CN101525415B - Polyester for bottle and method for preparing same - Google Patents
Polyester for bottle and method for preparing same Download PDFInfo
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- CN101525415B CN101525415B CN200810018612A CN200810018612A CN101525415B CN 101525415 B CN101525415 B CN 101525415B CN 200810018612 A CN200810018612 A CN 200810018612A CN 200810018612 A CN200810018612 A CN 200810018612A CN 101525415 B CN101525415 B CN 101525415B
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- polyester
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- terepthaloyl moietie
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Abstract
The invention discloses a polyester for a bottle and a method for preparing the same. The method comprises the following steps that: the polyester with low viscosity is sliced, dried and pre-crystallized, and is further subjected to solid phase coincidence treatment to obtain a high-viscosity polyester slice for the bottle. The carbon element in the ethylene glycol of the raw materials used for preparing the low-viscosity polyester slice is sourced from biological materials. The high-viscosity polyester slice prepared by the method has good IV value, COOH content, DEG content and color tone, and can be used for preparing various polyester bottles.
Description
Technical field:
The present invention relates to a kind of polyester for bottle and preparation method thereof.
Background technology:
In recent years, along with going from bad to worse of environment for human survival, People more and more is paid close attention to development environment friendly material and is used 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 the direct threats human existence.How substituting and reduce and use oil as starting material, is that people face one of research problem.
Polyethylene terephthalate (PET) product also is extended to fields such as all kinds of containers, wrapping material, film, film, engineering plastics except the application of fiber art.Because producing the raw material of PET all is the processed goods that derives from oil.How using non-petroleum exploitation PET product also is an important research project.
People use reproducible Biological resources; Various novel polyester have been developed; For example E.I.Du Pont Company through biology and chemical process, prepares 1 through corn is fermented; 3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not PTT (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 POLYACTIC ACID (PLA) polymkeric substance.
Glycol is that terepthaloyl moietie is the important source material of synthetic PET, and the weight ratio in PET is about 40%, and industry is at present gone up oxyethane direct hydration method or the ethene synthesis methods of adopting more and produced.Production stage is loaded down with trivial details, and the cost height has caused the price of terepthaloyl moietie high always, and consumes the great deal of raw materials and the energy, generates a lot of by products.Divalent alcohol is by biomaterial production among the present invention, is that carbon source in the biomaterial is transferred in the terepthaloyl moietie.
Farm crop are a kind of renewable resourcess, can be with airborne CO
2Being converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. through photosynthesis stores in farm crop fruit and stalk thereof.
Polyethylene terephthalate (PET) replaces glasswork gradually aspect packaging vessel, in the technology of preparation polyester for bottle, the method that generally adopts solid phase to overlap prepares full-bodied PET Resin/Poyester Chips Bottle Grade, to satisfy the requirement of pet bottle bottle producing process.
Summary of the invention:
The object of the present invention is to provide the carbon composition in a kind of raw material glycol component to derive from polyester for bottle of biomaterial and preparation method thereof.
Technical solution of the present invention is:
A kind of polyester for bottle and preparation method thereof is characterized in that: after low-viscosity polyester chip drying, preparatory crystallization, further carry out solid phase and overlap processing, make the HV polyester for bottle; Low-viscosity polyester section preparation raw material terepthaloyl moietie is that wherein carbon is the terepthaloyl moietie that derives from biomaterial.
Said biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.Wherein said corn, wheat are its seed and/or stalk.Terepthaloyl moietie is that biomaterial makes through the biological fermentation and/or the chemical industry course of processing.Glycol content is 95%～99.9% in the raw material terepthaloyl moietie, and biological ethylene glycol transmitance in the wavelength region of 190～350nm is more than 50%.Also contain carbon in the polyethylene terephthalate goods and derive from the diprotic acid of petroleum and the copolymer composition of divalent alcohol.The limiting viscosity of polyethylene terephthalate polymer is 0.55～0.75.
Biomaterial of the present invention is the stalk of corn, sugarcane, wheat or farm crop.Obtain terepthaloyl moietie through biology and/or chemical process.For example corn is through the bioprocess separating starch; Through processing the sugar that obtains 5 carbon and 6 carbon, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalysts, after the purifies and separates general procedure; Just can obtain raw material ethylene glycol component of the present invention; This terepthaloyl moietie carries out filtration treatment through heating with activated carbon, just obtain of the present invention in 190～350nm wavelength region transmitance be the biological ethylene glycol more than 50%.
Can contain other diol components in the terepthaloyl moietie raw material that uses in the present invention, for example have 1,2-Ucar 35,1,2-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol and 1, other diol component of 2-pentanediol.The purity of the terepthaloyl moietie that uses among the present invention is 95%～99.9%, and biological ethylene glycol transmitance in the wavelength region of 190～350nm is more than 50%, and the carbon of other compositions also is to derive from biomaterial.
Polyethylene terephthalate of the present invention can use the polymerization of still formula, the semi-continuous polymerzation of discontinuous, the method for successive polymerization to produce.Comprise that use biological ethylene glycol melt phase polycondensation makes the low-viscosity polyester section and process for solid state polycondensation makes polyester slice with high viscosity.The low-viscosity polyester section is meant that viscosity is 0.55～0.75 PET Resin/Poyester Chips Bottle Grade, and polyester slice with high viscosity is meant that viscosity is 0.8～1.2 PET Resin/Poyester Chips Bottle Grade.The preparation method of polyethylene terephthalate carries out esterification, polycondensation according to a certain percentage with terephthalic acid and terepthaloyl moietie, obtains the low-viscosity polyester section.
With carrying out solid state polymerization after the low-viscosity polyester chip drying 12～24.Vacuum tightness 10～1000Pa that solid phase overlaps, 120～230 ℃ of polymerization temperatures, polymerization time 8～24 hours obtains polyester slice with high viscosity.With polyester slice with high viscosity 90～120 ℃ of dryings of temperature 12～24 hours; Tc is 120～180 ℃ in advance, 24～40 hours time, then polyester is processed bottle base by the injection moulding machine injection moulding; Heating bottle blank; It is stretch blow-molded then bottle base to be put into the mold heat of stretch blow machine, and cooling, the demoulding make pet bottle then.The percent crystallinity of polyester for bottle section is 30%～50%, and isothermal crystal speed is less than 6 μ m/min.Acetaldehyde≤the 1.5ppm of polyester for bottle section, dust content≤100ppm.
Carbon composition during low-viscosity polyester is cut into slices among the present invention in the glycol component derives from biomaterial but not petroleum, thereby significantly reduces the CO that outwards discharges owing to smelt oil
2Amount.
The polyester slice with high viscosity that the present invention obtains can be processed the pet bottle of various different purposes through the pet bottle moulding process.
Below in conjunction with embodiment the present invention is described further.
Embodiment:
Biogenetic derivation terepthaloyl moietie: great achievement group in Changchun produces, and the carbon source is corn, purity: 97%.Filtration treatment is carried out with gac in above-mentioned terepthaloyl moietie heating back, obtain transmitance at the 250nm wavelength and be 65%, the transmitance of 300nm wavelength is 90% terepthaloyl moietie.
Terephthalic acid: sub-petrochemical iy produced, polymerization-grade are raised by China.
Oil source terepthaloyl moietie: raise sub-petro-chemical corporation and produce, the carbon source is oil, purity: more than 99%.
Embodiment 1
Melt phase polycondensation: terephthalic acid (TPA) and biogenetic derivation terepthaloyl moietie (EG) are prepared into the TPA/EG slurry according to mol ratio at 1: 1.15, carry out esterification, collect water byproduct; When reaching 95%, esterification yield finishes esterification when above.Resulting esterification reaction product is divided a word with a hyphen at the end of a line in the polycondensation vessel, add Antimony Trioxide: 99.5Min 300ppm and phosphoric acid 80ppm (wherein addition is the addition with respect to weight polyester), under atmospheric pressure warp was decompressed to about 300Pa in one hour; Temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, the temperature in the reaction kettle was 290 ℃; Resulting pressure is about 200Pa; The viscosity of gained polyester is 0.550, the polymkeric substance that spues, pelletizing.
Dry, crystallization in advance: with the resulting polymkeric substance of melt phase polycondensation under 100 ℃ condition dry 16 hours, crystallization 30 hours in advance under the condition of 130 ℃ of temperature.
Solid phase coincidence method: the resulting polymkeric substance of preparatory crystallization solid phase under 220 ℃ condition is overlapped, overlap reaction 8 hours, vacuum tightness 200Pa; Make viscosity and be 0.76 section, percent crystallinity 35%, crystallization rate 5.8 μ m/min; Acetaldehyde 1.5ppm, dust content 96ppm.
A system bottle process: solid phase overlaps resulting polyester and processes bottle base by the injection moulding machine injection moulding, heating bottle blank, and it is stretch blow-molded then bottle base to be put into the mold heat of stretch blow machine, and cooling, the demoulding make pet bottle then.
The preparation technology of embodiment 2～embodiment 3 is as embodiment 1
Comparative example
The raw material biological ethylene glycol is replaced by oil source terepthaloyl moietie, and preparation technology is as embodiment 1
Evaluation method:
Limiting viscosity (IV) is (dL/g):
With 0.5 gram polyester/milliliter phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, in 25 ℃ times mensuration its limiting viscosities (IV).
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 Pottasium Hydroxide of 0.05N then.
Tone b value:
Measure by GB GB/T 14190-1993.
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 UW and add terephthalic acid and neutralize, stir, cooling, filter the back and filter with quantitative paper, filtrating adds among the GC with microsyringe to be analyzed.
Percent crystallinity:
Use dsc (DSC) to measure crystallinity of polymer,
Crystallinity Xc=(Δ H
m/ Δ H
0m) * 100%,
Δ H in the formula
mThe melting enthalpy of expression polymer sample,
Δ H
0mMelting enthalpy during the complete crystallization of expression polymer sample
Crystallization rate:
Adopt optics depolarization method to measure the crystallization rate of polymkeric substance, the depolarization light intensity 0, when t and crystallization are accomplished is I
0, I
tAnd I
∞, then with (I
∞-I
t)/(I
∞-I
0) mapping can obtain the isothermal crystal curve to crystallization time, adopts crystallization to accomplish half the time t
1/2Inverse as the crystallization velocity of polymkeric substance.The DSC test curve of Tc and melt temperature set basis polymkeric substance is set
Acetaldehyde, dust content:
According to GB GB/T 17931-2003.
Claims (4)
1. a polyester for bottle is characterized in that: after low-viscosity polyester chip drying, preparatory crystallization, further carry out the polyester slice with high viscosity that makes after solid state polymerization is handled; Said low-viscosity polyester section; Its preparation raw material terepthaloyl moietie is that wherein carbon is the terepthaloyl moietie that derives from biomaterial; And be with the biological ethylene glycol behind the activated carbon filtration through the heating back; Glycol content is 95%～99.9% in the raw material terepthaloyl moietie, and biological ethylene glycol transmitance in the wavelength region of 190～350nm is more than 50%; The percent crystallinity of this polyester for bottle section is 35%～50%, and isothermal crystal speed is less than 6 μ m/min; Said low-viscosity polyester section is meant that limiting viscosity is the PET Resin/Poyester Chips Bottle Grade of 0.55～0.75dL/g, and polyester slice with high viscosity is meant that limiting viscosity is the PET Resin/Poyester Chips Bottle Grade of 0.8～1.2dL/g.
2. polyester for bottle according to claim 1 is characterized in that: said biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.
3. polyester for bottle according to claim 1 and 2 is characterized in that: the acetaldehyde≤1.5ppm of polyester for bottle section, dust content≤100ppm.
4. the preparation method of a polyester for bottle as claimed in claim 1 is characterized in that: after low-viscosity polyester chip drying, preparatory crystallization, further carry out making polyester slice with high viscosity after solid state polymerization is handled; Said low-viscosity polyester section; Its preparation raw material terepthaloyl moietie is that wherein carbon is the terepthaloyl moietie that derives from biomaterial; And be with the biological ethylene glycol behind the activated carbon filtration through the heating back; Glycol content is 95%～99.9% in the raw material terepthaloyl moietie, and biological ethylene glycol transmitance in the wavelength region of 190～350nm is more than 50%; Vacuum tightness 10～the 1000Pa of solid state polymerization wherein, 120～230 ℃ of polymerization temperatures, polymerization time 8～24 hours, 90～120 ℃ of drying temperatures, 12～24 hours time; Tc is 120～180 ℃ in advance, 24～40 hours time; Said low-viscosity polyester section is meant that limiting viscosity is the PET Resin/Poyester Chips Bottle Grade of 0.55～0.75dL/g, and polyester slice with high viscosity is meant that limiting viscosity is the PET Resin/Poyester Chips Bottle Grade of 0.8～1.2dL/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810018612A CN101525415B (en) | 2008-03-04 | 2008-03-04 | Polyester for bottle and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810018612A CN101525415B (en) | 2008-03-04 | 2008-03-04 | Polyester for bottle and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101525415A CN101525415A (en) | 2009-09-09 |
| CN101525415B true CN101525415B (en) | 2012-09-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810018612A Expired - Fee Related CN101525415B (en) | 2008-03-04 | 2008-03-04 | Polyester for bottle and method for preparing same |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254859A (en) * | 2009-03-03 | 2016-01-20 | 可口可乐公司 | Bio-based polyethylene terephthalate packaging and method of making thereof |
| CN103772671A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Polymerization method of polyester resin |
| CN103772684B (en) * | 2012-10-25 | 2016-05-18 | 中国石油化工股份有限公司 | The production method of the polyester of titanium catalysis |
| ITTO20130711A1 (en) * | 2013-09-02 | 2015-03-03 | Biochemtex Spa | COMPOSITIONS OF BIODERIVATED ETHYLENE GLYCOL FOR POLYESTER BOTTLES |
| CN104558554B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | The preparation method of polyester resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176264A (en) * | 1996-09-12 | 1998-03-18 | 三井石油化学工业株式会社 | Preparation method of polyethylene terephthalate |
| US5864005A (en) * | 1996-10-07 | 1999-01-26 | Skc, Limited | Process for the preparation of copolyester resin having low acetaldehyde content |
| CN1931895A (en) * | 2006-10-12 | 2007-03-21 | 东华大学 | Solid phase polymerization process of PET/PTT copolyester |
-
2008
- 2008-03-04 CN CN200810018612A patent/CN101525415B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176264A (en) * | 1996-09-12 | 1998-03-18 | 三井石油化学工业株式会社 | Preparation method of polyethylene terephthalate |
| US5864005A (en) * | 1996-10-07 | 1999-01-26 | Skc, Limited | Process for the preparation of copolyester resin having low acetaldehyde content |
| CN1931895A (en) * | 2006-10-12 | 2007-03-21 | 东华大学 | Solid phase polymerization process of PET/PTT copolyester |
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| CN101525415A (en) | 2009-09-09 |
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Effective date of registration: 20160612 Address after: Japan Tokyo central Nihonbashi Muromachi 2-1-1 Patentee after: Toray Industries, Inc. Address before: 226009 Nantong Province Economic and Technological Development Zone, the New South Road, No. 58, No. Patentee before: Toray Fiber Research Institute (China) Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20180304 |