CN101525416A - Biobased polyethylene terephthalate - Google Patents
Biobased polyethylene terephthalate Download PDFInfo
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- CN101525416A CN101525416A CN200810018614A CN200810018614A CN101525416A CN 101525416 A CN101525416 A CN 101525416A CN 200810018614 A CN200810018614 A CN 200810018614A CN 200810018614 A CN200810018614 A CN 200810018614A CN 101525416 A CN101525416 A CN 101525416A
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- ethylene glycol
- polyethylene terephthalate
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- terephthalate
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Abstract
The invention discloses a biobased polyethylene terephthalate. The melting point of the biobased polyethylene terephthalate is between 255 and 270 DEG C, and the ethylene glycol in the raw materials is a biobased ethylene glycol, namely the carbon element in the ethylene glycol component of the raw materials is sourced from biological materials. The polyethylene terephthalate sourced from biobased materials has excellent performances, and the melting point, the diethylene glycol content, the terminal group content, the characteristic viscosity of the biobased polyethylene terephthalate are the same as those of the polyethylene terephthalate sourced from common petroleum based materials; moreover, the biobased polyethylene terephthalate also meets the requirements on environmental protection.
Description
Technical field:
The present invention is a kind of polyethylene terephthalate.
Background technology:
In recent years, along with going from bad to worse of environment for human survival, people more and more pay close attention to development environment friendly material and use renewable starting material.Oil is most important industrial chemicals as Nonrenewable resources, but owing to a large amount of CO in using engineering and in final the discarding
2Discharging, CO
2A large amount of dischargings have caused a series of problems such as global warming, and directly threaten human existence.If utilize biological raw material, then can not increase the CO in the environment again newly
2Content reaches the purpose that reduces Greenhouse effect protection environment, can also increase income for farm crop market.Therefore how utilizing organism-based raw material, reduce the use of oil, is that people face one of important research problem.
Polyethylene terephthalate (PET) fiber is the synthon kind of present world wide production maximum, more than 10,000,000 tons, is an important chemical product in the domestic production capacity of China.Because producing the raw material of PET all is the processed goods that derives from oil, how using non-petroleum exploitation production of polyester raw produce and PET product is an important research project.
People have utilized renewable biological source to produce multiple polymers raw materials for production product and multiple polymers product at present, for example E.I.Du Pont Company is by fermenting to corn, through biology and chemical process, prepare 1,3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not Poly(Trimethylene Terephthalate) (PTT) polymkeric substance of oil material.Natureworks company is raw material equally with farm crop, through biology and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable poly(lactic acid) (PLA) polymkeric substance.In CN200610028411.7, the ethylene glycol direct polymerization that Donghua University discloses a kind of preparation method of corn-based ethylene glycol and utilizes this method to prepare prepares the method for PDT copolyester fiber, the bio-based ethylene glycol content that this method obtains is up to 98%, do not reach the requirement of purity more than 99.5% of polyester spent glycol, and the performance of itself and normal polyester is had any different because introduce copolymer composition, also easily fade as this copolyester fiber easy dyeing.
Summary of the invention:
The object of the present invention is to provide a kind of biological poly ethylene glycol terephthalate that meets the environmental protection needs.
Technical solution of the present invention is:
A kind of biological poly ethylene glycol terephthalate is characterized in that: 1. the fusing point of biological poly ethylene glycol terephthalate is 255-270 ℃; 2. its raw material ethylene glycol is biological ethyl glycol, and promptly the carbon in the raw material glycol component is to derive from biomaterial.
Described biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.Wherein corn, wheat are its seed and/or stalk.
The purity of bio-based ethylene glycol is between 99%-100%.
Polyethylene terephthalate by bio-based ethylene glycol by with the terephthalic acid direct esterification or and the dimethyl terephthalate (DMT) transesterify prepare.
The limiting viscosity of polyethylene terephthalate is 0.55～0.75dl/g.
Dibasic alcohol in the polyethylene terephthalate is important raw materials for production, and the PET that common every production is a ton just needs about 0.35 ton ethylene glycol, just relates to petroleum more than six tons and make one ton ethylene glycol.Among the present invention in the polyethylene terephthalate starting material of dibasic alcohol production derive from biomaterial.Biomaterial wherein is the stalk of corn, sugarcane, wheat or other farm crop.
Corn, wheat, sugarcane farm crop and other agricultural crop straws are a kind of renewable resourcess, airborne CO2 can be passed through photosynthesis, being converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. stores in farm crop fruit and stalk thereof, even also can produce CO2 after farm crop and agricultural crop straw are discarded, utilize farm crop and agricultural crop straw to produce polyester and can not increase CO2 gas in the environment newly, have good environmental-protection function with raw material for feedstock production.The present invention utilizes farm crop such as corn, wheat, sugarcane and agricultural crop straw to prepare polyethylene terephthalate through the glycol that biological fermentation and/or the chemical industry course of processing make.
The present invention uses the rich former group in Anhui bio-based product of ethylene oxide to prepare ethylene glycol.Bio-based oxyethane adopts the stalk fermentation of corn, sugarcane, wheat or other farm crop to prepare ethanol, hydrogenation preparing ethene, and oxygenation prepares and obtains again.What prepared by bio-based oxyethane is thick ethylene glycol, thick ethylene glycol concentrates the operational path that obtains ethylene glycol after adopting the process rectification and purification to isolate catalyzer, other two pure and mild unstable organism and ring-type organic impurity and water then, make bio-based ethylene glycol purity reach 99-100%, satisfy the production of polyester requirement, get rid of other glycol, unstable organism and the organic influence of ring-type.Other glycol, unstable organism and the organic existence of ring-type can have influence on the performance of polyester.
Most critical of the present invention is characterised in that adopting purity is that the fusing point of the polyethylene terephthalate that obtains of 99-100% bio-based ethylene glycol is 255-270 ℃.Organism-based raw material prepares polyester, owing in the bio-based raw polyol, contain other glycol, as 1,2-propylene glycol, 1, ammediol, butyleneglycol, and other organic substances, these other two pure and mild organic substances can influence the performance of polymerization time, polymerization velocity and final product when carrying out polymerization with acid, the fusing point of polyester slice is reduced, and the fusing point of the polyethylene terephthalate that general bio-based raw polyol prepares is littler about 10 ℃ with the fusing point of diol ester than the poly terephthalic acid that conventional oil base raw polyol prepares.And generally the bio-based raw polyol contains coloring matter, and this coloring matter has seriously influenced the tone of final polyester slice.The present invention uses the bio-based oxyethane of the rich former group in Anhui from preparing ethylene glycol, prepare bio-based ethylene glycol behind the bio-based oxyethane hydrogenation with the rich former group in Anhui, the concentrated purity that obtains bio-based ethylene glycol reached 99-100% after the process rectification and purification was isolated catalyzer, other two pure and mild unstable organism and ring-type organic impurity and water again.The terminal carboxyl(group) content that obtains polyester slice after bio-based ethylene glycol after the self-control and terephthalic acid or the dimethyl terephthalate (DMT) polymerization is 8--30eq/ton, the content of DEG is 0.3-1.5wt%, and the synthetic performance that obtains polyester slice of performance and conventional oil raw material does not have difference.
The present invention relates to by Esterification Stage by terephthalic acid and biological ethylene glycol, perhaps react by DMT and biological ethylene glycol by the transesterify stage, carry out polycondensation and polymkeric substance then and finish the stage, the performance that successfully makes the PET that is obtained by the performance of bio-based PET and conventional oil source feedstock production is than as broad as long.Adopt the ordinary method of existing preparation polyester: continuous processing, semicontinuous or interrupter method production, the polyethylene terephthalate viscosity for preparing is 0.55～0.75dl/g.
The polyester that the present invention obtains can use by various ordinary methods, can carry out modification with the compound use of inorganic materials, and as carrying out modification with various inorganic materials nanoparticles, spinning obtains various functional fibers then; The present invention can add other polymer manufacture block polymer in the process of preparation PET; Bio-based ethylene glycol among the present invention can mix with other petroleum base glycol or bio-based glycol with diacid reactant and prepare PBT, PPT, PTT or copolyesters; Polyester among the present invention can also use the polyester processing units of various routines that it is processed, and is applied in various fields such as plastics, film.The present invention meets the environmental protection needs.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Raw material sources
Bio-based ethylene glycol: 99.3% self-control.With the bio-based oxyethane of the rich former group in Anhui from preparing ethylene glycol, prepare bio-based ethylene glycol behind the bio-based oxyethane hydrogenation with the rich former group in Anhui, the concentrated purity that obtains bio-based ethylene glycol reached 99.3% after the process rectification and purification was isolated catalyzer, other two pure and mild unstable organism and ring-type organic impurity and water again.
Petroleum base ethylene glycol: 99.5% raises sub-petrochemical industry
Terephthalic acid: 99.8% raises sub-petrochemical industry
Dimethyl terephthalate (DMT): 99.8% Iranian Fiber Intermediate Products Co. produces polymerization-grade
Antimonous oxide: group of analytical pure Du Pont
Comparative Examples
Be aggregated on the 15Kg level PET polymerization production line and finish.12.97kg terephthalic acid and 5.57kg petroleum base ethylene glycol after the making beating, are infeeded esterifying kettle and carry out esterification in the making beating still, move into polycondensation vessel again and carry out polycondensation.Main polymerization technique is: 1) main additive: catalyzer ANTIMONY TRIOXIDE SB 203 99.8 PCT, 300ppm; Half TITANIUM DIOXIDE DELUSTRANT, 0.3% (pressing product quality per-cent); The antioxidant triphenyl phosphite, 20ppm; 2) esterification temperature: 250 ℃, esterification time: 3 hours 30 minutes; 3) condensation temperature: 280 ℃, the polycondensation time: 3 hours 10 minutes.
Embodiment 1
Be aggregated on the 15Kg level PET polymerization production line and finish.12.97kg terephthalic acid and 5.57kg bio-based ethylene glycol after the making beating, are infeeded esterifying kettle and carry out esterification in the making beating still, move into polycondensation vessel again and carry out polycondensation.Main polymerization technique is: 1) main additive: catalyzer ANTIMONY TRIOXIDE SB 203 99.8 PCT, 300ppm; Half TITANIUM DIOXIDE DELUSTRANT, 0.3% (pressing product quality per-cent); The antioxidant triphenyl phosphite, 20ppm; 2) esterification temperature: 250 ℃, esterification time: 3 hours 40 minutes; 3) condensation temperature: 280 ℃, the polycondensation time: 3 hours 20 minutes.
Embodiment 2
Be aggregated on the 15Kg level PET polymerization production line and finish.After 15.16kg dimethyl terephthalate (DMT) and the esterification of 9.2kg bio-based ethylene glycol, move into polycondensation vessel again and carry out polycondensation.Main polymerization technique is: 1) main additive: catalyzer ANTIMONY TRIOXIDE SB 203 99.8 PCT, 300ppm; Half TITANIUM DIOXIDE DELUSTRANT, 0.3% (pressing product quality per-cent); The antioxidant triphenyl phosphite, 20ppm; 2) esterification temperature: 235 ℃, esterification time: 3 hours 10 minutes; 3) condensation temperature: 280 ℃, the polycondensation time: 3 hours 20 minutes.
Table 1 bio-based PET and conventional PET performance index are relatively
| Viscosity | Fusing point Tm (℃) | DEG (％) | -COOH(％) | b | |
| Comparative Examples | 0.66 | 258 | 1.540 | 25.0 | 1.20 |
| Embodiment 1 | 0.65 | 258 | 1.541 | 22.6 | 1.21 |
| Embodiment 2 | 0.70 | 260 | 0.901 | 14.2 | 1.21 |
Evaluation method
Limiting viscosity (IV): adopt polyester national standard testing method: GB/T-14190-1993 tests.
Fusing point (Tm): constant temperature is 3 minutes after using differential scanning calorimeter (DSC) to be warmed up to 280 ℃ from 20 ℃ with 16 ℃ of per minutes, eliminates thermal history; Cool to 20 ℃ with 16 ℃ of per minutes again, constant temperature 3 minutes; Be warmed up to 280 ℃ with 16 ℃ of per minutes again, finish.The melt temperature that obtains in the intensification with the second time is a fusing point.
Carboxyl-content (COOH): adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N then
Glycol ether content (DEG): adopt gas chromatography determination.Solvent is added in the polyester heating polyester is decomposed, add the methyl alcohol postcooling, pulverize the back with ultrasonic wave and add terephthalic acid and neutralize, stir, cooling, filter the back and filter with quantitative paper, filtrate adds among the GC with microsyringe to be analyzed.
Tone b value: measure by GB GB/T14190-1993.
Claims (5)
1, a kind of biological poly ethylene glycol terephthalate is characterized in that: 1. the fusing point of biological poly ethylene glycol terephthalate is 255-270 ℃; 2. its raw material ethylene glycol is biological ethyl glycol, and promptly the carbon in the raw material glycol component is to derive from biomaterial.
2, biological poly ethylene glycol terephthalate according to claim 1 is characterized in that: described biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.
3, biological poly ethylene glycol terephthalate according to claim 1 and 2, it is characterized in that: the purity of bio-based ethylene glycol is between 99%-100%.
4, biological poly ethylene glycol terephthalate according to claim 1 and 2 is characterized in that: polyethylene terephthalate by bio-based ethylene glycol by with the terephthalic acid direct esterification or and the dimethyl terephthalate (DMT) transesterify prepare.
5, biological poly ethylene glycol terephthalate according to claim 1 and 2 is characterized in that: the limiting viscosity of polyethylene terephthalate is 0.55～0.75dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810018614A CN101525416A (en) | 2008-03-04 | 2008-03-04 | Biobased polyethylene terephthalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810018614A CN101525416A (en) | 2008-03-04 | 2008-03-04 | Biobased polyethylene terephthalate |
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| CN101525416A true CN101525416A (en) | 2009-09-09 |
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| CN200810018614A Pending CN101525416A (en) | 2008-03-04 | 2008-03-04 | Biobased polyethylene terephthalate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202012103846U1 (en) | 2012-10-08 | 2012-10-25 | Heimbach Gmbh & Co. Kg | The paper machine belt |
| EP2403894A4 (en) * | 2009-03-03 | 2012-11-07 | Coca Cola Co | Bio-based polyethylene terephthalate packaging and method of making thereof |
| CN103320081A (en) * | 2013-05-23 | 2013-09-25 | 济南大学 | High-molecular composite adhesive, and preparation method and application thereof |
| CN104774321A (en) * | 2015-04-24 | 2015-07-15 | 广东顺德顺炎新材料有限公司 | Bio-based polyethylene glycol terephthalate and preparation method thereof |
| JPWO2016186122A1 (en) * | 2015-05-20 | 2018-03-01 | 東洋紡株式会社 | Polyester resin |
| AU2018282377B2 (en) * | 2009-03-03 | 2021-03-04 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
| CN113518613A (en) * | 2019-02-27 | 2021-10-19 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN113717326A (en) * | 2021-09-24 | 2021-11-30 | 张家港市顾乐仕生活家居科技有限公司 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
-
2008
- 2008-03-04 CN CN200810018614A patent/CN101525416A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3878887A1 (en) * | 2009-03-03 | 2021-09-15 | The Coca-Cola Company | Method of making a bio-based polyethylene terephthalate |
| AU2018282377B2 (en) * | 2009-03-03 | 2021-03-04 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
| AU2021203660B2 (en) * | 2009-03-03 | 2023-04-20 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
| EP3130623A1 (en) * | 2009-03-03 | 2017-02-15 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
| EP2403894A4 (en) * | 2009-03-03 | 2012-11-07 | Coca Cola Co | Bio-based polyethylene terephthalate packaging and method of making thereof |
| EP2403894B1 (en) | 2009-03-03 | 2016-06-01 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
| EP2716813A1 (en) | 2012-10-08 | 2014-04-09 | Heimbach GmbH & Co. KG | Paper machine fabric |
| DE202012103846U1 (en) | 2012-10-08 | 2012-10-25 | Heimbach Gmbh & Co. Kg | The paper machine belt |
| CN103320081A (en) * | 2013-05-23 | 2013-09-25 | 济南大学 | High-molecular composite adhesive, and preparation method and application thereof |
| CN104774321A (en) * | 2015-04-24 | 2015-07-15 | 广东顺德顺炎新材料有限公司 | Bio-based polyethylene glycol terephthalate and preparation method thereof |
| JPWO2016186122A1 (en) * | 2015-05-20 | 2018-03-01 | 東洋紡株式会社 | Polyester resin |
| CN113518613A (en) * | 2019-02-27 | 2021-10-19 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN113518613B (en) * | 2019-02-27 | 2023-12-01 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN113717326A (en) * | 2021-09-24 | 2021-11-30 | 张家港市顾乐仕生活家居科技有限公司 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
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Application publication date: 20090909 |