CN1143088A - Preparing method for super high molecular weight polyester - Google Patents
Preparing method for super high molecular weight polyester Download PDFInfo
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- CN1143088A CN1143088A CN 96116245 CN96116245A CN1143088A CN 1143088 A CN1143088 A CN 1143088A CN 96116245 CN96116245 CN 96116245 CN 96116245 A CN96116245 A CN 96116245A CN 1143088 A CN1143088 A CN 1143088A
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Abstract
The present invention prepares superhigh molecular weight polyester through sectional solid polymerization (polycondensation) via polyester prepolymer with modified size and low crystallinity. The polyester produced has an intrinsic viscosity greater than 3.0 dl/g. The said technological process is suitable for commercial prodn.
Description
The invention relates to the preparation of super high molecular weight polyester, belong to the macromolecular compound class.It is that the performed polymer of the low-crystallinity polyester with certain size profile is handled, and carries out the high vacuum solid-phase polymerization subsequently in four stages, is prepared into the preparation method of super high molecular weight polyester thus.
As everyone knows, in bulk polymerization, because polyreaction reversible, polyreaction and depolymerization reaction reach balance soon, so method can only acquired character viscosity less than the polymer of 1dl/g.For improving polymeric molecular weight, people have adopted the method for solid state polymerization, this method has suppressed reversed reaction and has paid the generation of reaction, but acquired character viscosity is about the polymer of 1.2dl/g thus, for further improving polymeric molecular weight, United States Patent (USP) 4,792, the 573 insufficient problems of molecular weight that make at aforesaid method, carried out process modification, its technology characteristics is: the performed polymer of low-molecular-weight polyester is dissolved in the mixed solvent of trifluoroacetic acid and methylene dichloride, inject methanol solution then lentamente and be frozen into the gelinite that contains a large amount of methyl alcohol, to its gelinite methanol wash, remove the trifluoroacetic acid and the methylene dichloride that remain in the gelinite afterwards, and carry out vacuum-drying, obtain cavernous object thus, the columniform porous body of compressed one-tenth places solid state polymerization reactor, and nitrogen limit heating carrying out solid-phase polymerization is filled on the limit.This method is by polyester being dissolved, precipitate into powder, the granulation solid state polymerization, and dissolving precipitates into powder again, and the circulation means of granulation and solid state polymerization makes the polymer that limiting viscosity is 3.5～5.1dl/g.This shows that this method technical process is long, consumes a large amount of solvents, cause environmental pollution and can't implement problem such as suitability for industrialized production.
The objective of the invention is to prepare the existing defective of super high molecular weight polyester at above-mentioned several solid state polymerizations, it is simple to seek a kind of technological process, and generation of decontamination source and the solid state polymerization of cutting down expenses prepare the method for super high molecular weight polyester.
By research, the present invention proposes and progressively improve temperature of reaction to increase speed of reaction to solid state polymerization mechanism; Reduce the physical dimension of performed polymer, to accelerate internal divergence; The supra polymer structure of control performed polymer makes macromole have means such as certain reaction ability and obtains super high molecular weight polyester.
The invention relates to a kind of method for solid phase polymerization for preparing limiting viscosity greater than the 3.0d1/g polyester, it has comprised the requirement that performed polymer is had certain physical dimension, the physical dimension two-dimensional directional of performed polymer should be less than 0.05mm, performed polymer can have certain orientation degree but tangible degree of crystallinity (X-ray degree of crystallinity is zero, and densimetry is measured degree of crystallinity less than 14%) can not be arranged.Performed polymer is carried out pre-treatment and high vacuum solid-phase polymerization in four stages, make super high molecular weight polyester thus.
This technology is carried out pretreated condition to the performed polymer of polyester: pretreatment temperature is 90～110 ℃, and pretreatment time is 4～8 hours, and vacuum tightness is 0.1mmHg; More desirable pretreatment condition is: pretreatment temperature is 100～105 ℃, and pretreatment time is 5 hours, and vacuum tightness is less than 0.1mmHg.
This technology is carried out the condition of solid state polymerization and is carried out for dividing four sections to estrodur performed polymer, body is:
Fs: 160～200 ℃ of temperature of reaction, 1～5 hour reaction times, vacuum tightness 0.1mmHg.
Subordinate phase: 190～210 ℃ of temperature of reaction, 1～5 hour reaction times, vacuum tightness 0.1mmHg.
Phase III: 200～240 ℃ of temperature of reaction, 4～8 hours reaction times, vacuum tightness 0.1mmHg.
Quadravalence section: 230～270 ℃ of temperature of reaction, 4～8 hours reaction times, vacuum tightness 0.1mmHg.
More desirable estrodur performed polymer solid phase polymerization conditions is:
Fs: 175～185 ℃ of temperature of reaction, 2～3 hours reaction times, vacuum tightness 0.1mmHg.
Subordinate phase: 195～205 ℃ of temperature of reaction, 2～3 hours reaction times, vacuum tightness 0.1mmHg.
Phase III: 220～235 ℃ of temperature of reaction, 7～8 hours reaction times, vacuum tightness 0.1mmHg.
Quadravalence section: 245～255 ℃ of temperature of reaction, 16 hours reaction times, vacuum tightness 0.1mmHg.
The present invention and United States Patent (USP) 4,792,573 compare, cancelled loaded down with trivial details technological processs such as polyester dissolving, precipitation, granulations, exempted adopting costing an arm and a leg and the poisonous and harmful solvent, and the problem of environmental pollution that brings thus, having reduced production cost, is a kind of effective way of suitability for industrialized production.
The present invention is further specified in following experiment, is no longer illustrated but be only limited to below the example case.Example 1:
With the performed polymer of polyester, its two-dimensional is 0.026mm, double refraction 0.041, and degree of crystallinity 10% places the rotation vacuum unit (to see accompanying drawing 1, solid state polymerization setting drawing, 1-rotary type vacuum reactor; 2-insulation jacket; 3-thermometer; 4-airbath; 5-powerstat; 6-electric furnace; 7-single neck flask; 8-separation net) in, open vacuum pump and reach 0.1mmHg to the interior vacuum tightness of bottle, oil bath is heated to 105 ℃ and carries out 6 hours drying treatment, speed of rotation 35rpm.After pre-treatment finished, oil bath was warming up to 180 ℃, carried out pre-crystallisation process of fs in 2 hours; Subordinate phase solid-phase polymerization temperature is 200 ℃, and the reaction times is 2 hours; Phase III solid-phase polymerization temperature is 235 ℃, and the reaction times is 8 hours; Quadravalence section solid-phase polymerization temperature is 245 ℃, and the reaction times is 255 ℃ of 8 hours and temperature of reaction, and in 8 hours reaction times, solid-phase polymerization finishes, and is retained under the vacuum state and is cooled to room temperature, can get the polyester body of [η]=3.54 thus.
The mensuration of polymer viscosity: weigh 0.125 gram sample, (50: 50, V: V) being dissolved to concentration is that the solution of 0.5g/dl carries out viscosimetric analysis with 25 milliliters of trifluoroacetic acids and methylene dichloride mixed solution, it is Ubbelohde viscometer about 0.5mm that detected solution is placed capillary diameter, controlled temperature is 25 ℃, and recording above-mentioned gained polymer limiting viscosity is 3.54dl/g.Comparative example 2:
With two-dimensional is 0.064, degree of crystallinity 3%, and double refraction is that 0.01 estrodur performed polymer places in the rotation vacuum unit, carries out solid state polymerization by last routine processing condition, and is final that limiting viscosity be the polymer of 2.08dl/g.
Comparative example 3:
With two-dimensional is 0.019, degree of crystallinity 35%, and double refraction is that 0.127 estrodur performed polymer places in the rotation vacuum unit, carries out solid state polymerization by example 1 processing condition, and is final that limiting viscosity be the polymer of 1.54dl/g.
Claims (6)
1, a kind of method of estrodur performed polymer being carried out the super high molecular weight polyester preparation of solid state polymerization that comprises is characterized in that: the degree of crystallinity and the physical dimension of control performed polymer, and performed polymer is carried out pre-treatment and carries out the high vacuum solid state polymerization in four stages.
2, by the degree of crystallinity and the physical dimension of the described control performed polymer of claim 1, the degree of crystallinity that it is characterized in that performed polymer is less than 14% (densimetry mensuration), and the physical dimension two-dimensional directional is less than 0.05mm.
3, by claim 1 is described performed polymer is carried out pretreated method, it is characterized in that treatment temp is 90～110 ℃, the treatment time is 4～8 hours, and vacuum tightness is 0.1mmHg.
4, described performed polymer is carried out pretreated method by claim 1,3, it is characterized in that treatment temp is 100～105 ℃, the treatment time is 5～6 hours, vacuum tightness 0.1mmHg.
5, by claim 1 is described performed polymer is carried out the method for solid state polymerization in four stages, it is characterized in that:
Fs: temperature of reaction is 160～200 ℃, and the reaction times is 1～5 hour, vacuum tightness 0.1mmHg.
Subordinate phase: 190～210 ℃ of temperature of reaction, 1～5 hour reaction times, vacuum tightness 0.1mmHg.
Phase III: 200～240 ℃ of temperature of reaction, 4～8 hours reaction times, vacuum tightness 0.1mmHg.
Quadravalence section: 230～270 ℃ of temperature of reaction, 4～20 hours reaction times, vacuum tightness 0.1mmHg.
6, by claim 1,5 describedly carry out method for solid phase polymerization in four stages to performed polymer, it is characterized in that:
Fs: 175～185 ℃ of temperature of reaction, 2～3 hours reaction times, vacuum tightness 0.1mmHg.
Subordinate phase: 195～205 ℃ of temperature of reaction, 2～3 hours reaction times, vacuum tightness 0.1mmHg.
Phase III: 230～235 ℃ of temperature of reaction, 7～8 hours reaction times, vacuum tightness 0.1mmHg.
Quadravalence section: 245～255 ℃ of temperature of reaction, 15～16 hours reaction times, vacuum tightness 0.1mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116245A CN1063196C (en) | 1996-02-09 | 1996-02-09 | Preparing method for super high molecular weight polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116245A CN1063196C (en) | 1996-02-09 | 1996-02-09 | Preparing method for super high molecular weight polyester |
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| Publication Number | Publication Date |
|---|---|
| CN1143088A true CN1143088A (en) | 1997-02-19 |
| CN1063196C CN1063196C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116245A Expired - Fee Related CN1063196C (en) | 1996-02-09 | 1996-02-09 | Preparing method for super high molecular weight polyester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344673C (en) * | 2003-01-23 | 2007-10-24 | 住友化学工业株式会社 | Solid phase polymerization method of polymer |
| CN101486790B (en) * | 2009-02-20 | 2011-07-20 | 中国石化仪征化纤股份有限公司 | Method for producing high molecular weight polyester |
| CN109081907A (en) * | 2018-06-29 | 2018-12-25 | 浙江尤夫高新纤维股份有限公司 | High viscosity polyester and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876326A (en) * | 1987-03-26 | 1989-10-24 | The Goodyear Tire & Rubber Company | Solid state polymerization of polyester prepolymers |
| US4755587A (en) * | 1987-03-26 | 1988-07-05 | The Goodyear Tire & Rubber Company | Solid state polymerization of polyester prepolymers |
| US4792573A (en) * | 1988-04-01 | 1988-12-20 | The Goodyear Tire & Rubber Company | Preparation of ultra-high molecular weight polyester |
-
1996
- 1996-02-09 CN CN96116245A patent/CN1063196C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344673C (en) * | 2003-01-23 | 2007-10-24 | 住友化学工业株式会社 | Solid phase polymerization method of polymer |
| CN101486790B (en) * | 2009-02-20 | 2011-07-20 | 中国石化仪征化纤股份有限公司 | Method for producing high molecular weight polyester |
| CN109081907A (en) * | 2018-06-29 | 2018-12-25 | 浙江尤夫高新纤维股份有限公司 | High viscosity polyester and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1063196C (en) | 2001-03-14 |
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