CN1772792A - Solid phase polymerization process for preparing ethylene telephthalate and dihydric alcohol copolymer - Google Patents
Solid phase polymerization process for preparing ethylene telephthalate and dihydric alcohol copolymer Download PDFInfo
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- CN1772792A CN1772792A CN 200510110057 CN200510110057A CN1772792A CN 1772792 A CN1772792 A CN 1772792A CN 200510110057 CN200510110057 CN 200510110057 CN 200510110057 A CN200510110057 A CN 200510110057A CN 1772792 A CN1772792 A CN 1772792A
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Abstract
The present invention relates to solid phase polymerization process for preparing ethylene terephthalate and dihydric alcohol copolymer. The copolymer is prepared through the primary mixing of poly ethylene terephthalate chip and dihydric alcohol monomer, extruding and pelletizing in a double screw extruder, drying the chip and solid phase condensation polymerization inside a solid phase polymerization reactor to obtain copolyester with the required material ratio and characteristic viscosity. The preparation process is simple and suitable for industrial production.
Description
Technical field
This invention relates generally to a kind of polyethylene terephthalate (PET) modification by copolymerization method, is the solid phase polymerization method of the multipolymer (PETG) of a kind of polyethylene terephthalate and dibasic alcohol furtherly.
Background technology
Polyester-polyether series segmented copolymer has become the research topic of comparatively paying attention to both at home and abroad because its unique molecular chain structure and aggregated structure, still is all to have broad application prospects aspect the fiber at plastics, rubber.
Polyethylene terephthalate and polyethyleneglycol block copolymer (PET-PEG) are a kind of thermoplastic elastomers, and its molecular structure has the alternate constructional feature of soft or hard section, and PET-PEG is as the existing many reports of terylene static inhibitor.
The high symmetry and the segmental rigidity of polyethylene terephthalate (PET) molecular structure make the PET material have favorable mechanical physicals, solvent resistance and wear resistance, and cheap, thereby are widely used in producd fibers, film and polyester bottles.When yet PET is used as engineering plastics, because its crystallization is slow, injection mold temperature height (often die temperature will reach 130 ℃), shaping cycle is long, and problems such as shock strength difference are restricted.Adopt interpolation nucleator and crystallization promoter to improve the PET crystallization velocity at present mostly.
Solid phase polycondensation is a kind of new polycondensation method that grows up nearly decades.Adopt process for solid state polycondensation can avoid many side reactions that under the high-temperature fusion polycondensation, take place, thereby to improve the purity and the quality of resin comparing demulcent condition (temperature is lower) synthetic macromolecular compound down.Also can prepare high molecular weight polymers for special requirement.As can only making the polyester of molecular weight about 23000, and just can make molecular weight at the polyester more than 30000 (as plastics and tire cord) with process for solid state polycondensation with melt phase polycondensation.Very high or more than fusing point, be easy to the monomer polycondensation of decomposing for those fusing points, and the preparation of high-temperature polymer, solid phase polycondensation is very suitable implementation method.
The patent of publication number CN1388177 provides a kind of rapid crystallization polyethylene terephthalate mixture and preparation method thereof.This mixture is formed through melt extruding by 30-80 part (parts by weight, down together) polyethylene terephthalate, 0.2-8 part compound crystal nucleator, 10-25 part composite flame-retardant agent, 10-60 part filling toughener, other processing aid of 0.1-5 part.Adopt the rapid crystallization technology, solved when polyethylene terephthalate uses as engineering plastics in the molding process that crystallization rate is slow, injection molding temperature height, molding cycle long shortcoming, can be widely used in the component of making electronic apparatus, machine machinery, household electrical appliances etc.
US6537679B1 provides has fluorescent effect also with the material of a kind of usefulness 1,4 cyclohexanedimethanol modified PET as matrix.This PETG fluorescent material can increase the railway mark visibility on real daytime.
Synthesized a kind of new packaging film material under the effect of WO2005028188 with a kind of Resins, epoxy and a kind of catalyzer, PET/PETG/ polyester elastomer segmented copolymer.This material has improved the shortcoming of conventional P ET film.
US2004091651 provides a kind of container material and synthetic method, this material is that the ratio of other dibasic alcohol and acid is between 0.2 and 2.2 molar percentages by ethylene glycol and other dibasic alcohol and terephthalic acid and the PET multipolymer of other diprotic acid as repeating unit.
It is a kind of than PET homopolymer with have the Novel PET multipolymer of the barrier of better oxygen and carbonic acid gas with 1,4 cyclohexanedimethanol modified PET multipolymer that US6103857 provides.This multipolymer is that copolymerization in 1: 1 forms by the ratio of 1,4 cyclohexanedimethanol and m-phthalic acid
DE10002161 has related to a kind of polyester film of coextrusion diaxial orientation, and with the solubility ignition dope extrude together make its have the resistance right property.
Summary of the invention
The object of the invention provides a kind of method that is prepared the multipolymer of polyethylene terephthalate and dibasic alcohol by solid state polymerization, it is polyethylene terephthalate (PET) modification by copolymerization method, be the solid phase polymerization method of the multipolymer (PETG) of a kind of polyethylene terephthalate and dibasic alcohol furtherly, will contain dibasic alcohol and introduce in the PET molecular backbone chain.
Synthetic method is as follows:
With low viscosity PET is body material, and dibasic alcohol is a comonomer, polyoxyethylene glycol, polypropylene glycol or 1,4 cyclohexane dimethanol, 1, the 4-butyleneglycol is the blend extruding pelletization in twin screw extruder, then blended slice is carried out solid state polymerization, finishes copolymerization under solid state shape.
Technology of the present invention is as shown in Figure 1: dry PET section, PET section and the preliminary blend of comonomer, blend extruding pelletization and solid phase polycondensation in twin screw extruder.
PET material as packing or the application of other aspects all needs quite high molecular weight, therefore usually carries out solid phase polycondensation, the industrial aftercondensated that is called behind melt phase polycondensation.So the present invention adopts the method for solid phase polycondensation to carry out copolymerization in industrial easy realization and can not increase the cost of polymerization process.
The PET suggestion low viscosity PET of intrinsic viscosity between 0.5-0.7 of this employing of the present invention.
Blend is in twin screw extruder PET to be cut into slices and the even blend of dibasic alcohol comonomer among the present invention, respectively distinguishes temperature according to blend ratio difference and will suitably adjust, and blending temperature is generally 200-280 ℃.Twin screw extruder Zhong Ge district temperature is controlled following scope: a district: 200-220 ℃; Two district's temperature are in fusing point ± 10 ℃; Three districts look to extrude blend melt viscosity mobile and fix on 260-230 ℃; Four district's temperature can not be low excessively, otherwise stifled head is advised 218-250 ℃.Visual fusion liquid flowability and deciding, general copolymerization 2min-8min.
This synthetic route the first step adopts PET section and the blend granulation in twin screw extruder of blend small molecule monomer dibasic alcohol.For small molecules blend monomer powders shape can be directly with both can blend granulation in twin screw extruder after the PET section is carried out just mixing, and just mix with the PET section again after need pulverizing granular monomer, can guarantee that like this powder wrapped melt extrudes evenly and makes melt flow smooth and easy, continues to flow in section.
What polymerization process of the present invention adopted is the method for solid state polymerization, the temperature of selected solid phase polycondensation below the PET fusing point 10 ℃～40 ℃, promptly 210 ℃～240 ℃, comonomer is in molten state in this temperature range, in non-crystalline region and PET molecular chain generation copolyreaction.The time of solid state polymerization on blend after PET molecular weight and final desired molecule amount decide, be generally 1～30 hour.
The used dibasic alcohol of the present invention can be different molecular weight polyethylene glycol (PEG), polypropylene glycol or 1,4 cyclohexane dimethanol, 1,4-butyleneglycol etc.Used polyoxyethylene glycol (PEG) molecular weight of the present invention can be 1500-8000, is preferably 2000-6000.
The polyethylene terephthalate that present method was suitable for and the weight ratio of dibasic alcohol are 1: 0.01-0.5.Preferably 1: 0.10-0.5.
Synthetic route of the present invention is considered small molecules and copolymer blended back flowability, and expect that co-monomer content is than under the condition with higher, adopt following improving one's methods: when dry PET section, PET section and copolymerization monomer weight ratio example are smaller, preliminary blend blend extruding pelletization, solid phase polycondensation in twin screw extruder; Again with gained multipolymer section and comonomer through the twin screw blend, then carry out solid phase polycondensation once more, obtain final co-monomer content and cut into slices than the multipolymer of higher required ratio and intrinsic viscosity.
The inventive method is easy, can be fit to need of industrial production.
Description of drawings
Fig. 1 is an artwork of the present invention,
Fig. 2 is an improvement artwork of the present invention,
Fig. 3 is copolymerization time and tackify procedure chart.
In the accompanying drawing 3, X-coordinate is the copolymerization time, hour; Ordinate zou is an intrinsic viscosity.
Embodiment
Will be further understood that the present invention by following embodiment, but can not limit content of the present invention.
Synthesizing of embodiment 1 PET-PEG (10wt%) multipolymer
Earlier with in 110 ℃ of a conventional ovens of 3kgPET section dry one day, with standby after the polyoxyethylene glycol (PEG) of 333g molecular weight 1500 just mixes.
The temperature of respectively distinguishing of setting twin screw is 220,260,245,235 ℃, and the mixture batten of extruding is through the condensate draining granulation.80 ℃ of dryings of blend section and in 90 ℃ of pre-crystallization 4h.Obtained the multipolymer section of required viscosity then in 15 hours at 210 ℃ of following solid state polymerizations, sampling in per 5 hours is no more than 5 minutes sample time.
Table 1 different copolymer time PET-PEG and pure PET are relatively
| Sample | Tm(℃) | Tc(℃) | ΔH m(J/g) | ΔH c(J/g) | Degree of crystallinity (%) |
| PET after the extraction 0 hour 5 | 256.8 255.2 254.7 255.1 255.3 | 202.1 209.2 201.7 200.1 196.0 | -48.82 -51.99 -43.28 -44.40 -46.04 | 48.85 48.03 41.52 43.23 43.85 | 40.7 40.0 34.6 36.0 36.5 |
Gained copolymerization time and tackify process are as shown in Figure 3.
Synthesizing of embodiment 2 PET-PEG1500 (20wt%) multipolymer
Earlier with 90 ℃ of dryings in 3kgPET section and a conventional oven 4 hours, again 120 ℃ of vacuum drying ovens dry 4 hours down.Just mix back standby with polyoxyethylene glycol (PEG) 750g of molecular weight 1500 then.
The temperature of respectively distinguishing of setting twin screw is 220,260,240,230 ℃, and the mixture batten of extruding is through the condensate draining granulation.80 ℃ of dryings of blend section and in 90 ℃ of pre-crystallization 4h.Obtain the multipolymer section of required viscosity then 210 ℃ of corresponding times of following solid state polymerization.
The synthetic method of embodiment 3 PET-PEG1500 (40wt%) multipolymer is identical with example 2.
Synthesizing of embodiment 4 PET-PEG4000 (10wt%) multipolymer
Earlier with in 110 ℃ of a conventional ovens of 3kgPET section dry one day, with standby after the polyoxyethylene glycol (PEG) of 333g molecular weight 4000 just mixes.
The temperature of respectively distinguishing of setting twin screw is 220,260,250,245 ℃, and the mixture batten of extruding is through the condensate draining granulation.80 ℃ of dryings of blend section and in 110 ℃ of pre-crystallization 2h.Obtain the multipolymer section of required viscosity then 240 ℃ of corresponding times of following solid state polymerization.
Claims (7)
1, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate and dibasic alcohol is characterized in that the section of polyethylene terephthalate just mixes with the dibasic alcohol monomer; Blend extruding pelletization in 200-280 ℃ of twin screw extruder; Again 210 ℃～240 ℃ solid phase polycondensation 1-30 hour; The weight ratio of described polyethylene terephthalate and dibasic alcohol is 1: 0.01-0.5; Described dibasic alcohol is a polyoxyethylene glycol, polypropylene glycol or 1,4 cyclohexane dimethanol, 1,4-butyleneglycol.
2, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 1 and dibasic alcohol is characterized in that described twin screw extruder temperature is usually at 200-280 ℃; The temperature in one～four district is respectively: a district: 200-220 ℃; Two district's temperature are in PET fusing point ± 10 ℃; Three district 260-230 ℃; Four district 210-255 ℃; Blend 2-8 minute.
3, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 1 and dibasic alcohol is characterized in that described and PET is a low viscosity, intrinsic viscosity 0.5～0.7.
4, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 1 and dibasic alcohol is characterized in that described solid phase polymerization temperature at 210～240 ℃, 1～30 hour solid state polymerization time.
5, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 1 and dibasic alcohol is characterized in that described dibasic alcohol is a polyoxyethylene glycol, polypropylene glycol or 1,4 cyclohexane dimethanol, 1,4-butyleneglycol.
6, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 5 and dibasic alcohol is characterized in that described molecular weight polyethylene glycol is 1500-8000.
7, the solid phase polymerization method of the multipolymer of a kind of polyethylene terephthalate as claimed in claim 1 and dibasic alcohol, it is characterized in that in the solid phase polycondensation product that described method obtains, when the part by weight of polyethylene terephthalate and dibasic alcohol hour, the solid phase polycondensation product that is obtained once more with the preliminary blend of dibasic alcohol, in twin screw extruder blend extruding pelletization, solid phase polycondensation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510110057 CN1772792A (en) | 2005-11-04 | 2005-11-04 | Solid phase polymerization process for preparing ethylene telephthalate and dihydric alcohol copolymer |
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| CN 200510110057 CN1772792A (en) | 2005-11-04 | 2005-11-04 | Solid phase polymerization process for preparing ethylene telephthalate and dihydric alcohol copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412105C (en) * | 2006-10-12 | 2008-08-20 | 东华大学 | Solid phase polymerization process of PET/PTT copolyester |
| CN102345188A (en) * | 2010-07-23 | 2012-02-08 | 东丽纤维研究所（中国）有限公司 | Polymer alloy fiber and polyphenylene sulfide (PPS) ultrafine fiber |
| CN104177605A (en) * | 2014-08-04 | 2014-12-03 | 浙江大学 | Antistatic agent for PET polyester film and preparation method of antistatic agent |
-
2005
- 2005-11-04 CN CN 200510110057 patent/CN1772792A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412105C (en) * | 2006-10-12 | 2008-08-20 | 东华大学 | Solid phase polymerization process of PET/PTT copolyester |
| CN102345188A (en) * | 2010-07-23 | 2012-02-08 | 东丽纤维研究所（中国）有限公司 | Polymer alloy fiber and polyphenylene sulfide (PPS) ultrafine fiber |
| CN102345188B (en) * | 2010-07-23 | 2014-07-23 | 东丽纤维研究所（中国）有限公司 | Polymer alloy fiber and polyphenylene sulfide (PPS) ultrafine fiber |
| CN104177605A (en) * | 2014-08-04 | 2014-12-03 | 浙江大学 | Antistatic agent for PET polyester film and preparation method of antistatic agent |
| CN104177605B (en) * | 2014-08-04 | 2016-06-29 | 浙江大学 | A kind of PET mylar antistatic additive and preparation method thereof |
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