CN102924698A - Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate - Google Patents
Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate Download PDFInfo
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Abstract
The invention discloses a preparation method and a use of a titanium catalyst for synthesis of polybutylene terephthalate. The preparation method comprises the following steps that 1, at least one titanium compound, glycerol and at least one alkaline material undergo a reaction in the presence of at least one solvent at a temperature of 0 to 100 DEG C for 0.1 to 12 hours, wherein the titanium compound is Ti(OR)4 and R represents a C1-10 alkyl group; and 2, the reaction products are added with at least one phosphorus compound; the mixture and an acetate of Na, Li, Mg or Zn undergoes a reaction at a temperature of 50 to 200 DEG C for 0.1 to 12 hours; and micro-molecules in the reaction products are removed and the titanium catalyst which is uniform and stable and has hydrolysis resistance is obtained. The titanium catalyst as an esterification and polymerization catalyst can be directly added into raw materials for synthesis of polybutylene terephthalate, or can be added into the raw materials after being diluted and dissolved in 1,4-butanediol. In polybutylene terephthalate synthesis, the titanium catalyst has the advantages of good activity, small tetrahydrofuran produced by side reactions, stable slice hue and good slice heat stability.
Description
Technical field
The invention belongs to the polyester synthesis technical field, particularly relate to a kind of for polybutylene terephthalate synthetic Titanium series catalyst preparation method and application.
Background technology
Polybutylene terephthalate (be called for short PBT) have excellent machinery, electric, resistance to chemical attack, easy-formation and agent of low hygroscopicity can etc., be a kind of model engineering plastic of high comprehensive performance.Since coming out, developed quite rapid.Become at present in the five large-engineering plastics with fastest developing speed a kind ofly, be applied to many fields such as automobile, electronics, machinery, optical fiber coatings, fiber, and the constantly expansion of new Application Areas.
PBT production technology route can be divided into ester-interchange method and direct esterification, and wherein the direct esterification production technique is take pure terephthalic acid's (be called for short PTA) and BDO (abbreviation BD) as raw material.This technical process is short, and facility investment is lower, and energy consumption is also lower, but need properly settle the BDO dehydration problem.Because reaction conditions is relatively harsher, reaction medium is acid strong.Part BDO cyclodehydration generates tetrahydrofuran (THF) (being called for short THF), and quality product is had a negative impact.
The synthetic catalyzer of PBT has usually: organic titanate class, titanium salt class etc.At present in the actual production of PBT, mostly adopt tetrabutyl titanate as catalyzer, good catalytic activity, but defectiveness is easy to hydrolysis and the part inactivation, and its hydrolysis has not only reduced catalytic activity but also easy blocking pipe, cause the reactor fouling, stop up the heating tubulation, reduced the work-ing life of fondant filter, the device long-term operation is restricted; Thermostability, the melt stability of impact section when titanium content increases, molecular mass reduces, end carboxyl value raises, color and luster deepens thereby make.In addition, such as the titanium salt classes such as hydrolysate of titanous oxalate, titanium tetrachloride, titanium sulfate, solvability is bad in butyleneglycol, and catalytic effect is not as organic titanate.Therefore, select a kind of can suppress few, active high, the addition manner of tetrahydrofuran (THF) generation, hydrolysis, consumption easily catalyzer be necessary very much.
Patent CN 101253217B discloses the catalyzer of the synthetic PBT of compound conduct that uses a kind of element in titanium compound and periodictable 1 family and 2 families, this method has prevented the inactivation of titanium catalyst, suppress the rising of PBT section terminal carboxyl(group), obtain the PBT section of low-end base content, form and aspect and thermal stability are fine.But the described method catalyzer of patent 101253217B is respectively several compounds, the mode of adding reaction system to is comparatively loaded down with trivial details, and the still easy inactivation of hydrolysis not of titanium compound wherein.
Patent CN 1938361B discloses a kind of titanium compound and periodictable 2A family metallic element compound of using as the catalyzer that synthesizes PBT, the excellent performances such as the PBT tone that makes, thermostability, the transparency.But, catalyzer is the metallic element compound of a kind of titanium compound and another kind of periodictable 2A family, it is facile hydrolysis that employed titanium compound runs into water, long period is used easy fouling, influential to equipment and pipeline, another kind of metallic element compound is solid, and is inconvenient when being added continuously to reaction system.
Patent CN 101654511A discloses a kind of polymerizing catalysis stable method of polybutylene terephthalate, adopting tin protochloride and tosic acid in the synthesis technique is dual catalyst, and at the poly-stage adding of final minification stablizer triphenyl phosphite, this method has reduced catalyst levels, shorten generated time, improved the stability of polybutylene terephthalate.The method has used two kinds of compounds as catalyzer, uses again stablizer, and still not too convenient when practical application, chlorion and strongly-acid have corrosive nature to equipment in addition.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of preparation method for the synthetic Titanium series catalyst of polybutylene terephthalate, to overcome the following defective that exists in the prior art: at present in the actual production of PBT, mostly adopt tetrabutyl titanate as catalyzer, be easy to hydrolysis and the part inactivation, its hydrolysis has not only reduced catalytic activity but also easy blocking pipe, cause reactor and pipeline scaling, affect the long-term operation of device; Thermostability, the melt stability of impact section when titanium content increases, molecular mass reduces, end carboxyl value raises, color and luster deepens thereby make.
Of the present invention for the synthetic Titanium series catalyst of polybutylene terephthalate, this catalyzer is the liquid composition of stable, homogeneous, hydrolysis, the technical scheme that adopts may further comprise the steps: (A) titanium compound, glycerol, alkaline substance were reacted 0.1～12 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 Na, Li, Mg, Zn metallic element, under 50～200 ℃ of temperature condition, reacted 0.1～12 hour, remove small molecules, make the liquid catalyst of homogeneous, stable, hydrolysis.
Wherein the mol ratio of titanium compound and glycerol is 1:0.1～20, the mol ratio of titanium compound and alkaline substance is 1 :～0.05～5, the mol ratio of titanium compound and phosphorus compound is 1:0.1～10, the mol ratio of titanium compound and described metallic element is 1:0.02～10, and the mol ratio of titanium compound and solvent is 1:2～50.
In the technique scheme, the preferred version of titanium compound is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate, the tetrabutyl titanate.Described alkali is at least a in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood.The preferred version of 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 that described solvent is BDO, water or their two kinds of mixtures.
In the technique scheme, the mol ratio of titanium compound and glycerol is preferably 1:0.5～15, the mol ratio of titanium compound and alkaline substance is preferably 1:0.067～2, the mol ratio of titanium compound and phosphorus compound is preferably 1:0.1～5, the mol ratio of titanium compound and described metallic element is preferably 1:0.033～5, and the mol ratio of titanium compound and solvent is preferably 1:2～30.
Catalyzer of the present invention, in solvent, reacts titanium compound and glycerol and made intermediate product in 0.1～12 hour as the main body catalyzer with titanium elements under 0～100 ℃ of temperature condition; Introduce simultaneously phosphoric and other metallic element, adding phosphorus compound in the reaction intermediates that obtains further reacts with the another kind of acetate that is selected from Na, Li, Mg, Zn metallic element, under 50～200 ℃ of temperature condition, reacted 0.1～12 hour, add the heat extraction small molecules and be prepared from.
This Titanium series catalyst is the liquid of homogeneous, and stable in properties, hydrolysis can be stablized preservation.This catalyzer can directly or dilute and be dissolved in 1, add in the raw material of synthetic polybutylene terephthalate behind the 4-butyleneglycol, as the catalyzer of esterification and polymerization process, catalyst loading (take the weight ratio of the PBT polyester of contained titanium atom and preparation) is as 5 * 10
-6～200 * 10
-6, preferred add-on is 10 * 10
-6～150 * 10
-6The catalyzer that makes can use separately, does not need to add other auxiliary agents.
Catalyzer can directly or dilute and be dissolved in 1, add in the raw material of synthetic polybutylene terephthalate behind the 4-butyleneglycol, catalyzer as esterification and polymerization process, when using this catalyst to synthesize mutual-phenenyl two acid bromide two alcohol ester, active tetrahydrofuran (THF) good, that side reaction generates is few, the excellent performances such as the hue of chip that is synthesized, thermostability.
The catalyzer that makes can be used for producing the PBT polyester, and synthetic PBT polyester can for the production of fields such as resin, film, fibers, be made various subsequent products.
The preparation method of PBT polyester is as follows: the first step is by terephthalic acid and 1, the 4-butyleneglycol is mixed into slurry, stir after adding the prepared catalyzer of above-mentioned amount, carry out esterification, 200～250 ℃ of temperature of reaction, absolute pressure 202650～50pa reacted 0.5～4 hour, obtained intermediate product.Second step carries out polycondensation with intermediate product, and 230～260 ℃ of temperature of reaction, absolute pressure are 70～200Pa, reacts after 0.5～4 hour, obtains the PBT polyester product of certain viscosity.
Among the present invention, the analytical test by the following method such as THF content in the limiting viscosity of polyester, end carboxyl, form and aspect b value and the distillate:
(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) form and aspect b value: measure with the full-automatic colour examining colour-difference-metre of TC-P II G.
(4) by-product THF content: use gas chromatography determination.
The present invention adopts titanium compound, glycerol, alkaline substance to react under the certain condition in solvent and obtains intermediate product, intermediate product again with phosphorus compound and a kind of acetate that is selected from Na, Li, Mg, Zn metallic element, react under certain condition and remove small molecules, make the liquid catalyst of homogeneous, stable, hydrolysis.This catalyzer and 1, the 4-butyleneglycol dissolves each other, with certain add-on, add pure terephthalic acid (PTA) and 1 to after can directly adding or be mixed with certain density butanediol solution, in the slurry of 4-butyleneglycol, carry out esterification and polycondensation, the excellent performances such as the form and aspect of the PBT section of being synthesized, thermostability.
Embodiment
Embodiment 1
The mol ratio of titanium isopropylate and glycerol is 1:0.5, the mol ratio of titanium isopropylate and sodium hydroxide is 1:0.5, the mol ratio of titanium isopropylate and triethyl phosphate is 1:0.5, the mol ratio of titanium isopropylate and described four hydration magnesium acetates is 1:0.5, the mol ratio of titanium isopropylate and BDO solvent is 1:3.73.
In the reactor that agitator, separating funnel and condenser are housed, add 42.6g titanium isopropylate (0.15mol) and 6.9g glycerol (0.075mol) and 50g BDO (0.56mol), mix.Slowly splash into the solution of 3.0g sodium hydroxide (0.075mol) and 50g deionized water in the reactor, drip finish after, room temperature to 100 ℃ reaction 1 hour.Separate out white depositions, continue to add 16.1g four hydration magnesium acetates (0.075mol) and 13.7g triethyl phosphate (0.075mol), be warming up to gradually 160 ℃ of lower coreactions 3 hours 50 ℃ of beginnings, remove small molecules, become homogeneous liquid to system, obtain catalyst A.
The preparation of PBT polyester
With 500g terephthalic acid (PTA), 450g1, (based on the amount of the polyester that generates, the weight content of titanium atom is 70 * 10 for 4-butyleneglycol (BD) and catalyst A
-6), add the 2L polymerization reaction kettle.Carry out esterification under the condition of 200 ℃～250 ℃ and 50～202650Pa (absolute pressure), when distillate reaches 95% when above of theoretical value, esterification finishes.The intermediate product that esterification obtains is to carry out polycondensation under the condition of 70～200Pa in 230～260 ℃ of temperature of reaction, absolute pressure, reacted 0.5～4 hour, stopped reaction after polycondensation product reaches desired characteristic viscosity, afterwards reaction product is extruded with bar shaped continuously from the polymeric kettle bottom, through water cooling, pelletizing.
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 2
The mol ratio of tetrabutyl titanate and glycerol is 1:0.1, the mol ratio of tetrabutyl titanate and sodium hydroxide is 1:0.05, the mol ratio of tetrabutyl titanate and triethyl phosphate is 1:10, the mol ratio of tetrabutyl titanate and described sodium acetate trihydrate is 1:10, the mol ratio of tetrabutyl titanate and BDO solvent is 1:50.
In the reactor that agitator, separating funnel and condenser are housed, add 51.1g tetrabutyl titanate (0.15mol) and 1.4g glycerol (0.015mol) and 675g BDO (7.5mol), mix.Slowly splash into the solution of 0.3g sodium hydroxide (0.0075mol) and 50g deionized water in the reactor, drip finish after, room temperature to 50 ℃ reaction 0.1 hour.Separate out white depositions, continue to add 204.2g sodium acetate trihydrate (1.5mol) and 273.1g triethyl phosphate (1.5mol), be warming up to gradually 200 ℃ 50 ℃ of beginnings and reacted 12 hours, remove small molecules, become homogeneous liquid to system, obtain catalyst B.
The preparation of PBT
Adopt method similarly to Example 1 to prepare the PBT polyester, (based on the amount of the polyester that generates, the weight content of titanium atom is 5 * 10 as catalyzer to use catalyst B
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 3
The mol ratio of titanium isopropylate and glycerol is 1:20, the mol ratio of titanium isopropylate and yellow soda ash is 1:5, the mol ratio of titanium isopropylate and trimethyl phosphite 99 is 1:0.1, the mol ratio of titanium isopropylate and described four hydration magnesium acetates is 1:0.02, the mol ratio of titanium isopropylate and BDO solvent is 1:2.
In the reactor that agitator, separating funnel and condenser are housed, add 42.6g titanium isopropylate (0.15mol) and 276.0g glycerol (3.0mol) and 27.0g BDO (0.30mol), mix.Slowly splash into the solution of 79.5g yellow soda ash (0.75mol) and 100g deionized water in the reactor, drip finish after, room temperature to 100 ℃ reaction 12 hours.Separate out white depositions, continue to add 6.4g four hydration magnesium acetates (0.003mol) and 2.1g trimethyl phosphite 99 (0.015mol), be warming up to gradually 200 ℃ of reaction responses 0.1 hour 50 ℃ of beginnings, remove small molecules, become homogeneous liquid to system, obtain catalyzer C.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 200 * 10 as catalyzer to use catalyzer C
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 4
The mol ratio of titanium isopropylate and glycerol is 1:0.5, the mol ratio of titanium isopropylate and potassium hydroxide is 1:0.067, the mol ratio of titanium isopropylate and triethyl phosphate is 1:0.1, the mol ratio of titanium isopropylate and described two hydration lithium acetates is 1:0.033, the mol ratio of titanium isopropylate and BDO solvent is 1:2.
In the reactor that agitator, separating funnel and condenser are housed, add 42.6g titanium isopropylate (0.15mol) and 6.75g glycerol (0.075mol) and 27g BDO (0.3mol), mix.Slowly splash into the solution of 0.56g potassium hydroxide (0.01mol) and 25g deionized water in the reactor, drip finish after, room temperature to 90 ℃ reaction 2 hours.Separate out white depositions, continue to add 5.1g two hydration lithium acetates (0.05mol) and 2.7g triethyl phosphate (0.05mol), be warming up to 190 ℃ of lower reactions 2.5 hours at 50 ℃, remove small molecules, become homogeneous liquid to system, obtain catalyzer D.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 150 * 10 as catalyzer to use catalyzer D
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 5
The mol ratio of tetraethyl titanate and glycerol is 1:15, the mol ratio of tetraethyl titanate and potassium hydroxide is 1:2, the mol ratio of tetraethyl titanate and trimethyl phosphite 99 is 1:5, the mol ratio of tetraethyl titanate and described two hydration zinc acetates is 1:5, the mol ratio of tetraethyl titanate and BDO solvent is 1:30.
In the reactor that agitator, separating funnel and condenser are housed, add 34.2g tetraethyl titanate (0.15mol) and 207.0g glycerol (2.25mol) and 405g BDO (4.5mol), mix.Slowly splash into the solution of 16.8g potassium hydroxide (0.3mol) and 25g deionized water in the reactor, drip finish after, room temperature to 90 ℃ reaction 1.5 hours.Separate out white depositions, continue to add 164.6g two hydration zinc acetates (0.75mol) and 105.8g trimethyl phosphite 99 (0.75mol), be warming up to 190 ℃ of lower reactions 3 hours at 50 ℃, remove small molecules, become homogeneous liquid to system, obtain catalyzer E.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 50 * 10 as catalyzer to use catalyzer E
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 6
The mol ratio of tetraethyl titanate and glycerol is 1:0.5, the mol ratio of tetraethyl titanate and salt of wormwood is 1:0.067, the mol ratio of tetraethyl titanate and tributyl phosphate is 1:5, the mol ratio of tetraethyl titanate and described four hydration magnesium acetates is 1:5, the mol ratio of tetraethyl titanate and BDO solvent is 1:30.
In the reactor that agitator, separating funnel and condenser are housed, add 34.2g tetraethyl titanate (0.15mol) and 6.75g glycerol (0.075mol) and 405g BDO (4.5mol), mix.Slowly splash into the solution of 1.06g salt of wormwood (0.01mol) and 100g deionized water in the reactor, drip finish after, room temperature to 80 ℃ reaction 2 hours.Separate out white depositions, continue to add 160.5g four hydration magnesium acetates (0.75mol) and 66.5g tributyl phosphate (0.75mol), be warming up to 180 ℃ of lower reactions 4 hours at 50 ℃, remove small molecules, become homogeneous liquid to system, obtain catalyzer F.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 10 * 10 as catalyzer to use catalyzer F
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 7
The mol ratio of titanium isopropylate and glycerol is 1:15, the mol ratio of titanium isopropylate and sodium hydroxide is 1:2, the mol ratio of titanium isopropylate and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is 1:0.1, the mol ratio of titanium isopropylate and described two hydration zinc acetates is 1:0.033, the mol ratio of titanium isopropylate and BDO solvent is 1:2.
In the reactor that agitator, separating funnel and condenser are housed, add 42.6g titanium isopropylate (0.15mol) and 202.5g glycerol (2.25mol) and 27g BDO (0.15mol), mix.In reactor, slowly splash into 3.0g sodium hydroxide 12.0g(0.3mol) and the solution of 50g deionized water, drip finish after, room temperature to 60 ℃ reaction 0.1 hour.Separate out white depositions, continue to add 1.1g two hydration zinc acetates (0.005mol) and 6.2g 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (content is 50%) solution (0.015mol), be warming up to 200 ℃ of lower reactions 3.5 hours at 50 ℃, remove small molecules, become homogeneous liquid to system, obtain catalyzer G.
The preparation of PBT polyester
Adopt method similarly to Example 1 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 70 * 10 as catalyzer to use catalyzer F
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Embodiment 8
The mol ratio of metatitanic acid tetramethyl ester and glycerol is 1:0.5, the mol ratio of metatitanic acid tetramethyl ester and salt of wormwood is 1:067, the mol ratio of metatitanic acid tetramethyl ester and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is 1:5, the mol ratio of tetraethyl titanate and described sodium acetate trihydrate is 1:5, the mol ratio of metatitanic acid tetramethyl ester and BDO solvent is 1:30.
In the reactor that agitator, separating funnel and condenser are housed, add 25.8g metatitanic acid tetramethyl ester (0.15mol) and 6.8g glycerol (0.075mol) and 405g BDO (4.5mol), mix.Slowly splash into the solution of 13.8g salt of wormwood (0.1mol) and 100g deionized water in the reactor, drip finish after, room temperature to 80 ℃ reaction 2.5 hours.Separate out white depositions, continue to add 102.0g sodium acetate trihydrate (0.75mol) and 309.5g 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (content is 50%) solution (0.75mol), be warming up to 200 ℃ of lower reactions 5 hours at 50 ℃, remove small molecules, become homogeneous liquid to system, obtain catalyzer H.
The preparation of PBT
Adopt method similarly to Example 7 to prepare PBT, (based on the amount of the polyester that generates, the weight content of titanium atom is 10 * 10 as catalyzer to use catalyzer H
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Comparative example 1
Adopt method similarly to Example 1 to prepare the PBT polyester, (based on the amount of the polyester that generates, the weight content of antimony atoms is 150 * 10 as catalyzer to use tetrabutyl titanate (being called for short TBT)
-6).
Analyze tetrahydrofuran (THF) (THF) content in the distillate, and the PBT product that makes is carried out performance test, analytical results sees Table 1.
Table 1
Claims (9)
1. preparation method who is used for the synthetic Titanium series catalyst of polybutylene terephthalate, it is characterized in that may further comprise the steps: (A) titanium compound, glycerol, alkaline substance were reacted 0.1～12 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 Na, Li, Mg, Zn metallic element, under 50～200 ℃ of temperature condition, reacted 0.1～12 hour, make liquid catalyst;
Wherein the mol ratio of titanium compound and glycerol is 1:0.1～20, the mol ratio of titanium compound and alkaline substance is 1 :～0.05～5, the mol ratio of titanium compound and phosphorus compound is 1:0.1～10, the mol ratio of titanium compound and described metallic element is 1:0.02～10, and the mol ratio of titanium compound and solvent is 1:2～50.
2. in accordance with the method for claim 1, it is characterized in that, titanium compound is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate or the tetrabutyl titanate.
3. in accordance with the method for claim 1, it is characterized in that, alkaline substance is at least a in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood.
4. in accordance with the method for claim 1, it is characterized in that, 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 or the ethylenediamine tetraacetic fork phosphonic acids.
5. in accordance with the method for claim 1, it is characterized in that, described solvent is BDO, water or their two kinds of mixtures.
6. in accordance with the method for claim 1, it is characterized in that, the mol ratio of titanium compound and glycerol is 1:0.5～15, the mol ratio of titanium compound and alkaline substance is 1:0.067～2, the mol ratio of titanium compound and phosphorus compound is 1:0.1～5, the mol ratio of titanium compound and described metallic element is 1:0.033～5, and the mol ratio of titanium compound and solvent is 1:2～30.
7. in accordance with the method for claim 1, it is characterized in that, the Titanium series catalyst that makes is the liquid of hydrolysis, dissolves each other with butyleneglycol.
8. the catalyst system of claim 1 is used for the polybutylene terephthalate synthetic method, it is characterized in that catalyst loading, in the weight ratio of the PBT polyester of contained titanium atom and preparation in the catalyzer, is 5 * 10
-6～200 * 10
-6
9. method as claimed in claim 8 is characterized in that catalyst loading, in the weight ratio of the PBT polyester of contained titanium atom and preparation in the catalyzer, is 10 * 10
-6～150 * 10
-6
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| CN103342802A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Preparation method of polybutylene terephthalate |
| CN104558554A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyester resin |
| CN106084189A (en) * | 2015-04-28 | 2016-11-09 | 安庆和兴化工有限责任公司 | Liquid condition titanium series catalyst and the preparation method using its manufacture polyester polymers |
| WO2017061415A1 (en) * | 2015-10-09 | 2017-04-13 | 東洋紡株式会社 | Polyester composition for master batches, polyester composition for films, and polyester film |
| CN109666131A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of polybutylene terephthalate (PBT) resin |
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| CN104558554A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyester resin |
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| CN111087593A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Catalyst composition for inhibiting THF (tetrahydrofuran) generation and hydrolysis resistance as well as preparation method and application thereof |
| CN111484608A (en) * | 2020-03-16 | 2020-08-04 | 东华大学 | Preparation method capable of producing PBT resin stably for long period |
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| CN114672005A (en) * | 2022-03-16 | 2022-06-28 | 中国石油化工股份有限公司 | Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate |
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