240～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～295 ℃, and pounds per square inch absolute (psia) is 150Pa～50Pa.
For continuous production device, described prepolymerization reaction temperature is 260～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～290 ℃, and pounds per square inch absolute (psia) is 150Pa～60Pa.
The consumption of described liquid condition titanium series catalyst is with the content meter of titanium atom quality in made polyester gross weight, is 5 * 10 during not composite use antimony-based catalyst
-6～60 * 10
-6Ti content is 2.5 * 10 during the composite use antimony-based catalyst of 50% ratio
-6～30 * 10
-6Ti content is 4 * 10 during the composite use antimony-based catalyst of 80% ratio
-6～48 * 10
-6
Described liquid condition titanium series catalyst and preparation method thereof can adopt patented technology CN1320026C production, and titanium is that the mass concentration of atom is about 3.00% in this catalyzer.
Described liquid condition titanium series catalyst and preparation method thereof also can adopt another kind of prior art, and detailed report is arranged in Chinese patent application CN201010266068.6, and wherein, the titanium atom mass content is 2.00～5.00%.
The preparation method of Chinese patent application CN201010266068.6 technology is summarized as follows: (A) titanium compound, tetraethoxy, hydroxycarboxylic acid were reacted 0.1～24 hour under 0～100 ℃ of temperature condition in solvent, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom; (B) in the reaction product of above-mentioned (A) step, add phosphorus compound and a kind of acetate that is selected from the metallic element of Na, Mg, Al, Zn, La, under 50～200 ℃ of temperature condition, reacted 0.1～48 hour, remove small molecules, make liquid condition titanium series catalyst.
The micromolecular method in the reaction system is removed in described separation, is a kind of method of routine, such as the distillating method of routine.
Described titanium compound is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate, the tetrabutyl titanate.
Described hydroxycarboxylic acid is at least a in citric acid, tartrate, lactic acid, the oxysuccinic acid.
Described phosphorus compound is at least a in trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate, triphenylphosphate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, diethylene triamine pentamethylene phosphonic, the ethylenediamine tetraacetic fork phosphonic acids.Described solvent is ethanol, Virahol, water or their two kinds of mixtures.
The mol ratio of described titanium compound and tetraethoxy is 30: 1～1: 1, the mol ratio of titanium compound and hydroxycarboxylic acid is 1: 10～1: 0.1, the mol ratio of titanium compound and phosphorus compound is 1: 10～1: 0.1, the mol ratio of titanium compound and described metallic element is 50: 1～5: 1, and the mol ratio of titanium compound and solvent is 1: 1～1: 50.
Described liquid condition titanium series catalyst can add in the reaction system before esterification or after the esterification or before prepolymerization reaction.
Compare with the technique of using antimony-based catalyst to prepare polyester, method of the present invention has the following advantages: (1) Titanium series catalyst need not be modulated, and is easy to use.(2) reduce esterification temperature, reduce the heavy oil consumption of device.(3) throughput of the esterification process of raising device with the composite use of antimony catalyst, improves the production capacity of device.(4) chip property of producing improves, and greatly improves such as the L value, reduces the antimony ash look.(5) improve follow-up spinning process, the life cycle that prolongs filament spinning component.(6) can satisfy the needs that antimony content has higher limit or do not contain the environmental protection polyester product of antimony.
Therefore, use liquid condition titanium series catalyst to replace antimony-based catalyst and carry out production of polyester, meet polyester industrial environmental friendliness, energy-saving and cost-reducing development trend.In addition, compare with the Titanium series catalyst product of most of powdery type, this liquid condition titanium series catalyst can dissolve each other in any proportion with ethylene glycol, overcome that the powdery type Titanium series catalyst can't be dissolved in ethylene glycol and the shortcoming that can only form suspension, guaranteed that catalyzer adds the continous-stable of concentration, more meet existing installation to the requirement of catalyst concn stability and production stability, have good prospects for commercial application and value.
Among the present invention, the limiting viscosity of polyester, end carboxyl, glycol ether and form and aspect etc. are analytical test by the following method:
(1) limiting viscosity: take by weighing the sample of cutting into slices about 0.125g, be dissolved in the mixed solvent of phenol/tetrachloroethane (mass ratio is 1: 1), in 25 ± 0.5 ℃, NCY-2 type automatic viscosity measurer is measured.
(2) content of carboxyl end group: adopt volumetry, get 0.20-0.60g section sample dissolution in the mixing solutions of phenol/chloroform (volume ratio is 2: 3), with sodium hydroxide/methyl alcohol/phenylcarbinol standardized solution titration.
(3) glycol ether content: adopt the hydrazinolysis method, measure with Shimadzu GC-TAG flame gas chromatograph
(4) form and aspect b value, L value: measure with the full-automatic colour examining colour-difference-metre of TC-PIIG.
Embodiment:
A kind of method of using liquid condition titanium series catalyst to prepare polyester, the preparation method may further comprise the steps: (A) take at least a dicarboxylic acid and at least a dibasic alcohol as basic raw material, be prepared into slurry, join after stirring and carry out esterification in the reactor, temperature of reaction is 220～280 ℃, reaction pressure is normal pressure～0.3MPa, and the time is 1～4 hour, obtains esterification products; (B) be 240～280 ℃ in temperature of reaction then, reaction pressure is to carry out prepolymerization reaction under the condition of pounds per square inch absolute (psia) 101kPa～600Pa, and the precondensation time is 0.5～1.5 hour, obtains prepolymer; (C) prepolymer that step (B) is obtained is 270～295 ℃ in temperature of reaction, and pounds per square inch absolute (psia) is to carry out the poly-reaction of final minification under the condition of 150Pa～50Pa, and the poly-time of final minification is 0.5～2 hour, makes polyester product.It is characterized in that the antimony-based catalyst with liquid condition titanium series catalyst and certain usage ratio before esterification or after the esterification adds in the reaction system.
The invention will be further elaborated below by embodiment.
The preparation of liquid condition titanium series catalyst:
In the reactor that agitator, separating funnel and condenser are housed, add 42.6g titanium isopropylate (0.15mol) and 1.55g tetraethoxy (0.0075mol) and 100g dehydrated alcohol, mix.Slowly splash into the mixing solutions of 63.3g monohydrate potassium (0.3mol) and 100g dehydrated alcohol and 25g water in the reactor, drip finish after, room temperature to 100 ℃ reaction 1 hour.Separate out white depositions, continue to add 19.2g magnesium acetate (0.09mol) and 123.7g 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (content is 50%) solution (0.3mol), 50～200 ℃ of lower reactions 0.5～3 hour, remove small molecules, become homogeneous liquid to system, namely obtain the liquid catalyst that titaniferous is 3.15% (quality).
Embodiment 1
(A) adopt the 2L stainless steel cauldron to synthesize light PET section is arranged greatly.500g terephthalic acid (PTA) and 260g ethylene glycol (EG) are mixed, and (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition is 10 * 10 to add catalyst solution 0.159g
-6).At 240 ℃, pressure is to carry out esterification under 0.1～0.3MPa, and the reaction times is 2 hours;
(B) after esterification finishes, begin to vacuumize and carry out prepolymerization reaction, the prepolymerization reaction temperature is 265 ℃, and pressure is 101kPa, pounds per square inch absolute (psia) 1000Pa in still when precondensation finishes;
(C) the poly-reaction of final minification is carried out under 275 ℃, pressure 70Pa, and after 130 minute reaction times, obtaining limiting viscosity is that 0.670, L value is that 85, b value is 3.0 polymkeric substance.
Embodiment 2
(A) adopt the 2L stainless steel cauldron to synthesize light PET section is arranged greatly.500g PTA and 260g EG are mixed, and (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition is 15 * 10 to add catalyst solution 0.238g
-6).At 240 ℃, pressure is to carry out esterification under 0.1～0.3MPa, and the reaction times is 2 hours;
(B) after esterification finishes, begin to vacuumize and carry out prepolymerization reaction, the prepolymerization reaction temperature is 265 ℃, and pressure is 101kPa, pounds per square inch absolute (psia) 1000Pa in still when precondensation finishes;
(C) the poly-reaction of final minification is carried out under 275 ℃, pressure 70Pa, and after 130 minute reaction times, obtaining limiting viscosity is that 0.670, L value is that 85, b value is 3.1 polymkeric substance.
Embodiment 3
Identical with embodiment 2.Different is: (A) esterification reaction temperature is 240 ℃, and pressure is 0.1～0.25MPa, and the time is 2.5 hours; (B) esterification is added catalyzer after finishing, and the prepolymerization reaction temperature is 25O ℃, react to pounds per square inch absolute (psia) be I000Pa; (C) the poly-reaction of final minification is carried out under 285 ℃, pounds per square inch absolute (psia) 6OPa, and after 105 minute reaction times, the product property viscosity that obtains is that 0.668, L value is that 86, b value is 3.2.
Embodiment 4
Adopt 7000 ton/years of intermittent type polyester production devices production of two still flow processs that light PET section is arranged greatly.Reaction unit mainly comprises an esterifying kettle and a polycondensation vessel, and wherein the polycondensation vessel volume is 15.8m
3, the anchor formula stirs, the chuck heat-conducting oil heating.The charging capacity that PTA is every batch is 4.4 tons, after esterification finishes, oligopolymer is delivered to polycondensation vessel with nitrogen pressure, and this moment, (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition was 15 * 10 to wherein adding Titanium series catalyst solution 2095g
-6).Begin after mixing to vacuumize and carry out prepolymerization reaction, temperature of reaction is 255 ℃～275 ℃, and the interior pounds per square inch absolute (psia) of still was 700Pa when precondensation finished.After precondensation finishes, continue the intensification step-down and begin the poly-reaction of final minification, when reaching 60kw, the stirring rake power of agitator changes electric machine frequency to reduce rotating speed of agitator (behind the frequency modulation power of agitator as about 10kw), afterwards, when power of agitator rises to 40kw gradually, reach polymerization degree requirement, nitrogen extrudes material after the vacuum that disappears.The poly-temperature of reaction of final minification is 285 ℃～290 ℃, and pounds per square inch absolute (psia) is 40～60Pa in the still, and in 140 minutes reaction times, product property viscosity 0.675, L value are 86, b value 4.2.
Embodiment 5
Adopt 7000 tonnes of intermittent type polyester production devices production, half dull PET chip of three still flow processs.The main reaction device comprises an esterifying kettle, a precondensation still and a whole polycondensation vessel, and wherein the poly-kettle of final minification is long-pending is 15.8m3, and the anchor formula stirs, the chuck heat-conducting oil heating.The charging capacity that PTA is every batch is 3.0 tons, after esterification finishes, oligopolymer nitrogen is compressed into into the precondensation still, and this moment, (with the content meter of titanium atom quality in made weight polyester, the Ti addition was 15 * 10-6) and the TiO2 matting agent to wherein adding Titanium series catalyst solution 1428g.Mix rear beginning prepolymerization reaction, temperature of reaction is 260 ℃～275 ℃, and the interior pounds per square inch absolute (psia) of still was 600Pa when precondensation finished.Precondensation end afterreaction material nitrogen is compressed into into the poly-reactor of final minification and is begun the poly-reaction of final minification.Change electric machine frequency when the stirring rake power of agitator reaches 30kw, reduce mixing speed, power of agitator also is reduced to about 10kw, when power of agitator rises to 35kW after the frequency conversion, reaches polymerization degree requirement, and nitrogen extrudes material after the vacuum that disappears.The poly-temperature of reaction of final minification is 285～292 ℃, and pounds per square inch absolute (psia) is 40～60Pa in the still, and the reaction times is 130 minutes, and product property viscosity 0.670, L value are 86, b value 3.8.
Embodiment 6
Adopt 7000 tonnes of intermittent type polyester devices production, half dull PET chip of three still flow processs.Identical with embodiment 5, difference is the consumption of catalyzer: the add-on of Titanium series catalyst solution is that 714g is (with the content meter of titanium atom quality in made weight polyester, the Ti addition is 7.5 * 10-6), and antimony glycol 675g (be when separately using antimony glycol consumption 50%), other processing condition are identical with embodiment 5.The poly-reaction times of final minification is 130 minutes, and product property viscosity 0.668, L value are 84, b value 3.5.
Embodiment 7
Adopt the kiloton continous way polyester device preparation of three still flow processs that light PET section is arranged greatly.Complete assembly mainly comprises an esterifying kettle, a precondensation still (turbulent flow type spray tower) and a horizontal whole polycondensation vessel.PTA charging capacity every day is 1.0 tons, and the residence time of material in whole polycondensation vessel is 90 minutes.PTA and EG pull an oar in configured slot first, and the add-on of PTA is 1.0 tons in every batch of slurry, enters filling tank after the making beating and is sent to continuously esterifying kettle again.When each making beating, (with the content meter of titanium atom quality in made weight polyester, the Ti addition is 15 * 10-6) to add Titanium series catalyst solution 477g in the configured slot.Inlet temperature is 278.0 ℃ at the bottom of the precondensation tower, 280.5 ℃ of tower top outlet temperature, cat head pressure 700Pa.Pounds per square inch absolute (psia) is 60～80Pa in the whole polycondensation vessel, and the poly-temperature of charge of final minification is 275～276 ℃, and the reaction times is 120 minutes.Measure the kinetic viscosity of melt in the whole polycondensation vessel by in-line viscometer, the melt that reaches the polymerization degree adopts the underwater pelletizer pelletizing behind end of extruded band.The limiting viscosity 0.670 of products therefrom, L value are 87, b value 4.0.
Embodiment 8
Adopt 10 ton continous way polyester device productions, half dull PET chip of five autoclaves process, output is 380 ton per days.The complete assembly reactive moieties comprises esterification one still, esterification two stills, precondensation still, polycondensation one still and whole polycondensation vessel.PTA and EG be in proportion continuously to the making beating still in charging, in the making beating still, add continuously the EG modulation solution of Titanium series catalyst (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition is 7.5 * 10-6), and the EG of antimony glycol modulation solution is (with the content meter of antimony atoms quality in made polyester gross weight, the Sb addition is 120 * 10-6, when being independent use antimony glycol 50% of consumption); Continuously to esterification one still charging reaction, the material that flows out from esterification one still enters esterification two stills after the making beating, and the esterification total residence time is 4 hours, and temperature of reaction is that 255～270 ℃, reaction pressure are 0.1～0.2MPa; The material that flows out from esterification two stills enters the precondensation still, and the residence time is 30～40 minutes, and 272～275 ℃ of temperature of reaction, reaction pressure are 10Kpa; The material that flows out from the precondensation still successively enters polycondensation one still and polycondensation two stills, and the residence time is 140 minutes, 274～278 ℃ of temperature of reaction, and polycondensation two still reaction pressures are 60～80pa; The material that flows out from polycondensation two stills is products therefrom, and limiting viscosity 0.660, L value are 94, b value 3.2.
Embodiment 9
Adopt 10 ton continous way polyester device productions, half dull PET chip of five autoclaves process, output is 380 ton per days.Identical with embodiment 8, difference is the consumption of catalyzer: the EG modulation solution of Titanium series catalyst is (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition is 5.0 * 10-6), and the EG of antimony glycol modulation solution is (with the content meter of antimony atoms quality in made polyester gross weight, the Sb addition is 165 * 10-6, when being independent use antimony glycol 70% of consumption); Other processing condition are identical with embodiment 8.Product property viscosity 0.660, L value are 93, b value 2.8.
Embodiment 10
Adopt 10 ton continous way polyester device productions, half dull PET chip of five autoclaves process, output is 380 ton per days.Identical with embodiment 8, difference is the consumption of catalyzer: (with the content meter of titanium atom quality in made polyester gross weight, the Ti addition is 4.0 * 10 to the EG modulation solution of Titanium series catalyst
-6), and the EG of antimony glycol modulates solution, and (with the content meter of antimony atoms quality in made polyester gross weight, the Sb addition is 190 * 10
-6, when being independent use antimony glycol 80% of consumption); Other processing condition are identical with embodiment 8.Product property viscosity 0.660, L value are 92, b value 2.7.
Comparative example 1
According to the method identical with embodiment 2, difference is that spent glycol antimony catalyst 0.225g replaces the liquid condition titanium series catalyst among the embodiment 2, the poly-temperature of reaction of final minification is 275 ℃～285 ℃, through 130 minutes final minifications after the poly-reaction times, obtaining limiting viscosity is 0.670, the L value is that 81, b value is 3.8 polymkeric substance.
Comparative example 2
According to the method identical with embodiment 4, difference is that spent glycol antimony 1980g replaces the liquid condition titanium series catalyst among the embodiment 4, the poly-temperature of reaction of final minification is 285 ℃～290 ℃, pounds per square inch absolute (psia) is 40～60Pa in the still, 135 minutes reaction times, product property viscosity 0.674, L value are 82, b value 3.6.
Comparative example 3
According to the method identical with embodiment 7, difference is that spent glycol antimony 450g replaces the liquid condition titanium series catalyst among the embodiment 7.Pounds per square inch absolute (psia) is 60～80Pa in the whole polycondensation vessel, and the poly-temperature of charge of final minification is 275～276 ℃, and the reaction times is 120 minutes, and the limiting viscosity 0.668 of products therefrom, L value are 83, b value 3.7.
Comparative example 4
According to the method identical with embodiment 8, difference is the EG modulation solution that no longer adds Titanium series catalyst, but revert to 100% consumption when using the EG modulation solution of antimony glycol, namely with the content meter of antimony atoms quality in made polyester gross weight, the Sb addition is 240 * 10
-6The limiting viscosity 0.659 of products therefrom, L value are 89, b value 3.0.
The results of performance analysis of the PET product that obtains in embodiment 2～9 and the comparative example 1～4 is listed in table 1.
Table 1
Annotate
1And notes
2, Titanium series catalyst, antimony glycol are respectively with titanium, the content meter of antimony atoms quality in made polyester gross weight.
Claims (9)
1. method of using liquid condition titanium series catalyst to prepare polyester, it is characterized in that: this preparation method may further comprise the steps:
(A) take at least a dicarboxylic acid and at least a dibasic alcohol as basic raw material, be prepared into slurry, join after stirring and carry out esterification in the reactor, temperature of reaction is 220～280 ℃, reaction pressure is normal pressure～0.3MPa, and the time is 1～4 hour, obtains esterification products;
(B) be 240～280 ℃ in temperature of reaction then, reaction pressure is to carry out prepolymerization reaction under the condition of pounds per square inch absolute (psia) 101kPa～600Pa, and the precondensation time is 0.5～1.5 hour, obtains prepolymer;
(C) prepolymer that step (B) is obtained is 270～295 ℃ in temperature of reaction, and pounds per square inch absolute (psia) is to carry out the poly-reaction of final minification under the condition of 150Pa～50Pa, and the poly-time of final minification is 0.5～2 hour, makes polyester product.It is characterized in that the antimony-based catalyst with liquid condition titanium series catalyst and certain usage ratio before esterification or after the esterification adds in the reaction system.
2. use liquid condition titanium series catalyst according to claim 1 prepares the method for polyester, it is characterized in that: adopt the batch production mode or adopt the continous way mode of production.
3. use liquid condition titanium series catalyst according to claim 1 prepares the method for polyester, it is characterized in that: the antimony-based catalyst of described certain usage ratio, its usage ratio is antimony-based catalyst consumption meter required when preparing polyester for independent use antimony-based catalyst, and proportional range is 0～80%.
4. use liquid condition titanium series catalyst according to claim 2 prepares the method for polyester, it is characterized in that: for the batch production mode: described prepolymerization reaction thermotonus temperature is 240～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～295 ℃, and pounds per square inch absolute (psia) is 150Pa～50Pa.
5. use liquid condition titanium series catalyst according to claim 2 prepares the method for polyester, it is characterized in that: for continous way mode of production device: described prepolymerization reaction temperature is 260～280 ℃, and reaction pressure is pounds per square inch absolute (psia) 101kPa～600Pa; The poly-temperature of reaction of described final minification is 270～290 ℃, and pounds per square inch absolute (psia) is 150Pa～60Pa.
6. the method for preparing according to claim 1 polyester with 3 described use liquid condition titanium series catalysts, it is characterized in that: the consumption of described liquid condition titanium series catalyst, that Ti content is 5 * 10 during not composite use antimony-based catalyst with the content meter of titanium atom quality in made polyester gross weight
-6～60 * 10
-6
7. the method for preparing according to claim 1 polyester with 3 described use liquid condition titanium series catalysts, it is characterized in that: the consumption of described liquid condition titanium series catalyst, that Ti content is 2.5 * 10 during the composite use antimony-based catalyst of 50% ratio with the content meter of titanium atom quality in made polyester gross weight
-6～30 * 10
-6Ti content is 4 * 10 during the composite use antimony-based catalyst of 80% ratio
-6～48 * 10
-6
8. use liquid condition titanium series catalyst according to claim 1 prepares the method for polyester, it is characterized in that: the preparation method of polyester, at least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, and described dicarboxylic acid is selected from terephthalic acid, m-phthalic acid, naphthalic acid, cyclohexane cyclohexanedimethanodibasic, Succinic Acid, pentanedioic acid, hexanodioic acid etc.; Described dibasic alcohol is selected from ethylene glycol, 1,3-PD, naphthalene glycol, 1,2-PD, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, Diethylene Glycol, 1,3-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, triethylene glycol etc.
9. use liquid condition titanium series catalyst according to claim 8 prepares the method for polyester, it is characterized in that: the preparation method of polyester, and described dicarboxylic acid is terephthalic acid, described dibasic alcohol is ethylene glycol.
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| CN1610580A (en) * | 2000-11-21 | 2005-04-27 | 帝国化学工业公司 | Esterification catalyst, polyester process and polyester article |
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