CN108610477A - A method of inhibiting polymerization side reactions - Google Patents

A method of inhibiting polymerization side reactions Download PDF

Info

Publication number
CN108610477A
CN108610477A CN201810489007.2A CN201810489007A CN108610477A CN 108610477 A CN108610477 A CN 108610477A CN 201810489007 A CN201810489007 A CN 201810489007A CN 108610477 A CN108610477 A CN 108610477A
Authority
CN
China
Prior art keywords
acid
reaction
esterification
polymer
side reactions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810489007.2A
Other languages
Chinese (zh)
Other versions
CN108610477B (en
Inventor
王华平
吉鹏
王朝生
陈向玲
陈烨
乌婧
张婉迎
王宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
National Dong Hwa University
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN201810489007.2A priority Critical patent/CN108610477B/en
Publication of CN108610477A publication Critical patent/CN108610477A/en
Application granted granted Critical
Publication of CN108610477B publication Critical patent/CN108610477B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a kind of methods inhibiting polymerization side reactions, are 1 by the molar ratio added guiding thing in Esterification Stage, while controlling binary acid I and dihydric alcohol I during preparing polymer as primary raw material using binary acid I and dihydric alcohol I:1.05~1.10, the temperature of esterification is 180~240 DEG C, inhibits polymerization side reactions so that content≤1.0wt% of side reaction product in final product；Guiding thing is that binary acid II reacts the carboxylate generated with dihydric alcohol II, and binary acid I and binary acid II are identical or different, and dihydric alcohol I and dihydric alcohol II are identical or different.The weight average molecular weight breadth coefficient of final product is 1.2~1.6, and inherent viscosity is 0.60~1.20dL/g, color≤10.The method of the present invention side reaction is few, and esterification reaction rate is fast, and molecular weight of product distribution obtained is concentrated, by-product is few, quality is good, great application prospect.

Description

A method of inhibiting polymerization side reactions
Technical field
The invention belongs to polymer preparation fields, are related to a kind of method inhibiting polymerization side reactions, and in particular to Yi Zhong The method that guiding thing inhibits polymerization side reactions is added in esterification process.
Background technology
Polyester refers to the polymer general name obtained by polyalcohol and polyacid polycondensation.Refer mainly to polyethylene terephthalate (PET), also include traditionally linear thermoplastics' resins such as polybutylene terephthalate (PBT) and polyarylate.It is a kind of performance Excellent, widely used polymer.The fields such as fiber, plastics, film have been widely used in it at present.
The preparation method of existing polyester based on direct esterification route, be with the larger i.e. alcohol of molar ratio of alcohol to acid it is excessive compared with More lower progress esterifications.As patent CN201510081949.3 is disclosed using terephthalic acid (TPA), 1,3- propylene glycol as former Material prepares polyester, and alkyd material molar ratio reaches as high as 5:1；Terephthalic acid (TPA) disclosed in patent CN201610214745.7, 1,3- propylene glycol molar ratio is also up to 1.6；Patent CN00818908.0 discloses one kind with double -3- hydroxypropyls terephthalic acid (TPA)s And/or 1,3-PD and terephthalic acid (TPA) are the method that raw material prepares polyester, the molar ratio of alcohol acid starting material reaches as high as 2.2:1 and esterification after the completion of control prepolymer inherent viscosity in 0.25dL/g or more；Patent CN201510555840.9 The method for synthesizing poly- furandicarboxylic acid glycol ester is disclosed, wherein molar ratio of alcohol to acid is in 1.2 or more, up to 3:1.This is Because on the one hand excessive dihydric alcohol promotes esterification and carried out to positive reaction direction, still further aspect can will be to diformazan Acid is partly dissolved, and then further speeds up esterification, and what entire esterification system showed is heterogeneous reaction, ester Change reaction rate in first slow rear fast feature.
Larger molar ratio of alcohol to acid brings problems with：1) under the conditions of existing molar ratio of alcohol to acid is 1.2~1.5, Dihydric alcohol is issued in high alkyd mole is born from polycondensation, generates by-product, causes large effect to the fibre forming property of polyester, while high Molar ratio needs to consume more binary raw polyols, increases cost；2) for polyester Esterification Stage directly concerning most final minification The quality of poly- product, therefore the prior art is abundant by being carried out under 3 hours or more esterification times under high molar ratio of alcohol to acid Esterification, this easily causes the generation of side reaction in esterification process；3) it is needed after completing to be esterified poly- by precondensation, final minification Polyester could be made in reaction, and polyester is made which results in final generally in 0.25dL/g or more in the inherent viscosity of precondensation product Molecular weight distribution it is wider, polyester processing performance is bad, in process easily generate lousiness, broken end, waste silk phenomena such as.
Therefore, exploitation is a kind of can effectively inhibit polymerization side reactions so that polymer molecular weight distribution concentration, viscosity height is made The great realistic meaning of good method with quality.
Invention content
The purpose of the invention is to overcome above-mentioned problems of the prior art, providing a kind of can effectively inhibit to polymerize The method of side reaction.
In order to achieve the above object, the technical solution adopted by the present invention is：
A method of inhibiting polymerization side reactions, in the mistake for preparing polymer using binary acid I and dihydric alcohol I as primary raw material Cheng Zhong is 1 by the molar ratio added guiding thing in Esterification Stage, while controlling binary acid I and dihydric alcohol I:1.05~1.10, The temperature of esterification is 180~240 DEG C, inhibits polymerization side reactions so that the content of side reaction product in the polymer≤ 1.0wt%；The guiding thing is that binary acid II reacts the carboxylate generated, the binary acid I and binary acid II with dihydric alcohol II Identical or different, the dihydric alcohol I and dihydric alcohol II are identical or different.
As preferred technical solution：
A kind of method inhibiting polymerization side reactions as described above, the specific preparation process of the polymer are as follows：
(1) esterification；
By binary acid I and dihydric alcohol I with 1:After 1.05~1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyzing is added Esterification is carried out under conditions of 180~240 DEG C, 50~200KPa for agent, guiding thing until water yield reaches theoretical water yield 95% reaction terminating；The guiding thing is that binary acid II reacts the carboxylate generated with dihydric alcohol II；The esterification of the present invention is anti- It is 1.5~3.5h between seasonable, esterification, reaction time of esterification 3.5 is carried out with the molar ratio of alcohol to acid if do not added guiding thing ~5.0h.The molar ratio of binary acid I of the present invention and dihydric alcohol I esterifications is 1:1.05~1.10, existing molar ratio of alcohol to acid It is higher that dihydric alcohol is easily caused to occur to increase the ratio of side reaction product, but too low molar ratio of alcohol to acid meeting from polycondensation at high temperature Cause esterification reaction rate to be remarkably decreased, substantially prolongs the reaction time；The present invention controls esterification temperature at 180~240 DEG C, This is because esterification process is the endothermic reaction, it is same although excessively high temperature can further speed up esterification reaction rate The quickening of rate of side reactions, too low temperature can be caused to cannot be satisfied needs of the esterification with course of dissolution to heat；Esterification Reaction slightly positive pressure, control pressure is in 50~200KPa, this is because since reaction generates small molecule moisture, band in esterification process There is certain direct draught, the promotion of esterification reaction rate can be promoted.Excessively high pressure can propose esterification device higher It is required that esterification of the present invention carries out on existing apparatus, without further transformation, cost is reduced.Also it can be selected and remove Other catalyst other than titanium silicon cobalt composite catalyst, but the increase of side reaction and product color can be caused to be deteriorated, the present invention Higher catalytic activity may be implemented in compounded catalyst, while promoting the color and luster of product.
(2) prepolymerization reaction；
The agent of heat resistanceheat resistant oxygen and/or antioxidant are added in the product of step (1) at 200~260 DEG C and 100~1000Pa Under the conditions of carry out 15~45min prepolymerization reaction be made inherent viscosity≤0.15dL/g precondensation product；The precondensation The stir speed (S.S.) of reaction is 5~20rpm；Although low viscosity preshrunk can also be obtained by not adding the agent of heat resistanceheat resistant oxygen and/or antioxidant Poly- product, but easily lead to the precondensation product of the low viscosity degradation problem caused by thermal oxide in polycondensation process.
The present invention prepolymerization reaction temperature control at 200~260 DEG C, this is because too low reaction temperature cause it is pre- Polycondensation reaction can not carry out, and excessively high reaction temperature can lead to thermal degradation side reaction enhancing during prepolymerization reaction, formation Product color is deteriorated.
The prepolymerization reaction pressure control of the present invention is relatively low compared to the poly- vacuum degree of final minification in 100~1000Pa, too low Pressure (i.e. higher vacuum effectiveness) can cause the performed polymer of low viscosity in prepolymerization reaction to be extracted, and block pipeline, cause to contract Poly- accident；Excessively high pressure (i.e. worse vacuum effectiveness) can lead to not the removing for realizing polycondensation reaction small molecular, preshrunk Poly- reaction can not be normally carried out.
The prepolymerization reaction time control of the present invention is in 15~45min, substantially less than reaction time in the prior art, this hair The performed polymer viscosity that can be resulted in if the bright middle prepolymerization reaction time is too short is too low (being less than 0.15dL/g), at end below In high vacuum conditions easily as dihydric alcohol small molecule is extracted together in polycondensation reaction, pipeline is blocked；When prepolymerization reaction Between it is too long if the molecular weight of performed polymer that can result in gradually increase, the weight average molecular weight breadth coefficient of product broadens, then It further broadens after final polycondensation reaction, cannot achieve the mesh that the weight average molecular weight breadth coefficient that patent of the present invention proposes is concentrated 's.
The prepolymerization reaction stir speed (S.S.) of the present invention is 5~20rpm, and material viscosity is higher than esterification during prepolymerization reaction Reaction product, is less than final polycondensation reaction product, and too fast stir speed (S.S.) can cause the precondensation product compared with low viscosity in vacuum ring It is unfavorable to reacting as dihydric alcohol is carried over together under border.The uniform effect of material stirring is not had under too low stir speed (S.S.).
(3) final polycondensation reaction；
Precondensation product made from step (2) carries out 1.5~3.5h's under conditions of 220~280 DEG C and 10~100Pa Polymer is made in final polycondensation reaction；The stir speed (S.S.) of the final polycondensation reaction is 5~10rpm；Side reaction is produced in the polymer Content≤1.0wt% of object.
The final polycondensation reaction temperature control of the present 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 can lead to final polycondensation reaction, and the product color of formation becomes Difference.
The final polycondensation reaction pressure of the present invention is controlled in 10~100Pa, and too low pressure (i.e. higher vacuum effectiveness) is right The requirement higher of equipment；Excessively high pressure (i.e. worse vacuum effectiveness) can lead to not realize the de- of polycondensation reaction small molecular It removes, final polycondensation reaction can not be normally carried out.
The final polycondensation reaction time control of the present invention can lead to shape in 1.5~3.5h if the final polycondensation reaction time is too short At product spinning rank is not achieved；The thermal degradation of polymer under hot conditions can be caused aobvious if the prepolymerization reaction time is too long It writes and increases, product declines rapidly after reaching highest weight average molecular weight because of thermal degradation.
The final polycondensation reaction stir speed (S.S.) of the present invention is 5~10rpm, and material viscosity is higher than preshrunk during final polycondensation reaction Polybutadiene reaction product, product viscosity is higher, and stirring is more difficult to, and too fast stir speed (S.S.) both can not be real for highly viscous polymeric system The effect now stirred, simultaneously as the too big damage motor of electric current；Material stirring is not had under too low stir speed (S.S.) uniformly to imitate Fruit.
The additive amount of a kind of method inhibiting polymerization side reactions as described above, the guiding thing is binary in step (1) 0.5~5.0wt% of sour I additive amounts；The additive amount of the titanium silicon cobalt composite catalyst is binary acid I additive amounts in step (1) 100~200ppm；The titanium silicon cobalt composite catalyst is that titanium silicon composite catalyst is combined with cobalt series catalyst, and titanium silicon is multiple It closes catalyst to obtain for silicon systems catalyst carrying catalyst in titanium series, Titanium series catalyst, silicon systems catalysis in titanium silicon cobalt composite catalyst The molar ratio of agent and cobalt series catalyst is 1:0.1~10:0.1~10.
Purpose present invention introduces guiding thing be in order to reduce the ratio of dihydric alcohol in raw material, while accelerate esterification speed Rate.Guiding thing additive amount is too low, cannot achieve effective dissolving to binary acid in raw material, and esterification reaction rate accelerates unobvious, Reaction time of esterification can be extended instead；Guiding thing adding too much, though it can play the role of dissolving rapidly to binary acid, at This can increase, and economy is bad.
The additive amount of titanium silicon cobalt composite catalyst is 100~200ppm of binary acid I additive amounts, and the present invention is selected with compound Catalyst, which allows for, should ensure catalytic effect while can play the role of promotion to final product.Too low catalyst adds Dosage can cause catalytic effect to decline, and the reaction time is elongated, and efficiency reduces；Excessively high catalyst amount can lead to reaction excessively Soon, it is possible to " implode " danger occur, while also increase cost.
A kind of method inhibiting polymerization side reactions as described above, the Titanium series catalyst are butyl titanate or inclined titanium Acid；The silicon systems catalyst is silica；The cobalt series catalyst is cobalt acetate.Titanium series catalyst is carried on silica Form TiO2-SiO2It compounds with cobalt series catalyst to obtain titanium silicon cobalt composite catalyst after composite catalyst.
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, mixing speed 820r/min of heating temperature, flow back 2h.Wait for ethyl orthosilicate complete hydrolysis Afterwards, 40.0g butyl titanates are added into three-necked flask, stirring 20min makes it mix with reactant to hook.It is titrated using constant pressure Pipe is slowly added dropwise by given pace steams shop water in right amount.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, firing temperature is set as 500 DEG C, waits for Temperature starts timing, roast 3h after reaching set temperature.After the completion of waiting for roast, roast object is taken out, allows its natural cooling, is finally TiO can be obtained2-SiO2Composite catalyst.
A kind of method inhibiting polymerization side reactions as described above, the binary acid II react generation guiding with dihydric alcohol II The esterification yield of object is 90~98%, if esterification yield is less than this range, is esterified the carboxylate that guiding thing is partly completely reacted, part It is unreacted terephthalic acid (TPA) and dihydric alcohol, if using the esterification guiding thing, the dissolubility to binary acid can be lowered significantly Energy；The binary acid I and binary acid II is respectively terephthalic acid (TPA), M-phthalic acid, 5-sodium sulfo isophthalate, fourth two One kind in acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid；II points of the dihydric alcohol I and dihydric alcohol One kind that Wei be in ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and decanediol.
The addition of a kind of method inhibiting polymerization side reactions as described above, the heat resistanceheat resistant oxygen agent is two in step (1) 0.005~0.05wt% of first acid I additive amounts；The addition of the antioxidant is binary acid I additive amounts in step (1) 0.001~0.01wt%.
A kind of method inhibiting polymerization side reactions as described above, the heat resistanceheat resistant oxygen agent are phosphoric acid, phosphorous acid, tripotassium phosphate One or more of ester, Trimethyl phosphite and triphenyl phosphate；The antioxidant is antioxidant 1010, antioxidant One or more of 168 and antioxidant 616.
A kind of method inhibiting polymerization side reactions as described above, the weight average molecular weight breadth coefficient of the polymer are 1.2~1.6, inherent viscosity is 0.60~1.20dL/g, color≤10.The Weight-average molecular of polymer obtained in the prior art Breadth coefficient is measured 2.0 or more, color is 15~20.
A kind of method inhibiting polymerization side reactions as described above, POY, FDY, DTY or short fibre are made by the polymer Dimension, processing waste silk rate≤10kg/t, yarn unevenness≤1.0% of fiber.The polymer is alternatively arranged as in addition to fiber is made The raw material of the products such as film, plastics.
Invention mechanism：
Polymer preparation process is generally that esterification, esterification reaction product are carried out under the conditions of high molar ratio of alcohol to acid at present It after high inherent viscosity precondensation product is made in precondensation, then carries out final polycondensation reaction and ultimately generates polymer, existing asks Topic is that reaction time of esterification is long, and side reaction is more, of high cost, and the inherent viscosity of precondensation product is excessively high so that final to be made Polymer molecular weight wider distribution, polyester processing performance is bad.
In view of the above problems, the present invention uses relatively low molar ratio of alcohol to acid (1:1.05~1.10) esterification is carried out, significantly Improve raw material dihydric alcohol to occur from the problem of polycondensation side reaction.Due to relatively low molar ratio of alcohol to acid, raw material binary acid meltage is reduced, Esterification reaction rate declines, and to overcome the problems, such as this, the carboxylate that present invention addition is generated by binary acid and diol reaction is made For guiding thing, solubility of the raw material binary acid in the carboxylate that binary acid and diol reaction generate is high, is risen in esterification Stage beginning just adds guiding thing and can be dissolved in raw material binary acid wherein, dissolve raw material binary acid therein can rapidly with original Material dihydric alcohol carries out esterification and further generates the remaining raw material binary acid of carboxylate redissolution, accelerates esterification.This hair The bright method by adding guiding thing in esterification initial period, it is suppressed that polymerization side reactions realize the dynamics in esterification process Strengthen so that esterification enters homogeneous reaction system in advance, and entire esterification has been obviously improved compared to more existing technology Rate substantially reduces the time of esterification.
The present invention is existed the inherent viscosity control of precondensation product by controlling the prepolymerization reaction time (15~45min) Within 0.15dL/g (prior art polyester prepolymerization reaction time is 1.0~2.0h, and inherent viscosity is in 0.25dL/g or more), most Afterwards again through final polycondensation reaction, the molecular weight distribution that the polymer formed after final polycondensation reaction may be implemented in this way is concentrated, right It is obviously improved in its spinning process and quality.
Advantageous effect：
(1) method of a kind of inhibition polymerization side reactions of the invention controls binary acid and binary using low molar ratio of alcohol to acid Alcohol molar ratio of material is 1:1.05~1.10, on the one hand reduce dihydric alcohol and occur from polycondensation side reaction so that is finally formed The content of side reaction product is low in polymer, and product color degree is good, on the other hand, reduces the consumption of alcohol, reduces cost； Dihydric alcohol generation significantly improves from polycondensation side reaction problem under the conditions of low mole prop0rtion, by-product in finally formed polymer Content≤1.0% of object, color≤10；
(2) method of a kind of inhibition polymerization side reactions of the invention originates under conditions of low molar ratio of alcohol to acid in esterification Stage addition addition binary acid forms carboxylate as esterification guiding thing with dihydric alcohol, realizes that the dynamics in esterification process is strong To change so that esterification enters homogeneous reaction system in advance, and entire esterification reaction rate is obviously improved compared to existing technology, The time for substantially reducing esterification, further reduce side reaction；
(3) method of a kind of inhibition polymerization side reactions of the invention will control precondensation product after completing esterification Inherent viscosity within 0.15dL/g, can make the molecular weight distribution of the polymer formed after final polycondensation reaction in this way It concentrates, is obviously improved its spinning quality；
(4) method of a kind of inhibition polymerization side reactions of the invention, is distributed by polymer molecular weight made from this method 1.2~1.6, inherent viscosity is 0.60~1.20dL/g, can be used for POY, FDY, DTY and staple fiber is used, processing waste silk rate≤ 10kg/t, yarn unevenness≤1.0% of fiber can be used for fibre forming manufacture field, can apply in high-grade home textile, take Equal fields.
Specific implementation mode
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 method of inhibiting polymerization side reactions, polymer is being prepared as primary raw material using terephthalic acid (TPA) and ethylene glycol In the process, by adding guiding thing in esterification process, while mole of esterification raw material terephthalic acid (TPA) and ethylene glycol is controlled Than being 1:1.05, the temperature of esterification is 180 DEG C, inhibits polymerization side reactions so that side reaction in final polymer obtained The content of product is 0.9wt%；Guiding thing is that M-phthalic acid reacts the carboxylate generated with propylene glycol.
Final polymer preparation obtained is as follows：
(1) esterification；
By terephthalic acid (TPA) and ethylene glycol with 1:After 1.05 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 180 DEG C, 100KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that M-phthalic acid reacts that the esterification yield generated is 90% with propylene glycol to lead object, and the additive amount of guiding thing is to benzene two The 5.0wt% of formic acid, the additive amount of titanium silicon cobalt composite catalyst are the 110ppm of the quality of terephthalic acid (TPA), and titanium silicon cobalt is compound to urge Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:0.8:0.1 is combined；
(2) prepolymerization reaction；
The prepolymerization reaction that phosphoric acid carries out 20min under conditions of 200 DEG C, 1000Pa is added in the product of step (1) Be made inherent viscosity be 0.10dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 10rpm stirring under into Row, the addition of phosphoric acid are the 0.03wt% of addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 220 DEG C, 100Pa is final Polymer is made, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 6rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.2, inherent viscosity 1.1dL/g, and color is 10, the content of side reaction product is 0.9wt%.FDY is made in the polymer, processing waste silk rate is 9.2kg/t, the item of fiber Dry irregularity is 0.99%.
Embodiment 2
A method of inhibiting polymerization side reactions, using 5-sodium sulfo isophthalate and propylene glycol as primary raw material system During standby polymer, by adding guiding thing in esterification process, while esterification raw material M-phthalic acid -5- sulphurs are controlled The molar ratio of sour sodium and propylene glycol is 1:1.06, the temperature of esterification is 220 DEG C, inhibits polymerization side reactions so that final system The content of side reaction product is 0.8wt% in the polymer obtained；Guiding thing is that succinic acid reacts the carboxylate generated with propylene glycol.
Polymer preparation is as follows：
(1) esterification；
By 5-sodium sulfo isophthalate and propylene glycol with 1:After 1.06 molar ratio is mixed with beating, it is multiple that titanium silicon cobalt is added Close catalyst, guiding thing carries out under conditions of 220 DEG C, 150KPa until water yield reaches 95% reaction of theoretical water yield eventually Only, wherein guiding thing is carboxylate that succinic acid reacts that the esterification yield generated is 95% with propylene glycol, and the additive amount of guiding thing is The additive amount of the 4.5wt% of 5-sodium sulfo isophthalate, titanium silicon cobalt composite catalyst are 5-sodium sulfo isophthalate The 100ppm of quality, titanium silicon cobalt composite catalyst are 1 in molar ratio by metatitanic acid, silica and cobalt acetate:2.5:0.5 is compound It forms；
(2) prepolymerization reaction；
The prepolymerization reaction that phosphorous acid carries out 40min under conditions of 235 DEG C, 200Pa is added in the product of step (1) Be made inherent viscosity be 0.11dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 16rpm stirring under into Row, the addition of phosphorous acid are the 0.01wt% of addition 5-sodium sulfo isophthalate in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 250 DEG C, 20Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 6rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.6, inherent viscosity 1.10dL/g, and color is 9, the content of side reaction product is 0.8wt%.FDY is made in the polymer, processing waste silk rate is 8.9kg/t, the item of fiber Dry irregularity is 0.89%.
Embodiment 3
A method of inhibiting polymerization side reactions, in the process for preparing polymer using suberic acid and butanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material suberic acid and butanediol is 1: 1.07, the temperature of esterification is 230 DEG C, inhibits polymerization side reactions so that the content of side reaction product is in polymer 0.8wt%；Guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with pentanediol.
Polymer preparation is as follows：
(1) esterification；
By suberic acid and butanediol with 1:After 1.07 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 230 DEG C, 50KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 98% is reacted with pentanediol for terephthalic acid (TPA), the additive amount of guiding thing is suberic acid 4.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 130ppm of the quality of suberic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:5.0:4.0 being combined；
(2) prepolymerization reaction；
The precondensation that trimethyl phosphate carries out 25min under conditions of 240 DEG C, 100Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.12dL/g is made in reaction, and wherein prepolymerization reaction is in the case where stir speed (S.S.) is the stirring of 8rpm It carries out, the addition of trimethyl phosphate is the 0.006wt% of addition suberic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 260 DEG C, 10Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 0.85dL/g, and color is 8, the content of side reaction product is 0.85wt%.Staple fiber is made in the polymer, processing waste silk rate is 9.5kg/t, fiber Yarn unevenness be 0.85%.
Embodiment 4
A method of inhibiting polymerization side reactions, polymer is being prepared as primary raw material using terephthalic acid (TPA) and propylene glycol In the process, by adding guiding thing in esterification process, while esterification raw material terephthalic acid (TPA) and mole of propylene glycol being controlled Than being 1:1.08, the temperature of esterification is 235 DEG C, inhibits polymerization side reactions so that side reaction in final polymer obtained The content of product is 0.9wt%；Guiding thing is that succinic acid reacts the carboxylate generated with pentanediol.
Polymer preparation is as follows：
(1) esterification；
By terephthalic acid (TPA) and propylene glycol with 1:After 1.08 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 235 DEG C, 80KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that succinic acid reacts that the esterification yield generated is 92% with pentanediol to lead object, and the additive amount of guiding thing is terephthalic acid (TPA) 3.5wt%, the additive amount of titanium silicon cobalt composite catalyst is the 180ppm of the quality of terephthalic acid (TPA), titanium silicon cobalt composite catalyst It is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:0.1:5.7 being combined；
(2) prepolymerization reaction；
The preshrunk that Trimethyl phosphite carries out 35min under conditions of 245 DEG C, 100Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.13dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 17rpm in stir speed (S.S.) Lower progress is mixed, the addition of Trimethyl phosphite is the 0.015wt% of addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 240 DEG C, 30Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.2, inherent viscosity 0.90dL/g, and color is 8, the content of side reaction product is 0.9wt%.DTY is made in the polymer, processing waste silk rate is 9.5kg/t, the item of fiber Dry irregularity is 0.88%.
Embodiment 5
A method of inhibiting polymerization side reactions, in the process for preparing polymer using decanedioic acid and butanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material decanedioic acid and butanediol is 1: 1.09, the temperature of esterification is 240 DEG C, inhibits polymerization side reactions so that side reaction product in final polymer obtained Content is 1wt%；Guiding thing is that succinic acid reacts the carboxylate generated with hexylene glycol.
Polymer preparation is as follows：
(1) esterification；
By decanedioic acid and butanediol with 1:After 1.09 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 240 DEG C, 150KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 92% is reacted with hexylene glycol for succinic acid, the additive amount of guiding thing is decanedioic acid 3.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of the quality of decanedioic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:0.9:3.6 being combined；
(2) prepolymerization reaction；
The precondensation that triphenyl phosphate carries out 15min under conditions of 250 DEG C, 700Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.13dL/g is made in reaction, and wherein prepolymerization reaction is in the stirring that stir speed (S.S.) is 20rpm Lower progress, the addition of triphenyl phosphate are the 0.035wt% of addition decanedioic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 220 DEG C, 70Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.15, inherent viscosity 0.72dL/g, color It is 8, the content of side reaction product is 1wt%.FDY is made in the polymer, processing waste silk rate is 9kg/t, and the item of fiber is dry Irregularity is 0.93%.
Embodiment 6
A method of inhibiting polymerization side reactions, in the process for preparing polymer using azelaic acid and butanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material azelaic acid and butanediol is 1: 1.10, the temperature of esterification is 220 DEG C, inhibits polymerization side reactions so that side reaction product in final polymer obtained Content is 0.8wt%；Guiding thing is that decanedioic acid reacts the carboxylate generated with heptandiol.
Polymer preparation is as follows：
(1) esterification；
By azelaic acid and butanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 220 DEG C, 120KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 90% is reacted with heptandiol for decanedioic acid, the additive amount of guiding thing is azelaic acid 2.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of the quality of azelaic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:3.8:0.1 is combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of phosphoric acid and phosphorous acid is added in the product of step (1):And antioxidant 1) The precondensation that inherent viscosity is 0.14dL/g is made in 1010 prepolymerization reactions that 15min is carried out under conditions of 240 DEG C, 500Pa Product, wherein prepolymerization reaction are carried out in the case where stir speed (S.S.) is the stirring of 11rpm, the addition of the mixture of phosphoric acid and phosphorous acid Addition for the 0.005wt% of addition azelaic acid in step (1), antioxidant 1010 is addition azelaic acid in step (1) 0.001wt%；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 230 DEG C, 50Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.55, inherent viscosity 1.10dL/g, color It is 9, the content of side reaction product is 0.8wt%.FDY is made in the polymer, processing waste silk rate is 9.5kg/t, fiber Yarn unevenness is 0.95%.
Embodiment 7
A method of inhibiting polyester side reaction, polymerize using M-phthalic acid with hexylene glycol as primary raw material preparation During object, by adding guiding thing in esterification process, while esterification raw material M-phthalic acid and hexylene glycol are controlled Molar ratio is 1:1.07, the temperature of esterification is 228 DEG C, inhibits polymerization side reactions so that secondary in final polymer obtained The content of reaction product is 0.9wt%；Guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with ethohexadiol.
Polymer preparation is as follows：
(1) esterification；
By M-phthalic acid and hexylene glycol with 1:After 1.07 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 228 DEG C, 150KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that terephthalic acid (TPA) reacts that the esterification yield generated is 96% with ethohexadiol to lead object, and the additive amount of guiding thing is isophthalic two The 0.5wt% of formic acid, the additive amount of titanium silicon cobalt composite catalyst are the 160ppm of the quality of M-phthalic acid, and titanium silicon cobalt is compound to urge Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:8.2:0.8 is combined；
(2) prepolymerization reaction；
The mixture and antioxidant 168 of trimethyl phosphate and Trimethyl phosphite are added in the product of step (1) The precondensation product that inherent viscosity is 0.15dL/g is made in the prepolymerization reaction that 25min is carried out under conditions of 230 DEG C, 300Pa, Wherein prepolymerization reaction is carried out in the case where stir speed (S.S.) is the stirring of 10rpm, the mixture of trimethyl phosphate and Trimethyl phosphite Addition be addition M-phthalic acid in step (1) 0.04wt%, the addition of antioxidant 168 is to add in step (1) Add the 0.005wt% of M-phthalic acid；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 270 DEG C, 30Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 7rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.3, inherent viscosity 0.65dL/g, and color is 7, the content of side reaction product is 0.9wt%.FDY is made in the polymer, processing waste silk rate is 10kg/t, and the item of fiber is dry Irregularity is 0.85%.
Embodiment 8
A method of inhibiting polymerization side reactions, polymer is being prepared as primary raw material using terephthalic acid (TPA) and pentanediol In the process, by adding guiding thing in esterification process, while mole of esterification raw material terephthalic acid (TPA) and pentanediol is controlled Than being 1:1.06, the temperature of esterification is 234 DEG C, inhibits polymerization side reactions so that finally side reaction is produced in obtained polymer The content of object is 0.8wt%；Guiding thing is that decanedioic acid reacts the carboxylate generated with nonanediol.
Polyester preparation is as follows：
(1) esterification；
By terephthalic acid (TPA) and pentanediol with 1:After 1.06 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 234 DEG C, 180KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that decanedioic acid reacts that the esterification yield generated is 98% with nonanediol to lead object, and the additive amount of guiding thing is terephthalic acid (TPA) 0.5wt%, the additive amount of titanium silicon cobalt composite catalyst is the 200ppm of the quality of terephthalic acid (TPA), titanium silicon cobalt composite catalyst It is 1 in molar ratio by butyl titanate, silica and cobalt acetate:5.0:5.5 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of Trimethyl phosphite and triphenyl phosphate is added in the product of step (1):1) with And it is 0.10dL/g that antioxidant 616 carries out the prepolymerization reaction obtained inherent viscosity of 20min under conditions of 230 DEG C, 600Pa Precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 5rpm stirring under carry out, Trimethyl phosphite and tricresyl phosphate The addition of the mixture of phenyl ester is the 0.05wt% of addition terephthalic acid (TPA) in step (1), and the addition of antioxidant 616 is The 0.01wt% of addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 250 DEG C, 40Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.3, inherent viscosity 0.75dL/g, and color is 9, the content of side reaction product is 0.8wt%.FDY is made in the polymer, processing waste silk rate is 8.5kg/t, the item of fiber Dry irregularity is 0.85%.
Embodiment 9
A method of inhibiting polymerization side reactions, in the process for preparing polymer using decanedioic acid and nonanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material decanedioic acid and nonanediol is 1: 1.10, the temperature of esterification is 220 DEG C, inhibits polymerization side reactions so that side reaction product contains in final obtained polymer Amount is 0.85wt%；Guiding thing is that adipic acid reacts the carboxylate generated with ethohexadiol.
Polymer preparation is as follows：
(1) esterification；
By decanedioic acid and nonanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 220 DEG C, 70KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 91% is reacted with ethohexadiol for adipic acid, the additive amount of guiding thing is decanedioic acid 1.5wt%, the additive amount of titanium silicon cobalt composite catalyst are the 200ppm of the quality of decanedioic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:7.5:6.0 being combined；
(2) prepolymerization reaction；
The preshrunk that antioxidant 1010 carries out 35min under conditions of 250 DEG C, 400Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.10dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 15rpm in stir speed (S.S.) Lower progress is mixed, the addition of antioxidant 1010 is the 0.002wt% of addition decanedioic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 280 DEG C, 70Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.46, inherent viscosity 0.65dL/g, color It is 8, the content of side reaction product is 0.85wt%.FDY is made in the polymer, processing waste silk rate is 9kg/t, the item of fiber Dry irregularity is 0.88%.
Embodiment 10
A method of inhibiting polymerization side reactions, in the process for preparing polymer using azelaic acid and ethohexadiol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material azelaic acid and ethohexadiol is 1: 1.05, the temperature of esterification is 235 DEG C, inhibits polymerization side reactions so that side reaction product contains in final obtained polymer Amount is 0.9wt%；Guiding thing is that azelaic acid reacts the carboxylate generated with nonanediol.
Polymer preparation is as follows：
(1) esterification；
By azelaic acid and ethohexadiol with 1:1.05 molar ratio be mixed with beating after, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 235 DEG C, 200KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 98% is reacted with nonanediol for azelaic acid, the additive amount of guiding thing is azelaic acid 2.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 180ppm of the quality of azelaic acid, and titanium silicon cobalt composite catalyst is by inclined titanium Acid, silica and cobalt acetate are 1 in molar ratio:0.3:0.1 is combined；
(2) prepolymerization reaction；
The preshrunk that antioxidant 168 carries out 35min under conditions of 245 DEG C, 100Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.12dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 20rpm in stir speed (S.S.) Lower progress is mixed, the addition of antioxidant 168 is the 0.006wt% of addition azelaic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 270 DEG C, 50Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.56, inherent viscosity 1.10dL/g, color It is 9.5, the content of side reaction product is 0.9wt%.FDY is made in the polymer, processing waste silk rate is 9.7kg/t, fiber Yarn unevenness be 0.98%.
Embodiment 11
A method of inhibiting polymerization side reactions, in the process for preparing polymer using suberic acid and nonanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material suberic acid and nonanediol is 1: 1.08, the temperature of esterification is 231 DEG C, inhibits polymerization side reactions so that side reaction product in final polymer obtained Content is 0.78wt%；Guiding thing is that succinic acid reacts the carboxylate generated with heptandiol.
Polymer preparation is as follows：
(1) esterification；
By suberic acid and nonanediol with 1:After 1.08 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 231 DEG C, 100KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 94% is reacted with heptandiol for succinic acid, the additive amount of guiding thing is suberic acid 4.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of the quality of suberic acid, and titanium silicon cobalt composite catalyst is by inclined titanium Acid, silica and cobalt acetate are 1 in molar ratio:0.5:10 are combined；
(2) prepolymerization reaction；
The preshrunk that antioxidant 616 carries out 40min under conditions of 250 DEG C, 800Pa is added in the product of step (1) The precondensation product that inherent viscosity is 0.10dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 13rpm in stir speed (S.S.) Lower progress is mixed, the addition of antioxidant 616 is the 0.01wt% of addition suberic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 250 DEG C, 50Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 0.63dL/g, and color is 7, the content of side reaction product is 0.78wt%.Staple fiber is made in the polymer, processing waste silk rate is 8.5kg/t, fiber Yarn unevenness be 0.75%.
Embodiment 12
A method of inhibiting polymerization side reactions, in the process for preparing polymer using pimelic acid and heptandiol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material pimelic acid and heptandiol is 1: 1.08, the temperature of esterification is 231 DEG C, inhibits polymerization side reactions so that side reaction product contains in final obtained polymer Amount is 0.78wt%；Guiding thing is that succinic acid reacts the carboxylate generated with heptandiol.
Polymer preparation is as follows：
(1) esterification；
By pimelic acid and heptandiol with 1:After 1.08 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 223 DEG C, 80KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 96% is reacted with pentanediol for glutaric acid, the additive amount of guiding thing is pimelic acid 0.5wt%, the additive amount of titanium silicon cobalt composite catalyst are the 130ppm of the quality of pimelic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:6.0:0.7 is combined；
(2) prepolymerization reaction；
Phosphoric acid is added in the product of step (1) and antioxidant 1010 carries out 45min under conditions of 235 DEG C, 900Pa Prepolymerization reaction be made inherent viscosity be 0.15dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 7rpm Stirring under carry out, the addition of phosphoric acid is the 0.008wt% of addition terephthalic acid (TPA) in step (1), antioxidant 1010 Addition is the 0.009wt% of addition pimelic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.0h under conditions of 260 DEG C, 100Pa is final Polymer is made, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 1.12dL/g, and color is 9, the content of side reaction product is 0.8wt%.DTY is made in the polymer, processing waste silk rate is 9.5kg/t, the item of fiber Dry irregularity is 0.98%.
Embodiment 13
A method of inhibiting polymerization side reactions, in the process for preparing polymer using adipic acid and decanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material adipic acid and decanediol is 1: 1.05, the temperature of esterification is 226 DEG C, inhibits polymerization side reactions so that side reaction product contains in final obtained polymer Amount is 0.9wt%；Guiding thing is the carboxylate that suberic acid is generated with glycol reaction.
Polymer preparation is as follows：
(1) esterification；
By adipic acid and decanediol with 1:After 1.05 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 226 DEG C, 140KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The additive amount of the carboxylate that esterification yield for suberic acid and glycol reaction generation is 90%, guiding thing is adipic acid 3.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 180ppm of the quality of adipic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:9.2:7.1 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of antioxidant 1010 and antioxidant 168 is added in the product of step (1):1) exist 237 DEG C, the prepolymerization reaction for carrying out 15min under conditions of 400Pa the precondensation product that inherent viscosity is 0.14dL/g is made, Middle prepolymerization reaction is carried out in the case where stir speed (S.S.) is the stirring of 16rpm, the mixture of antioxidant 1010 and antioxidant 168 Addition is the 0.003wt% of addition adipic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.0h under conditions of 220 DEG C, 40Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 7rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.5, inherent viscosity 1.06dL/g, and color is 8, the content of side reaction product is 0.9wt%.DTY is made in the polymer, processing waste silk rate is 9kg/t, and the item of fiber is dry Irregularity is 0.9%.
Embodiment 14
A method of inhibiting polymerization side reactions, in the process for preparing polymer using glutaric acid and pentanediol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material glutaric acid and pentanediol is 1: 1.10, the temperature of esterification is 230 DEG C, inhibits polymerization side reactions so that side reaction product contains in final obtained polymer Amount is 0.75wt%；Guiding thing is that pimelic acid reacts the carboxylate generated with decanediol.
Polymer preparation is as follows：
(1) esterification；
By glutaric acid and pentanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 230 DEG C, 170KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 97% is reacted with decanediol for pimelic acid, the additive amount of guiding thing is glutaric acid 2.5wt%, the additive amount of titanium silicon cobalt composite catalyst are the 190ppm of the quality of glutaric acid, and titanium silicon cobalt composite catalyst is by inclined titanium Acid, silica and cobalt acetate are 1 in molar ratio:7.0:0.1 is combined；
(2) prepolymerization reaction；
Mixture (the matter of antioxidant 1010, antioxidant 168 and antioxidant 616 is added in the product of step (1) Amount is than being 1:1:1) inherent viscosity is made as 0.13dL/g in the prepolymerization reaction that 15min is carried out under conditions of 250 DEG C, 100Pa Precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 5rpm stirring under carry out, antioxidant 1010, antioxidant 168 and antioxidant 616 mixture addition be step (1) in addition glutaric acid 0.001wt%；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 230 DEG C, 60Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.2, inherent viscosity 0.70dL/g, and color is 7, the content of side reaction product is 0.75wt%.FDY is made in the polymer, processing waste silk rate is 9.4kg/t, the item of fiber Dry irregularity is 0.95%.
Embodiment 15
A method of inhibiting polymerization side reactions, in the process for preparing polymer using succinic acid and hexylene glycol as primary raw material In, by adding guiding thing in esterification process, while the molar ratio for controlling esterification raw material succinic acid and hexylene glycol is 1: 1.10, the temperature of esterification is 240 DEG C, inhibits polymerization side reactions so that side reaction product in final polymer obtained Content is 0.95wt%；Guiding thing is that glutaric acid reacts the carboxylate generated with decanediol.
Polymer preparation is as follows：
(1) esterification；
By succinic acid and hexylene glycol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added Object carries out under conditions of 240 DEG C, 200KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing The carboxylate that the esterification yield generated is 98% is reacted with decanediol for glutaric acid, the additive amount of guiding thing is succinic acid 5.0wt%, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of the quality of succinic acid, and titanium silicon cobalt composite catalyst is by metatitanic acid Four butyl esters, silica and cobalt acetate are 1 in molar ratio:10:0.4 is combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of phosphoric acid and trimethyl phosphate is added in the product of step (1):2) 230 DEG C, The precondensation product that inherent viscosity is 0.14dL/g, wherein preshrunk is made in the prepolymerization reaction that 20min is carried out under conditions of 300Pa Poly- reaction is carried out in the case where stir speed (S.S.) is the stirring of 18rpm, and the addition of the mixture of phosphoric acid and trimethyl phosphate is step (1) The 0.005wt% of middle addition succinic acid；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 230 DEG C, 70Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.59, inherent viscosity 1.18dL/g, color It is 9, the content of side reaction product is 0.95wt%.Staple fiber is made in the polymer, processing waste silk rate is 8.5kg/t, fine The yarn unevenness of dimension is 0.85%.
Embodiment 16
A method of inhibiting polymerization side reactions, polymer is being prepared as primary raw material using M-phthalic acid and propylene glycol In the process, by adding guiding thing in esterification process, while esterification raw material M-phthalic acid and mole of propylene glycol being controlled Than being 1:1.07, the temperature of esterification is 233 DEG C, inhibits polymerization side reactions so that side reaction in final polymer obtained The content of product is 0.99wt%；Guiding thing is that terephthalic acid (TPA) reacts the carboxylate generated with hexylene glycol.
Polymer preparation is as follows：
(1) esterification；
By M-phthalic acid and propylene glycol with 1:After 1.07 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 233 DEG C, 60KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that terephthalic acid (TPA) reacts that the esterification yield generated is 98% with hexylene glycol to lead object, and the additive amount of guiding thing is isophthalic two The 5.0wt% of formic acid, the additive amount of titanium silicon cobalt composite catalyst are the 200ppm of the quality of M-phthalic acid, and titanium silicon cobalt is compound to urge Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:8.8:10 are combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of antioxidant 1010 and antioxidant 168 is added in the product of step (1):1) and The precondensation that inherent viscosity is 0.12dL/g is made in the prepolymerization reaction that phosphoric acid carries out 30min under conditions of 250 DEG C, 200Pa Product, wherein prepolymerization reaction are carried out in the case where stir speed (S.S.) is the stirring of 6rpm, and the addition of phosphoric acid is between being added in step (1) The addition of the mixture of the 0.04wt% of phthalic acid, antioxidant 1010 and antioxidant 168 is between being added in step (1) The 0.001wt% of phthalic acid；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 260 DEG C, 10Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.6, inherent viscosity 1.19dL/g, and color is 9, the content of side reaction product is 0.99wt%.Polyester DTY is made in the polymer, processing waste silk rate is 9.5kg/t, fiber Yarn unevenness be 0.9%.
Embodiment 17
A method of inhibiting polymerization side reactions, polymer is being prepared as primary raw material using M-phthalic acid and propylene glycol In the process, by adding guiding thing in esterification process, while esterification raw material terephthalic acid (TPA) and mole of propylene glycol being controlled Than being 1:1.07, the temperature of esterification is 240 DEG C, inhibits polymerization side reactions so that side reaction in final polymer obtained The content of product is 0.9wt%；Guiding thing is that M-phthalic acid reacts the carboxylate generated with butanediol.
Polymer preparation is as follows：
(1) esterification；
By terephthalic acid (TPA) and propylene glycol with 1:After 1.07 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst, Guiding thing carries out under conditions of 240 DEG C, 50KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing It is the carboxylate that M-phthalic acid reacts that the esterification yield generated is 93% with butanediol to lead object, and the additive amount of guiding thing is to benzene two The 3.5wt% of formic acid, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of the quality of terephthalic acid (TPA), and titanium silicon cobalt is compound to urge Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:10:5.0 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of phosphoric acid and phosphorous acid is added in the product of step (1):And antioxidant 1010 1) With the mixture (mass ratio 3 of antioxidant 168:2) prepolymerization reaction of 45min is carried out under conditions of 260 DEG C, 150Pa Be made inherent viscosity be 0.13dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 19rpm stirring under into The addition of the mixture of row, phosphoric acid and phosphorous acid is the 0.05wt% of addition terephthalic acid (TPA) in step (1), antioxidant 1010 with the 0.01wt% that the addition of the mixture of antioxidant 168 is addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 250 DEG C, 30Pa is finally made Polymer is obtained, wherein final polycondensation reaction is carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final polymer obtained is 1.25, inherent viscosity 0.62dL/g, color It is 8, the content of side reaction product is 0.9wt%.Polyester FDY is made in the polymer, processing waste silk rate is 10kg/t, fiber Yarn unevenness be 1.0%.

Claims (9)

1. a kind of method inhibiting polymerization side reactions, it is characterized in that：It is poly- being prepared using binary acid I and dihydric alcohol I as primary raw material It is 1 by the molar ratio added guiding thing in Esterification Stage, while controlling binary acid I and dihydric alcohol I during closing object: 1.05~1.10, inhibit polymerization side reactions so that content≤1.0wt% of side reaction product in the polymer；
The guiding thing is that binary acid II reacts the carboxylate generated with dihydric alcohol II, and the binary acid I is identical as binary acid II Or it is different, the dihydric alcohol I and dihydric alcohol II are identical or different.
2. it is according to claim 1 it is a kind of inhibit polymerization side reactions method, which is characterized in that the polymer it is specific Preparation process is as follows：
(1) esterification；
After binary acid I and dihydric alcohol I are mixed with beating, titanium silicon cobalt composite catalyst and guiding thing is added at 180~240 DEG C and 50 Esterification is carried out under conditions of~200KPa until water yield reaches 95% reaction terminating of theoretical water yield；The titanium silicon cobalt Composite catalyst is that titanium silicon composite catalyst is combined with cobalt series catalyst, and titanium silicon composite catalyst loads for silicon systems catalyst Titanium series catalyst and obtain；
(2) prepolymerization reaction；
The agent of heat resistanceheat resistant oxygen and/or antioxidant are added in the product of step (1) in 200~260 DEG C and the condition of 100~1000Pa The precondensation product of inherent viscosity≤0.15dL/g is made in the lower prepolymerization reaction for carrying out 15~45min；The prepolymerization reaction Stir speed (S.S.) be 5~20rpm；
(3) final polycondensation reaction；
Precondensation product made from step (2) carries out the final minification of 1.5~3.5h under conditions of 220~280 DEG C and 10~100Pa Polymer is made in poly- reaction；The stir speed (S.S.) of the final polycondensation reaction is 5~10rpm.
3. a kind of method inhibiting polymerization side reactions according to claim 2, which is characterized in that the addition of the guiding thing Amount is 0.5~5.0wt% of binary acid I additive amounts in step (1)；The additive amount of the titanium silicon cobalt composite catalyst is step (1) 100~200ppm of binary acid I additive amounts in；Titanium series catalyst in the titanium silicon cobalt composite catalyst, silicon systems catalyst and The molar ratio of cobalt series catalyst is 1:0.1~10:0.1~10.
4. a kind of method inhibiting polymerization side reactions according to claim 3, which is characterized in that the Titanium series catalyst is Butyl titanate or metatitanic acid；The silicon systems catalyst is silica；The cobalt series catalyst is cobalt acetate.
5. a kind of method inhibiting polymerization side reactions according to claim 1, which is characterized in that the binary acid II and two The esterification yield that first alcohol II reactions generate guiding thing is 90~98%；The binary acid I and binary acid II be respectively terephthalic acid (TPA), M-phthalic acid, 5-sodium sulfo isophthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and the last of the ten Heavenly stems One kind in diacid；The dihydric alcohol I and dihydric alcohol II is respectively ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptan One kind in glycol, ethohexadiol, nonanediol and decanediol.
6. a kind of method inhibiting polymerization side reactions according to claim 2, which is characterized in that the heat resistanceheat resistant oxygen agent adds Enter 0.005~0.05wt% that amount is binary acid I additive amounts in step (1)；The addition of the antioxidant is in step (1) 0.001~0.01wt% of binary acid I additive amounts.
7. a kind of method inhibiting polymerization side reactions according to claim 6, which is characterized in that the heat resistanceheat resistant oxygen agent is phosphorus One or more of acid, phosphorous acid, trimethyl phosphate, Trimethyl phosphite and triphenyl phosphate；The antioxidant is antioxygen One or more of agent 1010, antioxidant 168 and antioxidant 616.
8. a kind of method inhibiting polymerization side reactions according to claim 1, which is characterized in that the weight of the polymer is equal Molecular weight distribution index is 1.2~1.6, and inherent viscosity is 0.60~1.20dL/g, color≤10.
9. a kind of method inhibiting polymerization side reactions according to claim 1, which is characterized in that the polymer to be made POY, FDY, DTY or staple fiber, processing waste silk rate≤10kg/t, yarn unevenness≤1.0% of fiber.
CN201810489007.2A 2018-05-21 2018-05-21 Method for inhibiting polymerization side reaction Active CN108610477B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810489007.2A CN108610477B (en) 2018-05-21 2018-05-21 Method for inhibiting polymerization side reaction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810489007.2A CN108610477B (en) 2018-05-21 2018-05-21 Method for inhibiting polymerization side reaction

Publications (2)

Publication Number Publication Date
CN108610477A true CN108610477A (en) 2018-10-02
CN108610477B CN108610477B (en) 2020-04-17

Family

ID=63663972

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810489007.2A Active CN108610477B (en) 2018-05-21 2018-05-21 Method for inhibiting polymerization side reaction

Country Status (1)

Country Link
CN (1) CN108610477B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111363128A (en) * 2020-04-27 2020-07-03 张家港美景荣化学工业有限公司 PTT polyester with intensively distributed molecular weight and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417247A (en) * 2001-11-08 2003-05-14 中国石化上海石油化工股份有限公司 Production process of polypropylene glycol terephthalate
CN1556127A (en) * 2003-12-31 2004-12-22 浙江恒逸集团有限公司 Dyeingable dalk coloured copolyester and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417247A (en) * 2001-11-08 2003-05-14 中国石化上海石油化工股份有限公司 Production process of polypropylene glycol terephthalate
CN1556127A (en) * 2003-12-31 2004-12-22 浙江恒逸集团有限公司 Dyeingable dalk coloured copolyester and its preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111363128A (en) * 2020-04-27 2020-07-03 张家港美景荣化学工业有限公司 PTT polyester with intensively distributed molecular weight and preparation method thereof
CN111363128B (en) * 2020-04-27 2022-08-09 张家港美景荣化学工业有限公司 PTT polyester with concentratedly distributed molecular weight and preparation method thereof

Also Published As

Publication number Publication date
CN108610477B (en) 2020-04-17

Similar Documents

Publication Publication Date Title
CN108727575A (en) A kind of preparation method of biology base 2,5- furandicarboxylic acids base copolyesters
CN108660537A (en) A kind of preparation method of thermal sensitivity copolyester fiber
CN109456469B (en) Preparation method of high-fluidity cation modified copolyester
CN109180918B (en) A kind of copoly type high flow polyester master batch basis material and preparation method thereof
CN109369893B (en) Polyester with low oligomer content and preparation method thereof
CN109180916B (en) Continuous preparation method of PTT polyester
CN102432849B (en) Polymerizing production method for transparent amorphous copolyester
CN113550022B (en) Preparation method of cation-dyeable regenerated polyester fiber and product thereof
CN108610477A (en) A method of inhibiting polymerization side reactions
CN108559068A (en) A kind of PTT polyester or copolyesters and preparation method thereof
CN109180923B (en) High-fluidity stain-resistant easy-to-dye polyester master batch and preparation method thereof
CN108624982A (en) A kind of preparation method of cation-modified PTT copolyester fibers
CN108892770B (en) Method for inhibiting side reaction of tetrahydrofuran in polymerization process
CN111363128B (en) PTT polyester with concentratedly distributed molecular weight and preparation method thereof
CN109456468A (en) Hydrophilic easy-to-dye polyester master batch basis material of copoly type high fluidity and preparation method thereof
KR102202138B1 (en) Method for Preparing Polycyclohexylenedimethylene Terephthalate Glycol
CN106832241A (en) A kind of method that utilization composite catalyst prepares polyethylene terephthalate
CN108774312B (en) Low-viscosity polyester and preparation method thereof
CN109134837B (en) Homogeneous high-viscosity polyester and preparation method thereof
CN111471166A (en) Method for improving polyester polycondensation reaction rate
JP4582393B2 (en) Polyester production method
CN117757046A (en) Disperse dye easy-to-dye functional polyester and preparation method thereof
CN114853994B (en) Preparation method of aromatic flame-retardant polyester polyol
CN109575253B (en) Preparation method of PTT-based low-melting-point copolyester
CN106608967B (en) A kind of composite catalyst for synthesizing polyethylene terephthalate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant