CN102924698B - 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 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, develop quite rapid.At present become one with fastest developing speed in five large-engineering plastics, be applied to many fields such as automobile, electronics, machinery, optical fiber are coated, fiber, and new Application Areas has constantly been expanded.
PBT production technology route can be divided into ester-interchange method and direct esterification, and wherein direct esterification production technique is taking 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 BDO dehydration problem.Because reaction conditions is 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 conventionally: 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 part inactivation, and its hydrolysis has not only reduced catalytic activity but also easy blocking pipe, cause reactor fouling, stop up heating tubulation, reduced the work-ing life of fondant filter, device long-term operation is restricted; Thermostability, the melt stability of impact section when titanium content increases, thus make molecular mass reduce, hold the rising of carboxyl value, color and luster to deepen.In addition, as titanium salt classes such as the hydrolysates of titanous oxalate, titanium tetrachloride, titanium sulfate, in butyleneglycol, solvability is bad, and catalytic effect is not as organic titanate.Therefore, select one 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 compound that uses a kind of element in titanium compound and periodictable 1 family and 2 families as the catalyzer of synthetic PBT, 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 method catalyzer described in 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 making, 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 the titanium compound using runs into water, long period is used easy fouling, equipment and pipeline is had to impact, another kind of metallic element compound is solid, inconvenience while being added continuously to reaction system.
Patent CN 101654511A discloses a kind of polymerizing catalysis stable method of polybutylene terephthalate, in synthesis technique, adopting tin protochloride and tosic acid is dual catalyst, and add stablizer triphenyl phosphite in whole polycondensation phase, this method has reduced catalyst levels, shorten generated time, improved the stability of polybutylene terephthalate.The method has been used two kinds of compounds as catalyzer, uses again stablizer, and still not too convenient in the time of 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 open a kind of preparation methods for the synthetic Titanium series catalyst of polybutylene terephthalate, to overcome the following defect existing in prior art: at present in the actual production of PBT, mostly adopt tetrabutyl titanate as catalyzer, be easy to hydrolysis and 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, thus make molecular mass reduce, hold the rising of carboxyl value, color and luster to deepen.
Of the present invention for the synthetic Titanium series catalyst of polybutylene terephthalate, this catalyzer be stablize, the liquid composition of homogeneous, hydrolysis, the technical scheme adopting comprises the following steps: (A) titanium compound, glycerol, alkaline substance are reacted 0.1～12 hour under 0～100 DEG C 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 the acetate of phosphorus compound and a kind of Na of being selected from, Li, Mg, Zn metallic element, under 50～200 DEG C of temperature condition, react 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 technique scheme, the preferred version of titanium compound is selected from least one in metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate, tetrabutyl titanate.Described alkali is at least one in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood.The preferred version of phosphorus compound is at least one 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, ethylenediamine tetraacetic fork phosphonic acids.Described solvent is that described solvent is BDO, water or their two kinds of mixtures.
In 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 is using titanium elements as main body catalyzer, and titanium compound and glycerol, in solvent, are reacted and within 0.1～12 hour, made intermediate product under 0～100 DEG C of temperature condition; Introduce phosphoric and other metallic element simultaneously, in the reaction intermediates obtaining, add phosphorus compound and the another kind of acetate that is selected from Na, Li, Mg, Zn metallic element further to react, under 50～200 DEG C of temperature condition, react 0.1～12 hour, add 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, after 4-butyleneglycol, add in the raw material of synthetic polybutylene terephthalate, as the catalyzer of esterification and polymerization process, catalyst loading (taking 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
-6.The catalyzer making can use separately, does not need to add other auxiliary agents.
Catalyzer can directly or dilute and be dissolved in 1, after 4-butyleneglycol, add in the raw material of synthetic polybutylene terephthalate, as the catalyzer of esterification and polymerization process, while 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 performance such as hue of chip, thermostability of synthesized.
The catalyzer making can be used for producing 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 1,4-butyleneglycol is mixed into slurry, after adding the prepared catalyzer of above-mentioned amount, stir, carry out esterification, 200～250 DEG C of temperature of reaction, absolute pressure 202650～50pa, reacts 0.5～4 hour, obtains intermediate product.Intermediate product is carried out polycondensation by second step, 230～260 DEG C of temperature of reaction, and absolute pressure is 70～200Pa, reacts after 0.5～4 hour, obtains the PBT polyester product of certain viscosity.
In 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 distillate:
(1) limiting viscosity: take 0.125g left and right section sample, be dissolved in the mixed solvent of phenol/tetrachloroethane (mass ratio is 1:1), in 25 ± 0.5 DEG C, 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 the titration of sodium hydroxide/methyl alcohol/phenylcarbinol standardized solution.
(3) form and aspect b value: by the full-automatic colour examining colour-difference-metre mensuration of TC-P II G.
(4) by-product THF content: use gas chromatography determination.
The present invention adopts titanium compound, glycerol, alkaline substance under certain condition, to react and obtain intermediate product in solvent, 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, making the liquid catalyst of homogeneous, stable, hydrolysis.This catalyzer and 1,4-butyleneglycol dissolves each other, with certain add-on, after can directly adding or be mixed with certain density butanediol solution, add pure terephthalic acid (PTA) and 1 to, in the slurry of 4-butyleneglycol, carry out esterification and polycondensation, the excellent performance such as form and aspect, thermostability of the PBT section of synthesized.
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.
Add 42.6g titanium isopropylate (0.15mol) and 6.9g glycerol (0.075mol) and 50g BDO (0.56mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 3.0g sodium hydroxide (0.075mol) and 50g deionized water in reactor, after dripping and finishing, room temperature to 100 DEG C reaction 1 hour.Separate out white depositions, continue to add 16.1g tetra-hydration magnesium acetates (0.075mol) and 13.7g triethyl phosphate (0.075mol), be warming up to gradually at 160 DEG C coreaction 3 hours 50 DEG C of beginnings, remove small molecules, become homogeneous liquid to system, obtain catalyst A.
The preparation of PBT polyester
By 500g terephthalic acid (PTA), 450g1, (amount of the polyester based on generating, the weight content of titanium atom is 70 × 10 for 4-butyleneglycol (BD) and catalyst A
-6), add 2L polymerization reaction kettle.Under the condition of 200 DEG C～250 DEG C and 50～202650Pa (absolute pressure), carry out esterification, when distillate reaches 95% when above of theoretical value, esterification finishes.Under the condition that the intermediate product that esterification obtains is 70～200Pa in 230～260 DEG C of temperature of reaction, absolute pressure, carry out polycondensation, react 0.5～4 hour, stopped reaction after polycondensation product reaches desired characteristic viscosity, afterwards reaction product is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 51.1g tetrabutyl titanate (0.15mol) and 1.4g glycerol (0.015mol) and 675g BDO (7.5mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 0.3g sodium hydroxide (0.0075mol) and 50g deionized water in reactor, after dripping and finishing, room temperature to 50 DEG C 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 DEG C of reactions 12 hours 50 DEG C of beginnings, remove small molecules, become homogeneous liquid to system, obtain catalyst B.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT polyester, (amount of the polyester based on generating, the weight content of titanium atom is 5 × 10 as catalyzer to use catalyst B
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in table 1.
Embodiment 3
The mol ratio of titanium isopropylate and glycerol is 1:20, the mol ratio of titanium isopropylate and sodium carbonate 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.
Add 42.6g titanium isopropylate (0.15mol) and 276.0g glycerol (3.0mol) and 27.0g BDO (0.30mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 79.5g sodium carbonate (0.75mol) and 100g deionized water in reactor, after dripping and finishing, room temperature to 100 DEG C reaction 12 hours.Separate out white depositions, continue to add 6.4g tetra-hydration magnesium acetates (0.003mol) and 2.1g trimethyl phosphite 99 (0.015mol), be warming up to gradually 200 DEG C of reaction responses 0.1 hour 50 DEG C 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, (amount of the polyester based on generating, the weight content of titanium atom is 200 × 10 as catalyzer to use catalyzer C
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 42.6g titanium isopropylate (0.15mol) and 6.75g glycerol (0.075mol) and 27g BDO (0.3mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 0.56g potassium hydroxide (0.01mol) and 25g deionized water in reactor, after dripping and finishing, room temperature to 90 DEG C reaction 2 hours.Separate out white depositions, continue to add 5.1g bis-hydration lithium acetates (0.05mol) and 2.7g triethyl phosphate (0.05mol), be warming up at 190 DEG C and react 2.5 hours at 50 DEG C, remove small molecules, become homogeneous liquid to system, obtain catalyzer D.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (amount of the polyester based on generating, the weight content of titanium atom is 150 × 10 as catalyzer to use catalyzer D
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 34.2g tetraethyl titanate (0.15mol) and 207.0g glycerol (2.25mol) and 405g BDO (4.5mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 16.8g potassium hydroxide (0.3mol) and 25g deionized water in reactor, after dripping and finishing, room temperature to 90 DEG C reaction 1.5 hours.Separate out white depositions, continue to add 164.6g bis-hydration zinc acetates (0.75mol) and 105.8g trimethyl phosphite 99 (0.75mol), be warming up at 190 DEG C and react 3 hours at 50 DEG C, remove small molecules, become homogeneous liquid to system, obtain catalyzer E.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (amount of the polyester based on generating, the weight content of titanium atom is 50 × 10 as catalyzer to use catalyzer E
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 34.2g tetraethyl titanate (0.15mol) and 6.75g glycerol (0.075mol) and 405g BDO (4.5mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 1.06g salt of wormwood (0.01mol) and 100g deionized water in reactor, after dripping and finishing, room temperature to 80 DEG C reaction 2 hours.Separate out white depositions, continue to add 160.5g tetra-hydration magnesium acetates (0.75mol) and 66.5g tributyl phosphate (0.75mol), be warming up at 180 DEG C and react 4 hours at 50 DEG C, remove small molecules, become homogeneous liquid to system, obtain catalyzer F.
The preparation of PBT
Adopt method similarly to Example 1 to prepare PBT, (amount of the polyester based on generating, the weight content of titanium atom is 10 × 10 as catalyzer to use catalyzer F
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 42.6g titanium isopropylate (0.15mol) and 202.5g glycerol (2.25mol) and 27g BDO (0.15mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.In reactor, slowly splash into 3.0g sodium hydroxide 12.0g(0.3mol) and the solution of 50g deionized water, after dripping and finishing, room temperature to 60 DEG C reaction 0.1 hour.Separate out white depositions, continue to add 1.1g bis-hydration zinc acetates (0.005mol) and 6.2g 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (content is 50%) solution (0.015mol), be warming up at 200 DEG C and react 3.5 hours at 50 DEG C, 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, (amount of the polyester based on generating, the weight content of titanium atom is 70 × 10 as catalyzer to use catalyzer F
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in 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.
Add 25.8g metatitanic acid tetramethyl ester (0.15mol) and 6.8g glycerol (0.075mol) and 405g BDO (4.5mol) to being equipped with in the reactor of agitator, separating funnel and condenser, mix.Toward the solution that slowly splashes into 13.8g salt of wormwood (0.1mol) and 100g deionized water in reactor, after dripping and finishing, room temperature to 80 DEG C 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 at 200 DEG C and react 5 hours at 50 DEG C, remove small molecules, become homogeneous liquid to system, obtain catalyzer H.
The preparation of PBT
Adopt method similarly to Example 7 to prepare PBT, (amount of the polyester based on generating, the weight content of titanium atom is 10 × 10 as catalyzer to use catalyzer H
-6).
Analyze tetrahydrofuran (THF) (THF) content in distillate, and the PBT product making is carried out to performance test, analytical results is in table 1.
Comparative example 1
Adopt method similarly to Example 1 to prepare PBT polyester, (amount of the polyester based on generating, 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 distillate, and the PBT product making is carried out to performance test, analytical results is in table 1.
Table 1
Claims (6)
1. the preparation method for the synthetic Titanium series catalyst of polybutylene terephthalate, it is characterized in that comprising the following steps: (A) titanium compound, glycerol, alkaline substance are reacted 0.1～12 hour under 0～100 DEG C 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 the acetate of phosphorus compound and a kind of Na of being selected from, Li, Mg, Zn metallic element, under 50～200 DEG C of temperature condition, react 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; Titanium compound is selected from least one in metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate or tetrabutyl titanate; Alkaline substance is at least one in sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood; Phosphorus compound is at least one 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 ethylenediamine tetraacetic fork phosphonic acids.
2. in accordance with the method for claim 1, it is characterized in that, described solvent is BDO, water or their two kinds of mixtures.
3. 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.
4. in accordance with the method for claim 1, it is characterized in that the liquid that the Titanium series catalyst making is hydrolysis dissolves each other with butyleneglycol.
5. the catalyst system of claim 1 for polybutylene terephthalate synthetic method, is characterized in that catalyst loading, in the weight ratio of the PBT polyester of contained titanium atom and preparation in catalyzer, is 5 × 10
-6～200 × 10
-6.
6. method as claimed in claim 5, is characterized in that catalyst loading, in the weight ratio of the PBT polyester of contained titanium atom and preparation in 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 |
| CN104558554B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | The 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 |
| JP6822144B2 (en) * | 2015-10-09 | 2021-01-27 | 東洋紡株式会社 | Polyester composition for masterbatch, polyester composition for film, and polyester film |
| CN109666131B (en) * | 2017-10-17 | 2022-02-01 | 中国石油化工股份有限公司 | Preparation method of polybutylene terephthalate resin |
| 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 |
| CN111484608B (en) * | 2020-03-16 | 2021-08-06 | 东华大学 | Preparation method capable of producing PBT resin stably for long period |
| CN114874424A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Preparation method of fast-crystallization type polyester |
| CN114874423A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method thereof, and titanium catalyst composition and preparation method thereof |
| CN114621425A (en) * | 2022-03-16 | 2022-06-14 | 中国石油化工股份有限公司 | Titanium composition for synthesizing poly (butylene succinate-co-terephthalate) and PBST (Poly-p-phenylene Benzene-succinate) synthesis method |
| 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 |
| CN116589670A (en) * | 2023-06-30 | 2023-08-15 | 浙江大学 | High-temperature-hydrolysis-resistant titanium alkoxide organic base catalyst, and preparation method and application thereof |
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| CN102382287A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Liquid titanium catalyst for polyester and copolyester and preparation method thereof |
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| CN1809605A (en) * | 2003-06-17 | 2006-07-26 | 三井化学株式会社 | Titanium-containing solutions, catalysts for production of polyester, processes for production of polyester resins, and blow moldings of polyester |
| CN102382287A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Liquid titanium catalyst for polyester and copolyester and preparation method thereof |
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