CN108892770A - A kind of method of tetrahydrofuran side reaction in inhibition polymerization process - Google Patents
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process Download PDFInfo
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- CN108892770A CN108892770A CN201810488973.2A CN201810488973A CN108892770A CN 108892770 A CN108892770 A CN 108892770A CN 201810488973 A CN201810488973 A CN 201810488973A CN 108892770 A CN108892770 A CN 108892770A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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Abstract
The present invention relates to a kind of methods of tetrahydrofuran side reaction in inhibition polymerization process, with terephthalic acid (TPA) and 1,4- butanediol is during primary raw material prepares polymer, by adding carboxylate, titanium silicon cobalt composite catalyzing agent dispersing liquid and the pH adjusting agent that terephthalic acid (TPA) and diol reaction generate in Esterification Stage, the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol simultaneously is 1:1.05~1.10, inhibit tetrahydrofuran side reaction so that in polymer tetrahydrofuran content≤10wt%；Decentralized medium in titanium silicon cobalt composite catalyzing agent dispersing liquid is 1,4-butanediol, and titanium silicon cobalt composite catalyst is that titanium silicon composite catalyst is combined with cobalt series catalyst, and titanium silicon composite catalyst obtains for silicon systems catalyst carrying catalyst in titanium series.The present invention inhibits tetrahydrofuran side reaction in polymerization process, and finally obtained molecular weight of product distribution is concentrated, by-product is few, quality is good, great application prospect.
Description
Technical field
The invention belongs to polyester preparation fields, are related to a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process, special
It is not related to a kind of method for inhibiting tetrahydrofuran side reaction in PBT polyester or copolyesters polymerization process.
Background technique
Polybutylene terephthalate (PBT) (PBT) has excellent crystal property, heat resistance, chemical corrosion resistance, molding
Performance and agent of low hygroscopicity energy are a kind of new materials of excellent combination property.Currently, the polymerization process of PBT fiber is by PET
What the polymerization technique of fiber developed, there are still many problems in the course of the polymerization process.For example, the raw material of PET is terephthaldehyde
Acid and ethylene glycol, the raw material of PBT are terephthalic acid (TPA) and 1,4-butanediol, two systems main difference is that carbon atom number in alcohol
It is different.In PBT polymerization system, 1,4-butanediol not only reacts to obtain carboxylate with terephthalic acid (TPA), while can intramolecular dehydration
It generates tetrahydrofuran (THF).Due to PBT main reaction with the side reaction for generating THF activation energy close to (main reaction is
127.7kJ/mol, side reaction 134.4kJ/mol) so that side reaction is inhibited to become difficult.
In entire polymerization system, THF mainly is dehydrated to obtain in esterification process by 1,4-butanediol, in addition, contracting
In collecting process, mutual-phenenyl two acid bromide two alcohol ester and some oligomer can also decompose and generate THF.Therefore, in order to inhibit side reaction
The generation of THF, people have carried out many researchs to the polymerizing condition of PBT.In past research, people are mainly by using work
Property higher catalyst improve esterification reaction rate, reduce 1,4-butanediol in the residence time of reaction system, to reduce pair
The generation of product.According to document patent report, catalyst used by PBT polyester is reacted at present mainly has：Antimony-based catalyst, germanium system
Catalyst and Titanium series catalyst etc..Wherein, antimony system and germanium series catalysts contain heavy metal, and environmental pollution is larger, therefore,
The more catalyst of application is Titanium series catalyst at present.But there are still some problems for Titanium series catalyst：Catalytic activity is higher,
It is that sample chromatism measurement jaundice and Titanium series catalyst facile hydrolysis in the course of the polymerization process need further to reduce catalytic activity etc.
Improve polymerization technique.
Patent CN 102924698 discloses a kind of Titanium series catalyst system for polybutylene terephthalate (PBT) synthesis
Preparation Method and application, are mainly prepared for a kind of novel Titanium series catalyst, and the polymerization for polybutylene terephthalate (PBT) is anti-
It answers, activity is higher, reduces the generation of side reaction；Patent CN102850534 discloses a kind of using TiO2/SiO2Composite Nano
The method of catalyst preparation high-quality PBT is mainly prepared for a kind of novel nano-composite catalyst, catalysis with higher
Activity can inhibit the generation of Tetrahydrofuran.Although the above method inhibits side reaction to a certain extent, above two
There is the problems such as molar ratio of alcohol to acid is larger, causes the waste of raw material, inhibits the effect of by-product undesirable in method.
Therefore, it is great existing to develop a kind of method for inhibiting tetrahydrofuran side reaction in PBT polyester or copolyesters polymerization process
Sincere justice.
Summary of the invention
The purpose of the invention is to overcome above-mentioned problems of the prior art, provide a kind of inhibition PBT polyester or
The method of tetrahydrofuran side reaction in copolyesters polymerization process.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05~1.10, inhibit tetrahydrofuran secondary anti-
Answer so that in the polymer tetrahydrofuran content≤10wt%；The content of tetrahydrofuran in polymer is made in the prior art
Generally in 18wt% or so.
Decentralized medium in the titanium silicon cobalt composite catalyzing agent dispersing liquid is 1,4-butanediol, the titanium silicon cobalt composite catalyzing
Agent is that titanium silicon composite catalyst is combined with cobalt series catalyst, and the titanium silicon composite catalyst is silicon systems catalyst supported titanium system
Catalyst and obtain, the guiding thing is the carboxylate that terephthalic acid (TPA) and diol reaction generate.As selected except titanium silicon cobalt is compound
Other catalyst other than catalyst, but will lead to the increase and product color variation of side reaction, Compositional type catalysis of the present invention
Higher catalytic activity may be implemented in agent, while promoting the color of product.
As a preferred technical scheme：
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the specific preparation of the polymer
Steps are as follows：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
It is stirred under dispersing titanium silicon cobalt composite catalyst in 1,4- butanediol under conditions of 300~350rpm and titanium is made
Silicon cobalt composite catalyzing agent dispersing liquid；It is on the one hand that composite catalyst is made to exist by the purpose that composite catalyst is mixed with 1,4- butanediol
Be uniformly dispersed in system, on the other hand, catalyst first is mixed with 1,4-butanediol, can activated partial hydroxyl, thus acceleration with it is right
The reaction of phthalic acid reduces the generation of by-product.
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing, pH tune is added
Esterification is carried out under conditions of 180~240 DEG C and 50~200kPa for section agent until water yield reaches theoretical water yield
95% reaction terminating；
The molar ratio of terephthalic acid (TPA) of the present invention and 1,4- butanediol esterification is 1:1.05~1.10, existing alkyd
Molar ratio is higher easily to cause dihydric alcohol that the ratio for increasing side reaction product from polycondensation occurs at high temperature, but too low alkyd rubs
You are remarkably decreased than will lead to esterification reaction rate, substantially prolong the reaction time；The present invention controls esterification temperature 180~
240 DEG C, this is because esterification process is the endothermic reaction, although excessively high temperature can further speed up esterification reaction rate,
It is the quickening for also resulting in rate of side reactions, too low temperature is unable to satisfy esterification and course of dissolution to the need of heat
It wants；Esterification slightly positive pressure controls pressure in 50~200kPa, this is because since reaction generates small molecule in esterification process
Moisture can promote the promotion of esterification reaction rate with certain direct draught.Excessively high pressure can propose esterification device
Higher requirement, esterification of the present invention carry out on existing apparatus, without further transformation, reduce cost.It is added
Na3PO4, the substances such as sodium citrate and para-phthalic sodium carry out the pH value of regulation system, avoid and promote because system is acid larger
The color of polymerizate is adjusted in the generation of THF, while the addition of the above substance to a certain extent, and sample is made to be easy dyeing.
(3) polycondensation reaction；
The agent of heat resistanceheat resistant oxygen and/or antioxidant are added in the product of step (2) in 200~260 DEG C and the condition of 1~30Pa
The lower prepolymerization reaction for carrying out 15~45min；Finally carry out 1.5~3.5h's under conditions of 220~280 DEG C and 5~10Pa
Polymer is finally made in final polycondensation reaction；The stirring rate of the prepolymerization reaction is 150~400rpm, the final polycondensation reaction
Stirring rate be 100~350rpm.Although not adding the agent of heat resistanceheat resistant oxygen and/or antioxidant yet available low viscosity precondensation
Product, but the precondensation product of low viscosity is easily led in polycondensation process because of degradation problem caused by thermal oxide.
Prepolymerization reaction temperature of the invention is controlled at 200~260 DEG C, this is because too low reaction temperature cause it is pre-
Polycondensation reaction can not carry out, and thermal degradation side reaction enhances during excessively high reaction temperature will lead to prepolymerization reaction, formation
Product color is deteriorated；Prepolymerization reaction pressure is controlled in 1~30Pa, and lower compared to the poly- vacuum degree of final minification, too low pressure is (i.e.
Higher vacuum effectiveness) performed polymer that will lead to low viscosity in prepolymerization reaction is extracted, blocks pipeline, cause polycondensation accident；
Excessively high pressure (i.e. worse vacuum effectiveness) will lead to the removing that cannot achieve polycondensation reaction small molecular, prepolymerization reaction without
Method is normally carried out；The prepolymerization reaction time controls in 15~45min, substantially less than reaction time in the prior art, in the present invention
It is too low to will lead to the performed polymer viscosity to be formed if the prepolymerization reaction time is too short, in high vacuum in final polycondensation reaction below
Under the conditions of easily as 1,4-butanediol small molecule is extracted together, block pipeline；It can be led if the prepolymerization reaction time is too long
The molecular weight of the performed polymer formed is caused to gradually increase, the weight average molecular weight breadth coefficient of product broadens, then after final polycondensation reaction
It further broadens, cannot achieve the purpose that the weight average molecular weight breadth coefficient of the invention patent proposition is concentrated.
Final polycondensation reaction temperature control of the invention at 220~280 DEG C, too low reaction temperature cause final polycondensation reaction without
Method carries out；Thermal degradation side reaction enhances during excessively high reaction temperature will lead to final polycondensation reaction, and the product color of formation becomes
Difference；Final polycondensation reaction pressure is controlled in 5~10Pa, and the requirement of too low pressure (i.e. higher vacuum effectiveness) to equipment is higher；
Excessively high pressure (i.e. worse vacuum effectiveness) will lead to the removing that cannot achieve polycondensation reaction small molecular, final polycondensation reaction without
Method is normally carried out；The control of final polycondensation reaction time will lead to the production to be formed if the final polycondensation reaction time is too short in 1.5~3.5h
Spinning rank is not achieved in object；The thermal degradation that will lead to polymer under hot conditions if the prepolymerization reaction time is too long significantly increases
Add, product declines rapidly after reaching highest weight average molecular weight because of thermal degradation；Final polycondensation reaction stirring rate is 5~10rpm,
Material viscosity is higher than prepolymerization reaction product during final polycondensation reaction, and product viscosity is higher, and stirring is more difficult to, too fast stirring speed
Rate both cannot achieve highly viscous polymeric system the effect of stirring, simultaneously as the too big damage motor of electric current；Too low
The uniform effect of material stirring is not had under stirring rate.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the titanium silicon cobalt composite catalyst
Account for 0.05~0.2mol% of 1,4- butanediol content；The Titanium series catalyst, silicon systems catalyst and cobalt series catalyst account for respectively
58~70wt%, 7~13wt% and the 17~32wt% of titanium silicon cobalt composite catalyst；The Titanium series catalyst is butyl titanate
Or metatitanic acid；The silicon systems catalyst is silica；The cobalt series catalyst is cobalt acetate.
Titanium silicon cobalt composite catalyst molar ratio is excessive to will cause catalyst waste, while will cause sample jaundice；Too small meeting
Keep catalytic activity inadequate, extend the reaction time, is that by-product THF increases, while extending reaction time.Titanium series catalyst is in titanium
It is major catalyst in silicon cobalt composite catalyst, excessively will cause polyester jaundice seriously, it is very few to will affect catalytic activity；Silicon systems catalysis
Agent, mainly as carrier loaded Titanium series catalyst, can make poor catalytic activity if too many, very little in complex catalyst system
Titanium series catalyst can not load completely, make Titanium series catalyst hydrolytic inactivation；Cobalt series catalyst is co-catalyst, is mainly used for preventing
The decomposition of polyester generates Nonferrous Metals Group, can reduce catalytic activity too much, makes sample jaundice serious very little.
The specific preparation method of titanium silicon cobalt composite catalyst is as follows：
Titanium silicon cobalt composite catalyst is by TiO2-SiO2Composite catalyst and cobalt series catalyst mix according to a certain percentage to be added
Enter into polymerization system.Wherein, TiO is obtained using sol-gal process2-SiO2Composite catalyzing agent method is：By suitable positive silicic acid
Ethyl ester, ethyl alcohol, distilled water and nitric acid are added sequentially in three-necked flask, and are uniformly mixed.Three-necked flask is placed on magnetic agitation
It is heated and refluxed on device, sets 65 DEG C of heating temperature, mixing speed 820r/min, flow back 2h.To ethyl orthosilicate complete hydrolysis
Afterwards, 40.0g butyl titanate is added into three-necked flask, stirring 20min mixes it with reactant to hook.It is titrated using constant pressure
Appropriate steaming shop water is slowly added dropwise by given pace in pipe.After dripping, then the 2h that flows back at 65 DEG C.It is placed it in after forming gel
It is aged 12h under room temperature.Dry 12h at 110 DEG C, removes the water and alcohol solvent in reaction system in air dry oven,
The solid after drying is ground in mortar.Powder after grinding is put into Muffle furnace, sets firing temperature as 500 DEG C, to
Temperature starts timing, roast 3h after reaching set temperature.After the completion of roast, roast object is taken out, allows its natural cooling, is finally
TiO can be obtained2-SiO2Composite catalyst.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the additive amount of the guiding thing are
0.5~5.0wt% of terephthalic acid (TPA) additive amount in step (2)；The additive amount of the titanium silicon cobalt composite catalyst is step (2)
100~200ppm of middle terephthalic acid (TPA) additive amount.
Purpose present invention introduces guiding thing is the ratio in order to reduce 1,4-butanediol in raw material, while it is anti-to accelerate esterification
Answer rate.Guiding thing additive amount is too low, cannot achieve effective dissolution to terephthalic acid (TPA) in raw material, and esterification reaction rate accelerates
It is unobvious, reaction time of esterification can be extended instead；Guiding thing adding too much, though rapid dissolution can be played to terephthalic acid (TPA)
Effect, but cost will increase, and economy is bad.
The additive amount of titanium silicon cobalt composite catalyst is 100~200ppm of terephthalic acid (TPA) additive amount, and the present invention selects to use
Composite catalyst, which allows for, should guarantee catalytic effect while can play the role of promotion to final product.Too low catalysis
Agent additive amount will lead to catalytic effect decline, and the reaction time is elongated, and efficiency reduces；Excessively high catalyst amount, which will lead to, to react
In fast, it is possible to " implode " danger occur, while also increase cost.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the additive amount of the pH adjusting agent
For 80~200ppm of terephthalic acid (TPA) additive amount in step (2)；The pH adjusting agent is Na3PO4, sodium citrate and to benzene two
One or more of sodium formate.The protection scope of pH adjusting agent of the present invention is not limited to that other can play system pH and adjust
The alkalescent substance of section effect is equally applicable to the present invention, and the additive amount of pH adjusting agent can be selected according to the actual situation, be added
Dosage is too small, effectively can not increase pH by control system pH, side reaction is inhibited to carry out, additive amount is excessive, and system pH is excessively high, influences
Reaction.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the terephthalic acid (TPA) and binary
The esterification yield that alcohol reaction generates guiding thing is 90~98%, and if esterification yield is lower than this range, esterification guiding thing is partially reaction
Good carboxylate, is partially unreacted terephthalic acid (TPA) and dihydric alcohol, if using the esterification guiding thing, it can attenuating pair significantly
The solubility property of terephthalic acid (TPA)；The dihydric alcohol is ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, pungent
One or more of glycol, nonanediol and decanediol.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the additional amount of the heat resistanceheat resistant oxygen agent
For 0.005~0.05wt% of terephthalic acid (TPA) additive amount in step (2)；The additional amount of the antioxidant is in step (2)
0.001~0.01wt% of terephthalic acid (TPA) additive amount.
A kind of method for inhibiting tetrahydrofuran side reaction in polymerization process as described above, the heat resistanceheat resistant oxygen agent be phosphoric acid,
One or more of phosphorous acid, trimethyl phosphate, Trimethyl phosphite and triphenyl phosphate；The antioxidant is antioxidant
1010, one or more of antioxidant 168 and antioxidant 616.
A kind of method inhibiting tetrahydrofuran side reaction in polymerization process as described above, the Weight-average molecular of the polymer
Measuring breadth coefficient is 1.2~1.6, and inherent viscosity is 1.00~1.25dL/g, color≤10.
A kind of method for inhibiting tetrahydrofuran side reaction in polymerization process as described above, by the polymer be made POY,
FDY or DTY fiber process waste silk rate≤10kg/t, yarn unevenness≤1.0% of fiber.The polymer removes and fiber is made
Outside, it is alternatively arranged as the raw material of the products such as film, plastics.
Invention mechanism：
Present invention utilizes terephthalic acid (TPA)s to the preferable characteristic of oligomer dissolubility, adds and draws in esterification reaction process
Leading object makes reaction system become liquid-liquid interface from solid-liquid interface, improves alkyd reaction rate, it is suppressed that the generation of THF, together
When so that esterification time is reduced to 1.5~3h.Esterification products are subjected to polycondensation reaction later, the prepolymerization temperature that this stage uses
Degree is 200~260 DEG C, and reaction pressure is 1~30pa；The final polycondensation reaction temperature used is 220 DEG C~280 DEG C, reaction pressure
For 5~10Pa, the polybutylene terephthalate (PBT) (PBT) or its copolyesters of fiber high molecular weight are finally obtained.
The titanium silicon cobalt composite catalyst that the present invention uses can effectively reduce the decomposition of polycondensation phase carboxylate and oligomer, suppression
THF side reaction processed, Nano-meter SiO_2 in titanium silicon cobalt composite catalyst2Presence not only avoid the hydrolysis of Titanium series catalyst, while can
The activity of Titanium series catalyst is efficiently controlled, polycondensation phase carboxylate is reduced and decomposes generation THF.In addition, cobalt series catalyst adds
Enter to improve the color of product, facilitates stock-dye uniformly secured.Na is added during prepolymerization reaction3PO4, citric acid
The pH value of the substances regulation system such as sodium and para-phthalic sodium, also can inhibit the generation of THF.
Beneficial effect：
(1) in a kind of inhibition polymerization process of the invention tetrahydrofuran side reaction method, drawn using terephthalic acid (TPA)
Leading has preferable dissolubility in object, reaction system is made to become lower liquid-liquid circle of energy from the higher solid-liquid interface of energy
Face, alkyd reaction rate improve rapidly, to reduce the generation of side reaction；
(2) in a kind of inhibition polymerization process of the invention tetrahydrofuran side reaction method, pass through be added guiding thing reduce
Molar ratio of alcohol to acid reduces the use of raw material, saves cost of material, improves esterification rate, shortens reaction time of esterification, mention
High efficiency；
(3) in a kind of inhibition polymerization process of the invention tetrahydrofuran side reaction method, using titanium-, silicon-cobalt is compound urges
Agent solves the hydrolysis problem of Titanium series catalyst, reduces carboxylate in polycondensation process and decomposes generation THF；In addition, cobalt system urges
The presence of agent has adjusted the color of polyester product, avoids the problem for keeping dyeing difficult because of sample jaundice；
(4) in a kind of inhibition polymerization process of the invention tetrahydrofuran side reaction method, pass through be added Na3PO4, lemon
The substances such as sour sodium and para-phthalic sodium carry out the pH value of regulation system, avoid and promote the generation of THF because system is acid larger；
Meanwhile the addition of these substances, the color of polymerizate is adjusted to a certain extent, sample is made to be easy dyeing；
(5) in a kind of inhibition polymerization process of the invention tetrahydrofuran side reaction method, easy to operate, effect is good, no
Cost of material has only been saved, meanwhile, THF separation and cost recovery are reduced, it is good in economic efficiency.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 5wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 300rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
70%, 13% and the 17% of catalyst, titanium silicon cobalt composite catalyst account for the 0.2mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, be added titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and
Na3PO4Esterification is carried out under conditions of 180 DEG C and 200KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, guiding thing is the carboxylate that terephthalic acid (TPA) and glycol reaction generate, and the esterification yield for generating guiding thing is 90%；Na3PO4
Additive amount be terephthalic acid (TPA) additive amount 200ppm, the additive amount of guiding thing is the 5.0wt% of terephthalic acid (TPA) additive amount,
The additive amount of titanium silicon cobalt composite catalyst is the 200ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
The prepolymerization reaction that phosphoric acid carries out 15min under conditions of 200 DEG C and 1Pa is added in the product of step (2)；Most
Polymer is finally made in the final polycondensation reaction for carrying out 1.5h under conditions of 220 DEG C and 5Pa eventually；The stirring rate of prepolymerization reaction
For 400rpm, the stirring rate of final polycondensation reaction is 350rpm；The additional amount of phosphoric acid is terephthalic acid (TPA) additive amount in step (2)
0.005wt%.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.6, inherent viscosity 1.25dL/g, and color is
10；POY fiber is made in the final polymer that is made, processing waste silk rate is 10kg/t, and the yarn unevenness of fiber is 1.0%.
Embodiment 2
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.10, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 10wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
Metatitanic acid is carried on after titanium silicon composite catalyst is made on silica, mixed with titanium silicon composite catalyst and acetic acid
Cobalt obtains titanium silicon cobalt composite catalyst, disperses the item in 1,4-butanediol in 300~350rpm for titanium silicon cobalt composite catalyst
It is stirred under part and titanium silicon cobalt composite catalyzing agent dispersing liquid is made, metatitanic acid, silica and cobalt acetate account for that titanium silicon cobalt is compound to urge respectively
60wt%, 11wt%, 29wt% of agent, titanium silicon cobalt composite catalyst account for the 0.05mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and lemon is added
Lemon acid sodium carries out esterification under conditions of 240 DEG C and 50KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with propylene glycol, and the esterification yield for generating guiding thing is 98%；Citric acid
The additive amount of sodium is the 80ppm of terephthalic acid (TPA) additive amount, and the additive amount of guiding thing is terephthalic acid (TPA) additive amount
0.5wt%, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
The precondensation that phosphorous acid progress 45min under conditions of 260 DEG C and 30Pa is added in the product of step (2) is anti-
It answers；Polymer is finally made in the final polycondensation reaction that 3.5h is finally carried out under conditions of 280 DEG C and 10Pa；Prepolymerization reaction stirs
Mixing rate is 300rpm, and the stirring rate of final polycondensation reaction is 300rpm；The additional amount of phosphorous acid is terephthaldehyde in step (2)
The 0.05wt% of sour additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.2, inherent viscosity 1.00dL/g, and color is
8；FDY fiber is made in the final polymer that is made, processing waste silk rate is 9.5kg/t, and the yarn unevenness of fiber is 0.8%.
Embodiment 3
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.07, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 7wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 320rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
65wt%, 8wt%, 27wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.1mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and right is added
Phthalic acid sodium at 200 DEG C and under conditions of 100KPa carry out esterification until water yield reach theoretical water yield it is 95% anti-
It should terminate, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with butanediol, and the esterification yield for generating guiding thing is 95%；It is right
The additive amount of phthalic acid sodium is the 140ppm of terephthalic acid (TPA) additive amount, and the additive amount of guiding thing is terephthalic acid (TPA) additive amount
2.5wt%, the additive amount of titanium silicon cobalt composite catalyst is the 150ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
The precondensation that trimethyl phosphate carries out 30min under conditions of 220 DEG C and 12Pa is added in the product of step (2)
Reaction；Polymer is finally made in the final polycondensation reaction that 2.5h is finally carried out under conditions of 250 DEG C and 6Pa；Prepolymerization reaction
Stirring rate is 330rpm, and the stirring rate of final polycondensation reaction is 270rpm；The additional amount of trimethyl phosphate is right in step (2)
The 0.01wt% of phthalic acid additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.4, inherent viscosity 1.12dL/g, and color is
9；DTY fiber is made in the final polymer that is made, processing waste silk rate is 8.9kg/t, and the yarn unevenness of fiber is 0.9%.
Embodiment 4
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.08, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 8wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 340rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
67wt%, 9wt%, 24wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.12mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, be added titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and
Na3PO4/ sodium citrate (mass ratio 1:1) esterification is carried out under conditions of 200 DEG C and 200KPa until water yield reaches reason
By 95% reaction terminating of water yield, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with pentanediol, generates guiding thing
Esterification yield be 92%；Na3PO4The additive amount of/sodium citrate is the 120ppm of terephthalic acid (TPA) additive amount, the addition of guiding thing
Amount is the 4.0wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst is terephthalic acid (TPA) additive amount
160ppm；
(3) polycondensation reaction；
The preshrunk that Trimethyl phosphite carries out 25min under conditions of 250 DEG C and 20Pa is added in the product of step (2)
Poly- reaction；Polymer is finally made in the final polycondensation reaction that 2h is finally carried out under conditions of 220 DEG C and 10Pa；Prepolymerization reaction
Stirring rate is 340rpm, and the stirring rate of final polycondensation reaction is 280rpm；The additional amount of Trimethyl phosphite is in step (2)
The 0.025wt% of terephthalic acid (TPA) additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.3, inherent viscosity 1.24dL/g, and color is
9.8；POY fiber is made in the final polymer that is made, processing waste silk rate is 10kg/t, and the yarn unevenness of fiber is 1.0%.
Embodiment 5
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.06, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 8.9wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
Metatitanic acid is carried on after titanium silicon composite catalyst is made on silica, mixed with titanium silicon composite catalyst and acetic acid
Cobalt obtains titanium silicon cobalt composite catalyst, disperses titanium silicon cobalt composite catalyst in 1,4-butanediol and stirs under conditions of 300rpm
Mixing obtains titanium silicon cobalt composite catalyzing agent dispersing liquid, and metatitanic acid, silica and cobalt acetate account for titanium silicon cobalt composite catalyst respectively
69wt%, 10wt%, 21wt%, the molar ratio that titanium silicon cobalt composite catalyst accounts for 1,4-butanediol is 0.11mol%；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and lemon is added
Lemon acid sodium/para-phthalic sodium (mass ratio 2:1) esterification is carried out under conditions of 180 DEG C and 150KPa until water yield reaches
To 95% reaction terminating of theoretical water yield, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with hexylene glycol, and generation is drawn
The esterification yield for leading object is 98%；Sodium citrate/para-phthalic sodium additive amount is the 100ppm of terephthalic acid (TPA) additive amount, is drawn
The additive amount for leading object is the 3.0wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst is terephthalic acid (TPA)
The 180ppm of additive amount；
(3) polycondensation reaction；
The precondensation that triphenyl phosphate carries out 15min under conditions of 260 DEG C and 8Pa is added in the product of step (2)
Reaction；Polymer is finally made in the final polycondensation reaction that 3.5h is finally carried out under conditions of 280 DEG C and 5Pa；Prepolymerization reaction
Stirring rate is 380rpm, and the stirring rate of final polycondensation reaction is 330rpm；The additional amount of triphenyl phosphate is right in step (2)
The 0.015wt% of phthalic acid additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 1.18dL/g, and color is
9；POY fiber is made in the final polymer that is made, processing waste silk rate is 9.4kg/t, and the yarn unevenness of fiber is 0.90%.
Embodiment 6
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 8.5wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 300rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
59wt%, 13wt%, 28wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.08mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and lemon is added
Lemon acid sodium carries out esterification under conditions of 180 DEG C and 50KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with heptandiol, and the esterification yield for generating guiding thing is 90%；Citric acid
The additive amount of sodium is the 100ppm of terephthalic acid (TPA) additive amount, and the additive amount of guiding thing is terephthalic acid (TPA) additive amount
2.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
The preshrunk that antioxidant 1010 carries out 22min under conditions of 250 DEG C and 12Pa is added in the product of step (2)
Poly- reaction；Polymer is finally made in the final polycondensation reaction that 1.5h is finally carried out under conditions of 250 DEG C and 5Pa；Prepolymerization reaction
Stirring rate be 280rpm, the stirring rate of final polycondensation reaction is 280rpm；The additional amount of antioxidant 1010 is step (2)
The 0.001wt% of middle terephthalic acid (TPA) additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.22, inherent viscosity 1.02dL/g, color
It is 8；POY fiber is made in the final polymer that is made, processing waste silk rate is 8.5kg/t, and the yarn unevenness of fiber is
0.9%.
Embodiment 7
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 7.9wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 350rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
63wt%, 11wt%, 26wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.15mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, be added titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and
Na3PO4/ para-phthalic sodium (mass ratio 3:1) esterification is carried out under conditions of 180 DEG C and 200KPa until water yield reaches
To 95% reaction terminating of theoretical water yield, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with ethohexadiol, and generation is drawn
The esterification yield for leading object is 95%；Na3PO4The additive amount of/para-phthalic sodium is the 180ppm of terephthalic acid (TPA) additive amount, guidance
The additive amount of object is the 2.6wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst adds for terephthalic acid (TPA)
The 190ppm of dosage；
(3) polycondensation reaction；
The preshrunk that antioxidant 168 carries out 45min under conditions of 200 DEG C and 30Pa is added in the product of step (2)
Poly- reaction；Polymer is finally made in the final polycondensation reaction that 1.5h is finally carried out under conditions of 280 DEG C and 10Pa；Prepolymerization reaction
Stirring rate be 150rpm, the stirring rate of final polycondensation reaction is 100rpm；The additional amount of antioxidant 168 is step (2)
The 0.01wt% of middle terephthalic acid (TPA) additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.55, inherent viscosity 1.24dL/g, color
It is 10；DTY fiber is made in the final polymer that is made, processing waste silk rate is 9.5kg/t, and the yarn unevenness of fiber is
0.95%.
Embodiment 8
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.10, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 9.8wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 350rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
59wt%, 9wt%, 32wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.09mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, be added titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and
Na3PO4/ sodium citrate/para-phthalic sodium (mass ratio 1:1:1) progress esterification is straight under conditions of 240 DEG C and 50KPa
Reach 95% reaction terminating of theoretical water yield to water yield, guiding thing is that terephthalic acid (TPA) reacts the esterification generated with nonanediol
Object, the esterification yield for generating guiding thing is 95%；Na3PO4/ sodium citrate/para-phthalic sodium additive amount adds for terephthalic acid (TPA)
The 80ppm of dosage, the additive amount of guiding thing are the 1.0wt% of terephthalic acid (TPA) additive amount, the addition of titanium silicon cobalt composite catalyst
Amount is the 200ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
The precondensation that antioxidant 616 carries out 35min under conditions of 240 DEG C and 8Pa is added in the product of step (2)
Reaction；Polymer is finally made in the final polycondensation reaction that 2h is finally carried out under conditions of 220 DEG C and 5Pa；Prepolymerization reaction stirs
Mixing rate is 260rpm, and the stirring rate of final polycondensation reaction is 320rpm；The additional amount of antioxidant 616 is right in step (2)
The 0.01wt% of phthalic acid additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.45, inherent viscosity 1.18dL/g, color
It is 9；POY fiber is made in the final polymer that is made, processing waste silk rate is 9kg/t, and the yarn unevenness of fiber is 0.9%.
Embodiment 9
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.06, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 8.8wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 350rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
62wt%, 11wt%, 27wt% of catalyst, the molar ratio that titanium silicon cobalt composite catalyst accounts for 1,4-butanediol is 0.13mol%；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and lemon is added
Lemon acid sodium carries out esterification under conditions of 240 DEG C and 100KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with decanediol, and the esterification yield for generating guiding thing is 98%；Citric acid
The additive amount of sodium is the 200ppm of terephthalic acid (TPA) additive amount, and the additive amount of guiding thing is terephthalic acid (TPA) additive amount
0.5wt%, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
Phosphoric acid and antioxidant 1010 are added in the product of step (2) and carries out 30min under conditions of 200 DEG C and 20Pa
Prepolymerization reaction；Polymer is finally made in the final polycondensation reaction that 1.5h is finally carried out under conditions of 220 DEG C and 10Pa；Preshrunk
The stirring rate of poly- reaction is 290rpm, and the stirring rate of final polycondensation reaction is 310rpm；The additional amount of phosphoric acid is in step (2)
The 0.05wt% of terephthalic acid (TPA) additive amount；The additional amount of antioxidant 1010 is terephthalic acid (TPA) additive amount in step (2)
0.01wt%.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.3, inherent viscosity 1.10dL/g, and color is
9；DTY fiber is made in the final polymer that is made, processing waste silk rate is 8.6kg/t, and the yarn unevenness of fiber is 0.92%.
Embodiment 10
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 9.5wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
Metatitanic acid is carried on after titanium silicon composite catalyst is made on silica, mixed with titanium silicon composite catalyst and acetic acid
Cobalt obtains titanium silicon cobalt composite catalyst, disperses titanium silicon cobalt composite catalyst in 1,4-butanediol and stirs under conditions of 350rpm
Mixing obtains titanium silicon cobalt composite catalyzing agent dispersing liquid, and metatitanic acid, silica and cobalt acetate account for titanium silicon cobalt composite catalyst respectively
62wt%, 10wt%, 28wt%, titanium silicon cobalt composite catalyst account for the 0.15mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and right is added
Phthalic acid sodium at 180 DEG C and under conditions of 50KPa carry out esterification until water yield reach theoretical water yield it is 95% anti-
It should terminate, guiding thing is terephthalic acid (TPA) and ethylene glycol/decanediol (mass ratio 1:1) carboxylate that reaction generates generates guidance
The esterification yield of object is 90%；The additive amount of para-phthalic sodium is the 200ppm of terephthalic acid (TPA) additive amount, the addition of guiding thing
Amount is the 5.0wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst is terephthalic acid (TPA) additive amount
200ppm；
(3) polycondensation reaction；
Phosphorous acid and antioxidant 616 are added in the product of step (2) to carry out under conditions of 200 DEG C and 30Pa
The prepolymerization reaction of 45min；The final polycondensation reaction that 3.5h is finally carried out under conditions of 220 DEG C and 5~10Pa is finally made poly-
Close object；The stirring rate of prepolymerization reaction is 290rpm, and the stirring rate of final polycondensation reaction is 300rpm；The additional amount of phosphorous acid
For the 0.05wt% of terephthalic acid (TPA) additive amount in step (2)；The additional amount of antioxidant 616 is terephthaldehyde in step (2)
The 0.001wt% of sour additive amount.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.55, inherent viscosity 1.20dL/g, color
It is 10；POY fiber is made in the final polymer that is made, processing waste silk rate is 10kg/t, and the yarn unevenness of fiber is
0.95%.
Embodiment 11
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.10, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 8.7wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
Metatitanic acid is carried on after titanium silicon composite catalyst is made on silica, mixed with titanium silicon composite catalyst and acetic acid
Cobalt obtains titanium silicon cobalt composite catalyst, disperses titanium silicon cobalt composite catalyst in 1,4-butanediol and stirs under conditions of 300rpm
Mixing obtains titanium silicon cobalt composite catalyzing agent dispersing liquid, and metatitanic acid, silica and cobalt acetate account for titanium silicon cobalt composite catalyst respectively
64wt%, 7wt%, 29wt%, titanium silicon cobalt composite catalyst account for the 0.16mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and lemon is added
Lemon acid sodium carries out esterification under conditions of 240 DEG C and 200KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, guiding thing is terephthalic acid (TPA) and ethylene glycol/propylene glycol (mass ratio 1:2) carboxylate that reaction generates, generates guiding thing
Esterification yield is 98%；The additive amount of sodium citrate is the 200ppm of terephthalic acid (TPA) additive amount, and the additive amount of guiding thing is to benzene
The 5.0wt% of dioctyl phthalate additive amount, the additive amount of titanium silicon cobalt composite catalyst are the 200ppm of terephthalic acid (TPA) additive amount；
(3) polycondensation reaction；
Phosphoric acid/phosphorous acid (mass ratio 2 is added in the product of step (2):And antioxidant 1010/antioxidant 168 1)
(mass ratio 1:2) prepolymerization reaction of 45min is carried out under conditions of 260 DEG C and 30Pa；Finally in 280 DEG C and the condition of 10Pa
Polymer is finally made in the lower final polycondensation reaction for carrying out 3.5h；The stirring rate of prepolymerization reaction is 240rpm, final polycondensation reaction
Stirring rate be 260rpm；Phosphoric acid/phosphorous acid additional amount is the 0.05wt% of terephthalic acid (TPA) additive amount in step (2)；
The additional amount of antioxidant 1010/antioxidant 168 is the 0.01wt% of terephthalic acid (TPA) additive amount in step (2).
The weight average molecular weight breadth coefficient of final polymer obtained is 1.2, inherent viscosity 1.05dL/g, and color is
8；POY fiber is made in the final polymer that is made, processing waste silk rate is 8kg/t, and the yarn unevenness of fiber is 0.85%.
Embodiment 12
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.08, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 7.5wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 350rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
67wt%, 10wt%, 23wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.17mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and right is added
Phthalic acid sodium at 180 DEG C and under conditions of 200KPa carry out esterification until water yield reach theoretical water yield it is 95% anti-
It should terminate, guiding thing is terephthalic acid (TPA) and ethylene glycol/butanediol (mass ratio 2:3) carboxylate that reaction generates generates guidance
The esterification yield of object is 90%；The additive amount of para-phthalic sodium is the 200ppm of terephthalic acid (TPA) additive amount, the addition of guiding thing
Amount is the 0.5wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst is terephthalic acid (TPA) additive amount
100ppm；
(3) polycondensation reaction；
Trimethyl phosphate and the (mass ratio 2 of antioxidant 1010/antioxidant 168 are added in the product of step (2):3)
The prepolymerization reaction of 15~45min is carried out under conditions of 260 DEG C and 10Pa；Finally carried out under conditions of 220 DEG C and 5Pa
Polymer is finally made in the final polycondensation reaction of 1.5h；The stirring rate of prepolymerization reaction is 255rpm, the stirring of final polycondensation reaction
Rate is 300rpm；The additional amount of trimethyl phosphate is the 0.05wt% of terephthalic acid (TPA) additive amount in step (2)；Antioxidant
The additional amount of 1010/ antioxidant 168 is the 0.001wt% of terephthalic acid (TPA) additive amount in step (2).
The weight average molecular weight breadth coefficient of final polymer obtained is 1.42, inherent viscosity 1.13dL/g, color
It is 9；POY fiber is made in the final polymer that is made, processing waste silk rate is 9kg/t, and the yarn unevenness of fiber is 0.91%.
Embodiment 13
A kind of method of tetrahydrofuran side reaction in inhibition polymerization process, based on terephthalic acid (TPA) and 1,4-butanediol
During wanting raw material to prepare polymer, by adding guiding thing, titanium silicon cobalt composite catalyzing agent dispersing liquid and pH in Esterification Stage
Regulator, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.10, inhibit tetrahydrofuran side reaction, so that
The content of tetrahydrofuran is 9.5wt% in polymer.
Specific preparation process is as follows for polymer：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
By butyl titanate be carried on silica be made titanium silicon composite catalyst after, mixed with titanium silicon composite catalyst with
Cobalt acetate obtains titanium silicon cobalt composite catalyst, disperses the condition in 1,4-butanediol in 350rpm for titanium silicon cobalt composite catalyst
Titanium silicon cobalt composite catalyzing agent dispersing liquid is made in lower stir, and it is compound that butyl titanate, silica and cobalt acetate account for titanium silicon cobalt respectively
58wt%, 10wt%, 32wt% of catalyst, titanium silicon cobalt composite catalyst account for the 0.18mol% of 1,4-butanediol；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and right is added
Phthalic acid sodium at 240 DEG C and under conditions of 50KPa carry out esterification until water yield reach theoretical water yield it is 95% anti-
It should terminate, guiding thing is terephthalic acid (TPA) and ethohexadiol/nonanediol (mass ratio 1:3) carboxylate that reaction generates generates guidance
The esterification yield of object is 96%；The additive amount of para-phthalic sodium is the 200ppm of terephthalic acid (TPA) additive amount, the addition of guiding thing
Amount is the 5.0wt% of terephthalic acid (TPA) additive amount, and the additive amount of titanium silicon cobalt composite catalyst is terephthalic acid (TPA) additive amount
200ppm；
(3) polycondensation reaction；
Trimethyl phosphate/Trimethyl phosphite (mass ratio 1 is added in the product of step (2):And antioxidant 616 1)
The prepolymerization reaction of 15min is carried out under conditions of 200 DEG C and 30Pa；Finally carry out 3h's under conditions of 280 DEG C and 10Pa
Polymer is finally made in final polycondensation reaction；The stirring rate of prepolymerization reaction is 360rpm, and the stirring rate of final polycondensation reaction is
310rpm；Trimethyl phosphate/Trimethyl phosphite additional amount is the 0.02wt% of terephthalic acid (TPA) additive amount in step (2)；
The additional amount of antioxidant 616 is the 0.005wt% of terephthalic acid (TPA) additive amount in step (2).
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 1.13dL/g, and color is
9；POY fiber is made in the final polymer that is made, processing waste silk rate is 9kg/t, and the yarn unevenness of fiber is 0.89%.
Claims (10)
1. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process, it is characterized in that：With terephthalic acid (TPA) and 1,4- fourth
Glycol is during primary raw material prepares polymer, by adding guiding thing, titanium silicon cobalt composite catalyst point in Esterification Stage
Dispersion liquid and pH adjusting agent, while the molar ratio for controlling terephthalic acid (TPA) and 1,4-butanediol is 1:1.05~1.10, inhibit tetrahydro
Furans side reaction so that in the polymer tetrahydrofuran content≤10wt%；
Decentralized medium in the titanium silicon cobalt composite catalyzing agent dispersing liquid is 1,4-butanediol, and the titanium silicon cobalt composite catalyst is
Titanium silicon composite catalyst is combined with cobalt series catalyst, and the titanium silicon composite catalyst is the catalysis of silicon systems catalyst supported titanium system
Agent and obtain, the guiding thing is the carboxylate that terephthalic acid (TPA) and diol reaction generate.
2. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 1, which is characterized in that institute
Stating polymer, specific preparation process is as follows：
(1) preparation of titanium silicon cobalt composite catalyzing agent dispersing liquid；
The obtained titanium silicon cobalt of stirring under conditions of 300~350rpm is dispersed in 1,4- butanediol by titanium silicon cobalt composite catalyst to answer
Close catalyst dispersion；
(2) esterification；
After terephthalic acid (TPA) is mixed with 1,4-butanediol, titanium silicon cobalt composite catalyzing agent dispersing liquid, guiding thing and pH is added and adjusts
Esterification is carried out under conditions of 180~240 DEG C and 50~200KPa for agent until water yield reaches the 95% of theoretical water yield
Reaction terminating；
(3) polycondensation reaction；
It is added in the product of step (2) after the agent of heat resistanceheat resistant oxygen and/or antioxidant under conditions of 200~260 DEG C and 1~30Pa
The prepolymerization reaction of 15~45min is carried out, the end of 1.5~3.5h is then carried out under conditions of 220~280 DEG C and 5~10Pa
Polymer is made in polycondensation reaction；The stirring rate of the prepolymerization reaction is 150~400rpm, the stirring of the final polycondensation reaction
Rate is 100~350rpm.
3. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 2, which is characterized in that institute
State 0.05~0.2mol% that titanium silicon cobalt composite catalyst accounts for 1,4- butanediol content；The Titanium series catalyst, silicon systems catalyst
And cobalt series catalyst accounts for 58~70wt%, 7~13wt% and the 17~32wt% of titanium silicon cobalt composite catalyst respectively；The titanium system
Catalyst is butyl titanate or metatitanic acid；The silicon systems catalyst is silica；The cobalt series catalyst is cobalt acetate.
4. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 2, which is characterized in that institute
The additive amount for stating guiding thing is 0.5~5.0wt% of terephthalic acid (TPA) additive amount in step (2)；The titanium silicon cobalt composite catalyzing
The additive amount of agent is 100~200ppm of terephthalic acid (TPA) additive amount in step (2).
5. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 2, which is characterized in that institute
The additive amount for stating pH adjusting agent is 80~200ppm of terephthalic acid (TPA) additive amount in step (2)；The pH adjusting agent is
Na3PO4, one or more of sodium citrate and para-phthalic sodium.
6. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 1, which is characterized in that institute
The esterification yield for stating terephthalic acid (TPA) and diol reaction generation guiding thing is 90~98%；The dihydric alcohol is ethylene glycol, the third two
One or more of alcohol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and decanediol.
7. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 2, which is characterized in that institute
The additional amount for stating heat resistanceheat resistant oxygen agent is 0.005~0.05wt% of terephthalic acid (TPA) additive amount in step (2)；The antioxidant
Additional amount is 0.001~0.01wt% of terephthalic acid (TPA) additive amount in step (2).
8. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 7, which is characterized in that institute
Stating heat resistanceheat resistant oxygen agent is one or more of phosphoric acid, phosphorous acid, trimethyl phosphate, Trimethyl phosphite and triphenyl phosphate；It is described
Antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 616.
9. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 1, which is characterized in that institute
The weight average molecular weight breadth coefficient for stating polymer is 1.2~1.6, and inherent viscosity is 1.00~1.25dL/g, color≤10.
10. a kind of method for inhibiting tetrahydrofuran side reaction in polymerization process according to claim 1, which is characterized in that
The polymer is made POY, FDY or DTY fiber, processes waste silk rate≤10kg/t, the yarn unevenness of fiber≤
1.0%.
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