CN105237754B - A kind of high efficiency polyester solid phase polycondensation method of high-pressure carbon dioxide auxiliary - Google Patents
A kind of high efficiency polyester solid phase polycondensation method of high-pressure carbon dioxide auxiliary Download PDFInfo
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- CN105237754B CN105237754B CN201410237802.4A CN201410237802A CN105237754B CN 105237754 B CN105237754 B CN 105237754B CN 201410237802 A CN201410237802 A CN 201410237802A CN 105237754 B CN105237754 B CN 105237754B
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Abstract
The present invention relates to a kind of high-pressure carbon dioxide（CO2）The high efficiency polyester solid phase polycondensation method of auxiliary, more particularly to one kind is with high pressure CO2The polyester solid phase polycondensation method of stage renewal.This method comprises the following steps：A. the polyester prepolyer synthesized in industrial processes is carried out pre-crystallized；B. pre-crystallized polyester prepolyer is placed in high-pressure reactor and seals reactor, rise temperature of reactor injects high pressure CO to reaction temperature2To reaction pressure, in CO2Auxiliary is lower to carry out first stage solid phase polycondensation；C. to the end of first stage polycondensation reaction, reactor pressure is let out to normal pressure, refills high pressure CO2Reactor pressure is risen into reaction pressure again, starts the polycondensation reaction of second stage.In pressurization-polycondensation ,-pressure release-pressurizes during this circulate operation, and reactor temperature remains unchanged, until obtaining the polyester product of certain degree of polymerization.Increased substantially using the polyester solid phase polycondensation efficiency of the method.
Description
Technical field
The present invention relates to a kind of new high efficiency polyester solid phase polycondensation method, more particularly to one kind is with high-pressure carbon dioxide
（CO2）The polyester solid phase polycondensation method of auxiliary.
Background technology
Polyester resin representated by polyethylene terephthalate generally has higher modulus of elasticity, glass transition
Temperature, and good crystallinity and chemical resistance, it is widely used in producing bottle, food service tray, fiber and tire
Cord.The prepolymer of polyester is generated by dihydric alcohol and binary acid reaction, and its degree of polymerization is 20-30.Generally, fiber-grade polyester by
Prepolymer obtains through melt polycondensation, and its degree of polymerization brings up to 100 or so.And in order to obtain bottle grade PET, then need to contract using solid phase
The degree of polymerization is further brought up to about 150 by polymerizing technology.
The polycondensation of polyester is reversible reaction, it is necessary to the volatile small molecule pair that elimination reaction generates from reaction system in time
Product, to promote balance to be moved to the direction that polyester molecule chain increases.In solid phase polycondensation process, because volatile byproducts exist
Diffusion mass transfer in polymeric matrix is restricted, traditional solid phase contracting carried out under the conditions of vacuum or inert gas purge
For poly- speed slowly, it is necessary to about 15-20 hours, production efficiency is relatively low.
The content of the invention
Deficiency in existing process, it is an object of the invention to provide one kind can improve polyester solid phase polycondensation speed,
It is adapted to industrial new polyester solid phase polycondensation method.
The polyester solid phase polycondensation technique of the present invention comprises the following steps：
A. the polyester prepolyer synthesized in industrial processes is carried out pre-crystallized 2-12 at a temperature of 100-140 DEG C
Hour, obtained crystallinity is 20-50%；B. pre-crystallized polyester prepolyer is placed in high-pressure reactor and seals reaction
Device.The temperature in high-pressure reactor is then increased to 180-250 DEG C, then CO is injected into reactor2Gas is to reaction pressure
The MPa of power 5-25, and carry out the polycondensation reaction of first stage.Per multi-stage polycondensation, the time of reaction is 0.5-5 hour；C. treat
First stage polycondensation reaction terminates, and reactor pressure is let out to normal pressure, refills high pressure CO2Reactor is boosted to
Reaction pressure, start the polycondensation reaction of second stage.It is temperature-resistant in maintenance reaction device in this gas phase renewal process；
D. repeat step c operation, including boosting, solid state polycondensation and pressure release, until obtaining the polyester product of certain degree of polymerization.This
Method needs to repeat 2-20 pressurization-polycondensation-decompression cycle cycles.
Advantages of the present invention is embodied in.
1st, the present invention takes full advantage of high pressure CO2Plastication to polyester matrix, improve the freedom of polymeric matrix
Volume, so as to improve the activity of reactive terminal group, while promote diffusion of the volatile byproducts in polymer matrix body.Cause
This, polyester solid phase polycondensation speed is greatly improved.Conventional solid polycondensation brings up to the degree of polymerization of polyester from 100
150 about need 15-20 hours, and use the new polyester polycondensation method of the present invention only to need 6 hours or so.
2nd, polyester solid phase polycondensation method of the invention is applied to the polyester prepolyer that the degree of polymerization is 20-100, than only fitting
With the conventional polyester solid phase polycondensation method that the degree of polymerization is 100 or so polyester prepolyers, the present invention can reduce melting aftercondensated rank
Equipment and the energy input of section.
3rd, polyester matrix is plastified than using organic solvent, CO2Not only more there is environment friendly, and instead
Only CO need to can be achieved by pressure release after should terminating2With the separation of polymer, it is not necessary to using the separation hand of the high energy consumptions such as evaporation
Section.
4th, new polyester polycondensation method of the invention is with CO2The interim renewal of gas is characterized, and is continuously blown than gas
The polycondensating process swept, the method also more save while gas usage amount is reduced.
Embodiment
Embodiment 1：The degree of polymerization of prepolymer in industrial polyester generating process is 30, and grain diameter is about 0.2mm.
It is 40 % that the pre-crystallized crystallinity 8 hours, obtained is carried out at a temperature of 110 DEG C；High pressure will be placed in through pre-crystallized polyester prepolyer
In reactor.The packing factor of high-pressure reactor is 5 kilograms/m3, prepolymer bulk density is 0.5 kilogram/m2.By reactor
Interior temperature rises to 210 DEG C, CO in reactor2Pressure rises to 25 MPa.It is 0.5 hour per the elementary reaction time.First stage is anti-
After should terminating, reactor pressure is let out to normal pressure, boosts to reaction pressure again；Repeat above-mentioned boosting, solid phase polycondensation and pressure release
Operation, the degree of polymerization of polyester reaches 150 after the reaction time is about 14 hours.
Embodiment 2：The degree of polymerization of prepolymer in industrial polyester generating process is 20, and grain diameter is about 1mm.120
It is 50 % that the pre-crystallized crystallinity 12 hours, obtained is carried out at a temperature of DEG C；It is anti-by high pressure is placed in through pre-crystallized polyester prepolyer
Answer in device.The packing factor of high-pressure reactor is 2 kilograms/m3, prepolymer bulk density is 3 kilograms/m2.Will be warm in reactor
Degree rises to 220 DEG C, CO in reactor2Pressure rises to 8 MPa.It is 1 hour per the elementary reaction time.First stage reaction terminates
Afterwards, reactor pressure is let out to normal pressure, boosts to reaction pressure again；Above-mentioned boosting, solid phase polycondensation and pressure discharge operations are repeated, instead
About the degree of polymerization of polyester reaches 100 after 6 hours between seasonable.
Embodiment 3：For the polyester that the degree of polymerization is 95 as solid phase polycondensation raw material, grain diameter is about 2mm.In 120 DEG C of temperature
It is lower to carry out the pre-crystallized crystallinity 5 hours, obtained as 25%；Crystallized poly- polyester prepolyer is placed in high-pressure reactor.It is high
The packing factor for pressing reactor is 10 kilograms/m3, prepolymer bulk density is 5 kilograms/m2.Reactor temperature is risen to
230 DEG C, CO in reactor2Pressure rises to 16 MPa.Per the elementary reaction time be 2 hours, the first stage reaction terminate after, let out to
Normal pressure, again by the CO in reactor2Boost to reaction pressure；Repeat above-mentioned boosting, solid phase polycondensation and pressure discharge operations, reaction time
The degree of polymerization of polyester reaches 150 after about 6 hours.
Embodiment 4：For the polyester that the degree of polymerization is 100 as solid phase polycondensation raw material, grain diameter is about 0.5mm.In 140 DEG C of temperature
Degree is lower to be carried out pre-crystallized 2 hours, and obtained crystallinity is 20%；Pre-crystallized poly- polyester prepolyer is placed in high-pressure reactor.
The packing factor of high-pressure reactor is 20 kilograms/m3, prepolymer bulk density is 0.5 kilogram/m2.By reactor temperature liter
To 250 DEG C, CO in reactor2Pressure rises to 20 MPa.It is 5 hours per the elementary reaction time, after first stage reaction terminates, lets out
To normal pressure, again by the CO in reactor2Boost to reaction pressure；Above-mentioned boosting, solid phase polycondensation and pressure discharge operations are repeated, during reaction
Between the degree of polymerization of polyester reaches 200 about after 12 hours.
Embodiment 5：The degree of polymerization of prepolymer in industrial polyester generating process is 50, and grain diameter is about 1mm.110
It is 40 % that the pre-crystallized crystallinity 10 hours, obtained is carried out at a temperature of DEG C；It is anti-by high pressure is placed in through pre-crystallized polyester prepolyer
Answer in device.The packing factor of high-pressure reactor is 5 kilograms/m3, prepolymer bulk density is 5 kilograms/m2.Will be warm in reactor
Degree rises to 230 DEG C, CO in reactor2Pressure rises to 6 MPa.It is 3 hours per the elementary reaction time.First stage reaction terminates
Afterwards, reactor pressure is let out to normal pressure, boosts to reaction pressure again；Above-mentioned boosting, solid phase polycondensation and pressure discharge operations are repeated, instead
About the degree of polymerization of polyester reaches 150 after 9 hours between seasonable.
Embodiment 6：The degree of polymerization of prepolymer in industrial polyester generating process is 80, and grain diameter is about 1.5mm.
It is 30 % that the pre-crystallized crystallinity 4 hours, obtained is carried out at a temperature of 130 DEG C；High pressure will be placed in through pre-crystallized polyester prepolyer
In reactor.The packing factor of high-pressure reactor is 15 kilograms/m3, prepolymer bulk density is 4 kilograms/m2.By reactor
Interior temperature rises to 240 DEG C, CO in reactor2Pressure rises to 15 MPa.It is 3 hours per the elementary reaction time.First stage reacts
After end, reactor pressure is let out to normal pressure, boosts to reaction pressure again；Repeat above-mentioned boosting, solid phase polycondensation and pressure release behaviour
Make, the degree of polymerization of polyester reaches 200 after the reaction time is about 15 hours.
Claims (7)
- A kind of 1. high pressure CO2The polyester solid phase polycondensation method of auxiliary, its production method include：A. the polyester prepolyer granule of certain molecular weight is carried out pre-crystallized；B. pre-crystallized polyester prepolyer is placed in high-pressure reactor and seals reactor, the temperature for raising reactor is extremely reacted Temperature, while inject high pressure CO2To reaction pressure, in CO2The lower solid phase polycondensation for carrying out the first stage of auxiliary；C. to the end of first stage polycondensation reaction, reactor pressure is let out to normal pressure, refills high pressure CO2By reactor Reaction pressure is boosted to, starts the polycondensation reaction of second stage；D. c operation is repeated, during-pressure release-pressurizes this circulate operation in pressurization-polycondensation, reactor temperature maintains not Become, until obtaining the polyester product of certain degree of polymerization；Wherein, the degree of polymerization of polyester prepolyer is 20-100 used by step a, and step a pre-crystallization temperature is 110-140 DEG C, the pre-crystallized time is 2-12 hours, and the crystallinity for the pre-crystallized polyester prepolyer that step a is obtained is 20-50%, step a Polyester prepolyer grain diameter be 0.2-2 millimeter；Step b reaction temperature is 180-250 DEG C, step b reaction pressure For 5-25MPa.
- 2. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, the filling system of step b high-pressure reactors Number is 2-20 kilograms/m3, bulk density is 0.5-5 kilogram/m2。
- 3. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, step b boost process are controlled 2-10 Minute.
- 4. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, when mono- multi-stage polycondensation of step b reacts Between control at 0.5-5 hour, each elementary reaction time is identical or different.
- 5. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, step c pressure leak processes are controlled 3-30 Minute.
- 6. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, step d need 2-30 pressurization-contractings Poly- pressure release-pressurized circulation cycle, reaction time are 6-15 hours.
- 7. high pressure CO according to claim 12The polyester solid phase polycondensation method of auxiliary, solid phase polycondensation polyester production obtained by step d The degree of polymerization of product is 100-200.
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| CN201410237802.4A CN105237754B (en) | 2014-06-01 | 2014-06-01 | A kind of high efficiency polyester solid phase polycondensation method of high-pressure carbon dioxide auxiliary |
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| CN105237754B true CN105237754B (en) | 2018-01-30 |
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| CN112409578B (en) * | 2020-10-20 | 2022-10-11 | 金聚合科技(宁波)有限公司 | Method for preparing high molecular weight PBAT by combining supercritical carbon dioxide induced PBAT crystallization/solid phase polycondensation |
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| IT1211471B (en) * | 1987-07-24 | 1989-11-03 | Cobarr Spa | PROCEDURE FOR THE REDUCTION OF IMPURSES OF POLYESTER RESINS |
| DE102004041370A1 (en) * | 2004-08-25 | 2006-03-02 | Bühler AG | Solid phase polycondensation of polyester with process gas purification |
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