CN104774321A - Bio-based polyethylene glycol terephthalate and preparation method thereof - Google Patents
Bio-based polyethylene glycol terephthalate and preparation method thereof Download PDFInfo
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- CN104774321A CN104774321A CN201510205782.7A CN201510205782A CN104774321A CN 104774321 A CN104774321 A CN 104774321A CN 201510205782 A CN201510205782 A CN 201510205782A CN 104774321 A CN104774321 A CN 104774321A
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Abstract
The invention discloses bio-based polyethylene glycol terephthalate and a preparation method thereof, and belongs to the technical field of high-molecular compounds and preparation of the high-molecular compounds. The bio-based polyethylene glycol terephthalate comprises, by weight, 25 parts to 35 parts of bio-based ethanediol, 65 parts to 75 parts of purified terephthalic acid, 0.1 part to 0.5 part of heat stabilizer, 0.1 part to 0.5 part of catalyst and 0.1 part to 0.5 part of antioxygen. The material performance of the prepared bio-based polyethylene glycol terephthalate is similar to that of polyethylene glycol terephthalate prepared through petroleum-based ethanediol. The bio-based polyethylene glycol terephthalate has important economic prospects and sustainable development prospects. Meanwhile, the invention opens up a new polyethylene glycol terephthalate synthetic route. The synthetic route is more environmentally friendly and lower in cost.
Description
Technical field
The invention belongs to macromolecular compound and preparing technical field thereof, especially relate to a kind of biobased polyethylene terephthalate and preparation method thereof.
Background technology
Polyethylene terephthalate vinegar (PET) is linear saturated thermoplastic polyester, is topmost kind in thermoplastic polyester, is commonly called as polyester resin.It is the polycondensate of terephthalic acid and ethylene glycol, is referred to as thermoplastic polyester together with PBT, or saturated polyester.PET molecular structure is regular, and Intermolecular Forces is comparatively strong, and molecular chain has kindliness, easy crystallization, has higher degree of crystallinity and orientation degree.
In recent years because PET has, physical strength, rigidity, hardness are high, sliding capability and abrasive wear resistance good, electric insulating quality is good, the characteristic that extraordinary creep resistance, low and stable coefficient of friction, excellent wear resistance etc. are excellent.Be widely used in the industries such as weaving, papermaking, food machinery, transport, harbour, medical treatment, colliery, chemical industry.Bearing, guide food processing machines head, piston, the tool of the food such as screw volume, component, the bearing of precision machinery, electrically insulating material etc., have a wide range of applications in national economy, national defense industry and new high-tech industry.
Along with the progressively construction of friendly environment society of China, the exploitation of petroleum resources reduces year by year.At present, the raw material of whole world production of polyester industry is all extract from petroleum products, and PET industry accounts for the output of more than 70% in whole chemical fibre industry, and limited petroleum resources seriously constrain the development of PET industry.Bio-based polyester mainly adopts the renewable agricultural wastes manufactures such as maize straw, aboundresources.Developing the bio-based polyester that can replace petroleum resources product, break away from the dependence of polyester to petroleum resources, is an important directions of development environment friendly PET industry.The preparation of bio-based ethylene glycol (BioEG) is by fermentation such as maize straws for polysaccharide, and obtained polyvalent alcohol, is obtained by polyvalent alcohol catalytic pyrolysis further.Different with petroleum base ethylene glycol, bio-based quality of glycol mark, only up to about 98%, is polymerized the purity 99.5% of required ethylene glycol lower than normal polyester.But other components in the bio-based ethylene glycol of different purity are the dibasic alcohol comprising propylene glycol, butyleneglycol, pentanediol etc., so bio-based ethylene glycol is called as multicomponent binary alcohol.This shows: in theory with the multicomponent binary alcohol that bio-based ethylene glycol is main component, can with PTA copolymerization.The utilization of Developing Biomass renewable resources, becomes trend gradually for the synthesis of industrial chemicals, produces polyester by reproducible biomass resource, has very important significance for saving petroleum resources, minimizing Carbon emission.This also provides a new approach for synthesis polyethylene terephthalate, and raw material sources of its synthesis is abundanter, cost is lower.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, provide the synthetic route of a new polyethylene terephthalate, namely provide a kind of biobased polyethylene terephthalate and preparation method thereof.Biobased polyethylene terephthalate environmental protection prepared by the present invention, cost are lower, it is the synthetic route of a Sustainable development, the bio-based ethylene glycol (BioEG) synthesizing preparation by techniques such as fermentations by the biomass such as corn cob, maize straw is utilized to be polymerized by polycondensation with smart poly terephthalic acid (PTA), to prepare a kind of biobased polyethylene terephthalate (PET) material, reach PET performance prepared by performance and conventional petroleum base ethylene glycol suitable.
For achieving the above object, present invention employs following technical proposals:
A kind of biobased polyethylene terephthalate, its raw materials by weight meter comprises following component:
Preferably, its raw materials by weight meter comprises following component:
Preferably, the mass percent of described bio-based ethylene glycol and pure terephthalic acid is 31:68.
Preferably, described catalyzer is one or more in nano silicon, titanium dioxide, antimony glycol, antimonous oxide.
Preferably, described thermo-stabilizer be in triphenyl phosphite, triphenylphosphate one or both.
Preferably, described oxidation inhibitor is phenolic antioxidant 1010 and phosphoric acid ester irgasfos 168.
Preferably, the weight ratio of described phenolic antioxidant 1010 and phosphoric acid ester irgasfos 168 is 1:2.
Present invention also offers the preparation method of described biobased polyethylene terephthalate, comprise the following steps:
(1) by pure terephthalic acid and the mixing of bio-based ethylene glycol, join polymeric kettle, then add catalyzer, stablizer, oxidation inhibitor carries out esterification;
(2) esterification vacuumizes after terminating and carries out polycondensation, namely obtains biobased polyethylene terephthalate after polycondensation terminates.
Preferably, in described step (1), the esterification temperature of esterification is 240-250 DEG C, and pressure is 0-0.3MPa, and esterification time is 3-4h.
Preferably, in described step (2), the temperature of polycondensation is 270-280 DEG C, and the polycondensation time is 5-6h.
Compared with prior art, the present invention has following beneficial effect:
1, can the pet material prepared of petroleum replacing ethyl glycol, performance is suitable, has important economic outlook and the prospect of Sustainable development.The bio-based ethylene glycol (BioEG) synthesizing preparation by techniques such as fermentations by the biomass such as corn cob, maize straw is utilized to be polymerized by polycondensation with smart poly terephthalic acid (PTA), prepare biobased polyethylene terephthalate (PET) material, reach PET performance prepared by performance and conventional petroleum base ethylene glycol suitable.
2, the synthetic route of a new polyethylene terephthalate is opened.The environmental protection more of this synthetic route, cost are lower, are the synthetic routes of a Sustainable development.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated, but the scope of protection of present invention is not limited to the scope that embodiment is expressed.
Embodiment 1
Prepare biobased polyethylene terephthalate, comprise the steps:
(1) get the raw materials ready by the formula 1 of table 1;
(2) add polymeric kettle after first being mixed by PTA and BioEG, add TiO
2, SiO
2and Sb
2o
3as catalyzer; Add triphenyl phosphite as stablizer, add antioxidant 1010 and antioxidant 168 carries out esterification as oxidation inhibitor, wherein the weight ratio of antioxidant 1010 and antioxidant is 1:2.Be 240 DEG C in temperature, pressure is 0.3MPa, and esterification time is carry out esterification under the condition of 4h.Esterification completes and vacuumizes polycondensation, carries out polycondensation temperature 270 DEG C, and the reaction times is time 5.5h; Biobased polyethylene terephthalate (PET) can be obtained after polycondensation completes.
Prepare petroleum base polyethylene terephthalate, comprise the steps:
(1) get the raw materials ready by the formula 2 of table 1;
(2) reactions steps and parameter are with preparing biobased polyethylene terephthalate, finally obtained petroleum base polyethylene terephthalate.
Polyethylene terephthalate formula prepared by table 1
Embodiment 2
Embodiment 1 to be filled a prescription the biobased polyethylene terephthalate of 1 preparation, and petroleum base polyethylene terephthalate prepared by formula 2 carries out test as shown in table 2, test result is also as shown in table 2:
The test result of table 2 polyethylene terephthalate
Above test result shows: biobased polyethylene terephthalate prepared by the present invention and same condition, all suitable in tensile strength, elongation at break, flexural strength, modulus in flexure, Izod notched impact strength, heat-drawn wire, density, intrinsic viscosity, these performances of fusing point with the petroleum base polyethylene terephthalate prepared under consumption, and some performance is even better than petroleum base polyethylene terephthalate.
And the lower and environmental protection more of its cost of biobased polyethylene terephthalate prepared by the present invention, it utilizes the bio-based ethylene glycol (BioEG) synthesizing preparation by techniques such as fermentations by the biomass such as corn cob, maize straw to be polymerized by polycondensation with smart poly terephthalic acid (PTA), prepares biobased polyethylene terephthalate (PET) material.
Therefore, biobased polyethylene terephthalate provided by the invention and preparation method thereof has important economic outlook, the prospect of concrete Sustainable development.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a biobased polyethylene terephthalate, is characterized in that, its raw materials by weight meter comprises following component:
2. a kind of biobased polyethylene terephthalate according to claim 1, is characterized in that, its raw materials by weight meter comprises following component:
3. a kind of biobased polyethylene terephthalate according to claim 2, is characterized in that, the mass percent of described bio-based ethylene glycol and pure terephthalic acid is 31:68.
4. a kind of biobased polyethylene terephthalate according to claim 2, is characterized in that, described catalyzer is one or more in nano silicon, titanium dioxide, antimony glycol, antimonous oxide.
5. a kind of biobased polyethylene terephthalate according to claim 2, is characterized in that, described thermo-stabilizer be in triphenyl phosphite, triphenylphosphate one or both.
6. a kind of biobased polyethylene terephthalate according to claim 2, is characterized in that, described oxidation inhibitor is phenolic antioxidant 1010 and phosphoric acid ester irgasfos 168.
7. a kind of biobased polyethylene terephthalate according to claim 6, is characterized in that, the weight ratio of described phenolic antioxidant 1010 and phosphoric acid ester irgasfos 168 is 1:2.
8. the preparation method of a kind of biobased polyethylene terephthalate according to claim 2, is characterized in that, comprise the following steps:
(1) by pure terephthalic acid and the mixing of bio-based ethylene glycol, join polymeric kettle, then add catalyzer, stablizer, oxidation inhibitor carries out esterification;
(2) esterification vacuumizes after terminating and carries out polycondensation, namely obtains biobased polyethylene terephthalate after polycondensation terminates.
9. the preparation method of a kind of biobased polyethylene terephthalate according to claim 8, is characterized in that, in described step (1), the esterification temperature of esterification is 240-250 DEG C, and pressure is 0-0.3MPa, and esterification time is 3-4h.
10. the preparation method of a kind of biobased polyethylene terephthalate according to claim 8, is characterized in that, in described step (2), the temperature of polycondensation is 270-280 DEG C, and the polycondensation time is 5-6h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762147A (en) * | 2017-11-09 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of polyethylene terephthalate composition and preparation method thereof |
| 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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| CN101525416A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Biobased polyethylene terephthalate |
| CN101525782A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Short fiber of polyethylene terephthalate and method for producing same |
| WO2013120989A2 (en) * | 2012-02-17 | 2013-08-22 | Uhde Inventa-Fischer Gmbh | Process for preparing a high molecular weight heteroaromatic polyester or copolyester |
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2015
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Patent Citations (3)
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| CN101525416A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Biobased polyethylene terephthalate |
| CN101525782A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Short fiber of polyethylene terephthalate and method for producing same |
| WO2013120989A2 (en) * | 2012-02-17 | 2013-08-22 | Uhde Inventa-Fischer Gmbh | Process for preparing a high molecular weight heteroaromatic polyester or copolyester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762147A (en) * | 2017-11-09 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of polyethylene terephthalate composition and preparation method thereof |
| 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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Address after: 5 road 528325 Guangdong city Foshan province wheat village Shunde District Xingtan town seven Kau Industrial Zone No. 2 Applicant after: GUANGDONG SHUNDE SHUNYAN NEW MATERIAL CO., LTD. Address before: 5 road 528325 Guangdong city Foshan province wheat village Shunde District Xingtan town seven Kau Industrial Zone No. 2 Applicant before: Guangdong Shunde New Materials Co., Ltd. |
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Inventor after: Zhang Zhaopeng Inventor after: Xiao Xiongwei Inventor after: Yao Daai Inventor after: Yang Zijiang Inventor after: Yang Rui Inventor after: Lin Yuankai Inventor after: Fu Hongmeng Inventor after: Lei Jian Inventor before: Yang Rui Inventor before: Yao Daai Inventor before: Zhang Zhaopeng Inventor before: Lin Yuankai Inventor before: Fu Hongmeng Inventor before: Zheng Chongshen |
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Application publication date: 20150715 |