CN100572417C - The preparation method of modified copolyester for non-fiber - Google Patents
The preparation method of modified copolyester for non-fiber Download PDFInfo
- Publication number
- CN100572417C CN100572417C CNB2005101278053A CN200510127805A CN100572417C CN 100572417 C CN100572417 C CN 100572417C CN B2005101278053 A CNB2005101278053 A CN B2005101278053A CN 200510127805 A CN200510127805 A CN 200510127805A CN 100572417 C CN100572417 C CN 100572417C
- Authority
- CN
- China
- Prior art keywords
- modified copolyester
- ethylene glycol
- compound
- preparation
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the modified copolyester for non-fiber field, particularly the non-fiber of the 1,4 cyclohexane dimethanol modification polyethylene terephthalate method of vibrin.The present invention is by common big bright PET chips is carried out alcoholysis, obtain the ethylene glycol terephthalate oligopolymer, with this oligopolymer is mother liquor, under normal pressure, make PTA and mix dibasic alcohol (EG+CHDM) and carry out esterification and polycondensation, prepared intrinsic viscosity at 0.65-0.85dl/g and have the modified copolyester product that use in the engineering plastics field that is applicable to of good transparency.This new operational path not only makes the esterification smooth operation, is easy to control, and side reaction is few, and makes the limiting viscosity of the finished product modified copolyester section and the requirement that the transparency all can satisfy the polyester transparent board materials production.
Description
Technical field
The invention belongs to the modified copolyester for non-fiber field, particularly the non-fiber of the 1,4 cyclohexane dimethanol modification polyethylene terephthalate method of vibrin.
Background technology
In the engineering plastics field, low-crystallinity or amorphism polyethylene terephthalate resin have been used to make plastic prods such as sheet material, sheet material and film.Polyethylene terephthalate belongs to the hemicrystalline superpolymer, under common processing conditions, can make product produce certain degree of crystallinity, and this point is very disadvantageous for plastics such as preparation polyester transparent sheet materials.Therefore, adopting the 3rd monomer to carry out modification by copolymerization, thereby the macromolecular regularity of polyethylene terephthalate is damaged, prepare the modified copolyester of noncrystalline or low-crystallinity, is an important channel that obtains polyester transparent sheet material.
U.S. Pat P5385773 (Eastman Chemical Company) discloses by dimethyl terephthalate (DMT) (DMT), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) is a reaction monomers, the synthetic method for preparing the 1,4 cyclohexane dimethanol modified copolyester.In preparation process, adopt zinc acetate, manganese acetate, titanium isopropylate and germanium oxide as catalyst for reaction, triethyl phosphate is as the stablizer of reaction, the conjugated polyester resin that has obtained having the better transparency through the rhythmic reaction process of transesterify and polycondensation.
Chinese patent CN1440993A (Eastman Chemical Company) has reported by the pure terephthalic acid (PTA), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) is a basic raw material, the reinforced mol ratio 1.7: 1～6.0: 1 of mixing dibasic alcohol (EG+CHDM) and diprotic acid (TPA) by control, at first under 240～280 ℃ and 0.2～0.65MPa condition, carry out esterification and form the esterification products that mixes dibasic alcohol and diprotic acid, and then add polycondensation catalyst and toning agent, under 260～290 ℃ and reduced pressure, form high-molecular weight modified copolyester product through step-reaction polymerization.
Summary of the invention
A purpose of the present invention provides a kind of esterification smooth operation, is easy to control, and side reaction is few, and the limiting viscosity of the finished product modified copolyester section and the transparent preparation method that all can satisfy the modified copolyester for non-fiber of polyester transparent board materials production requirement.
Another object of the present invention provides a kind of PTA method 1,4 cyclohexane dimethanol modification polyethylene terephthalate under normal pressure and prepares the method for non-fiber with vibrin.
The invention provides the industrialized preparing process that a kind of preparation has di-carboxylic acid component and diol component modified copolyester.It is that the common big bright PET chips of employing is a raw material, with its alcoholysis after product is mother liquor, in reactor, add terephthalic acid (PTA) then and mix dibasic alcohol (EG+CHDM) and carry out normal pressure esterification, obtain containing the intermediate product of ethylene glycol terephthalate oligopolymer and terephthalic acid mixing binary alcohol esters, require the copolyesters product by what catalyst type is selected and the adjustment of optimal addn, finally prepared to satisfy clear sheet production.Described mixing diol component contains 10～95% moles ethylene glycol and 5～90% moles 1,4 cyclohexane dimethanol, and wherein 1,4 cyclohexane dimethanol can be cis or trans isomer, or two kinds of mixture of isomers.
The preparation method of modified copolyester for non-fiber of the present invention may further comprise the steps:
(1). preparation ethylene glycol terephthalate oligopolymer
Directly join common big bright PET chips and ethylene glycol in the reaction kettle of the esterification, wherein the structural unit of common big bright PET chips (molar mass is 192) is 1～4: 1 with the mol ratio of ethylene glycol, be warming up to 230～260 ℃ and constant temperature 1～3 hour under normal pressure, the alcoholysis product that obtains is the ethylene glycol terephthalate oligopolymer of the polymerization degree 4～5;
(2). esterification
With terephthalic acid with mix the ratio of dibasic alcohol and directly add or be prepared into and join behind the slurry in the ethylene glycol terephthalate oligopolymer that step (1) obtains with mol ratio 1: 1.05～2.2, under condition of normal pressure, carry out esterification, the mixed diol ester of generation terephthalic acid or its oligopolymer in 230～265 ℃;
(3). polycondensation
The terephthalic acid that step (2) is obtained mixes in diol ester or its oligopolymer importing polycondensation vessel, in temperature is more than 250 ℃ the time, make reacting kettle inner pressure reduce to 10～150Pa through constantly reducing pressure in 40～60 minutes, constantly distillate by product ethylene glycol and 1 in this process, the 4-cyclohexanedimethanol, react whole temperature control at 280～290 ℃, at last polymer melt is carried out the Cast Strip pelletizing, obtain limiting viscosity in 0.65～0.85dl/g and the good modified copolyester section of form and aspect;
Can add the mixture catalyzer of zn cpds, germanium compound, titanium compound and cobalt compound toning agent in esterification or polycondensation stage; The organic compound stablizer that can add phosphorus in the polycondensation stage;
Wherein mix diol component and contain 10～95% moles ethylene glycol and 5～90% moles 1,4 cyclohexane dimethanol, wherein 1,4 cyclohexane dimethanol can be cis or trans isomer, or two kinds of mixture of isomers.
The present invention can adopt intermittently or continuation method is produced copolyesters, and continuous processing production can be derived the esterifying liquid continuously feeding by part and be realized.
The addition of described zn cpds is to be 60～160ppm with the content of zinc in the modified copolyester gross weight, and being preferably 65～120ppm is benchmark.
The addition of described titanium compound is to be 3～80ppm with the content of titanium in the modified copolyester gross weight, and being preferably 10～60ppm is benchmark.
The addition of described germanium compound is to be 80～180ppm with the content of germanium in the modified copolyester gross weight, and being preferably 100～150ppm is benchmark.
The addition of described cobalt compound is to be 10～80ppm with the content of cobalt in the modified copolyester gross weight, and being preferably 20～60ppm is benchmark.
The addition of described phosphorus compound is to be 10～70ppm with the content of phosphorus in the modified copolyester gross weight, and being preferably 20～60ppm is benchmark.
Described zn cpds is selected from a kind of in zinc acetate, zinc nitrate, the zinc lactate etc.
Described germanium compound is a germanium oxide.
Described titanium compound is selected from a kind of in organic titanate titanium ethylene glycolate, tetrabutyl titanate, the titanium isopropylate etc.
Described cobalt compound is selected from a kind of in Cobaltous diacetate tetrahydrate, cobaltous phosphate, the Xiao Suangu etc.
The organic compound of described phosphorus is selected from a kind of in trialkylphosphate, Triphenyl phosphate or the phosphoric acid etc.
The present invention is by common big bright PET chips being carried out alcoholysis, obtaining the ethylene glycol terephthalate oligopolymer, is mother liquor with this oligopolymer, makes PTA and mix dibasic alcohol (EG+CHDM) and carry out esterification and polycondensation under normal pressure.This new operational path not only makes the esterification smooth operation, is easy to control, and side reaction is few, and makes the limiting viscosity of the finished product modified copolyester section and the requirement that the transparency all can satisfy the polyester transparent board materials production.
The resulting modified copolyester product of the present invention is carried out performance test by GB/T14189-93, and the gained result is as follows: intrinsic viscosity 0.65-0.85dl/g, the b value is between-2～3.The modified copolyester section that the present invention obtains can be used for the production of transparent polyester sheet material, sheet material; Or carry out blend with polycarbonate (PC), partly or entirely substitute PC, thereby the cost of this series products is reduced significantly.
Main innovate point of the present invention is to use the resulting oligopolymer of alcoholysis process of common big glossy polyester to be mother liquor, under normal pressure, realized the esterification process of copolyesters, thereby solved the problem that esterification can only be finished in the present PTA route in autoclave pressure, this makes that not only the esterification operating process is easy to realize, has also reduced the generation of esterification by product and has improved quality product simultaneously.By this new operational path, the present invention has realized the suitability for industrialized production of above-mentioned modified copolyester product.
Embodiment
The following examples are to set forth rather than limit category of the present invention.Except as otherwise noted, all umber and percentage ratio all are that weight with modified copolyester is benchmark among the embodiment.
Embodiment 1
At a 20m that nitrogen inlet, condensation product outlet and agitator are housed
3Add 2 tons of common big bright PET chips and 300L ethylene glycol in the stainless steel esterifier, rise to 250 ℃ gradually from room temperature, normal pressure reaction was down finished alcoholysis process in 12 hours.Add 6 tons of pure terephthalic acids (PTA) to it then, 1.79 ton ethylene glycol (EG) and 2.68 ton 1, the slurry of 4-cyclohexanedimethanol (CHDM), temperature rise to 250 ℃ in the reactor under the normal pressure, when the amount that distillates water byproduct in the question response still reaches theoretical value, esterifying liquid is imported one the condensation product outlet is housed, in the polycondensation vessel of vacuum system and agitator, add the zinc acetate that is equivalent to 80ppm zinc, the germanium dioxide of the Cobaltous diacetate of 42ppm cobalt and 115ppm germanium, the trimethyl phosphite 99 of the tetrabutyl titanate of 20ppm titanium and 30ppm phosphorus, by vacuumizing, make the pressure in the polycondensation vessel in 60 minutes, be reduced to 60Pa, reaction is 130 minutes under this pressure, react whole temperature control in 280～290 ℃ of scopes, make reactive system return to normal pressure with nitrogen, polymer melt obtains water white copolyesters product after the pelletizing of Cast Strip.Test result shows: the intrinsic viscosity of modified copolyester [η] is 0.72dl/g, and form and aspect b value is 0.99.
Embodiment 2
At a 20m that nitrogen inlet, condensation product outlet and agitator are housed
3Add 2 tons of common big bright PET chips and 350L ethylene glycol in the stainless steel esterifier, rise to 250 ℃ gradually from room temperature, normal pressure reaction was down finished alcoholysis process in 10 hours.Add 6 tons of pure terephthalic acids (PTA) to it then, 1.79 ton ethylene glycol (EG) and 2.68 ton 1, the slurry of 4-cyclohexanedimethanol (CHDM), temperature rise to 250 ℃ in the reactor under the normal pressure, when the amount that distillates water byproduct in the question response still reaches theoretical value, esterifying liquid is imported one the condensation product outlet is housed, in the polycondensation vessel of vacuum system and agitator, add the zinc acetate that is equivalent to 70ppm zinc, the germanium dioxide of the Cobaltous diacetate of 35ppm cobalt and 100ppm germanium, the trimethyl phosphite 99 of the tetrabutyl titanate of 15ppm titanium and 30ppm phosphorus, by vacuumizing, make the pressure in the polycondensation vessel in 60 minutes, be reduced to 60Pa, reaction is 150 minutes under this pressure, react whole temperature control in 280～290 ℃ of scopes, make reactive system return to normal pressure with nitrogen, polymer melt obtains water white product after the pelletizing of Cast Strip.Test result shows: the intrinsic viscosity of modified copolyester [η] is 0.69dl/g, and form and aspect b value is-0.13.
Embodiment 3
At a 20m that nitrogen inlet, condensation product outlet and agitator are housed
3Add 2 tons of common big bright PET chips and 450L ethylene glycol in the stainless steel esterifier, rise to 250 ℃ gradually from room temperature and rise, normal pressure reaction was down finished alcoholysis process in 9 hours.Add 6 tons of pure terephthalic acids (PTA) to it then, 2.24 ton ethylene glycol (EG) and 1.34 ton 1, the slurry of 4-cyclohexanedimethanol (CHDM), add the zinc acetate that is equivalent to 70ppm zinc, the germanium dioxide of the Cobaltous diacetate of 35ppm cobalt and 100ppm germanium, temperature rise to 250 ℃ in the reactor under the normal pressure, when the amount that distillates water byproduct in the question response still reaches theoretical value, esterifying liquid is imported one the condensation product outlet is housed, in the polycondensation vessel of vacuum system and agitator, add and be equivalent to the tetrabutyl titanate of 15ppm titanium and the trimethyl phosphite 99 of 30ppm phosphorus, by vacuumizing, make the pressure in the polycondensation vessel in 40 minutes, be reduced to 60Pa, reaction is 160 minutes under this pressure, react whole temperature control in 280～290 ℃ of scopes, make reactive system return to normal pressure with nitrogen, polymer melt obtains water white product after the pelletizing of Cast Strip.Test result shows: the intrinsic viscosity of modified copolyester [η] is 0.70dl/g, and form and aspect b value is 1.67.
Embodiment 4
At a 20m that nitrogen inlet, condensation product outlet and agitator are housed
3Add 2 tons of common big bright PET chips and 500L ethylene glycol in the stainless steel esterifier, be raised to 250 ℃ from room temperature, normal pressure reaction was down finished alcoholysis process in 8 hours.Add 6 tons of pure terephthalic acids (PTA) to it then, 2.24 ton ethylene glycol (EG) and 1.34 ton 1, the slurry of 4-cyclohexanedimethanol (CHDM), add the zinc nitrate that is equivalent to 70ppm zinc, the titanium ethylene glycolate of 10ppm titanium, the germanium dioxide of the Xiao Suangu of 35ppm cobalt and 100ppm germanium, temperature rise to 250 ℃ in the reactor under the normal pressure, when the amount that distillates water byproduct in the question response still reaches theoretical value, esterifying liquid is imported one the condensation product outlet is housed, in the polycondensation vessel of vacuum system and agitator, add the trimethyl phosphite 99 that is equivalent to 30ppm phosphorus, vacuumize continuously, make the pressure in the polycondensation vessel in 60 minutes, be reduced to 60Pa, reaction is 95 minutes under this pressure, react whole temperature control in 280-290 ℃ of scope, make reactive system return to normal pressure with nitrogen, polymer melt obtains water white product after the pelletizing of Cast Strip.Test result shows: the intrinsic viscosity of modified copolyester [η] is 0.77dl/g, and form and aspect b value is 2.24.
Claims (6)
1. the preparation method of a modified copolyester for non-fiber is characterized in that:
This method may further comprise the steps:
(1). preparation ethylene glycol terephthalate oligopolymer
Directly join common big bright PET chips and ethylene glycol in the reaction kettle of the esterification, wherein the mol ratio of the structural unit of common big bright PET chips and ethylene glycol is 1～4: 1, under normal pressure, be warming up to 230～260 ℃ and constant temperature, the alcoholysis product that obtains is the ethylene glycol terephthalate oligopolymer of the polymerization degree 4～5, and the structural unit molar mass of common big bright PET chips is 192;
(2). esterification
With terephthalic acid with mix the ratio of dibasic alcohol and directly add or be prepared into and join behind the slurry in the ethylene glycol terephthalate oligopolymer that step (1) obtains with mol ratio 1: 1.05～2.2, under condition of normal pressure, carry out esterification, the mixed diol ester of generation terephthalic acid or its oligopolymer in 230～265 ℃;
(3). polycondensation
The terephthalic acid that step (2) is obtained mixes in diol ester or its oligopolymer importing polycondensation vessel, in temperature is more than 250 ℃ the time, make reacting kettle inner pressure reduce to 10～150Pa through constantly reducing pressure in 40～60 minutes, constantly distillate by product ethylene glycol and 1 in this process, the 4-cyclohexanedimethanol, react whole temperature control at 280～290 ℃, at last polymer melt is carried out the Cast Strip pelletizing, obtain the modified copolyester section;
Add the mixture catalyzer of zn cpds, germanium compound, titanium compound and cobalt compound toning agent in esterification or polycondensation stage; The organic compound stablizer that adds phosphorus in the polycondensation stage;
Wherein mix diol component and contain 10～95% moles ethylene glycol and 5～90% moles 1,4 cyclohexane dimethanol, wherein 1,4 cyclohexane dimethanol is cis or trans isomer, or two kinds of mixture of isomers;
The addition of described zn cpds is to be that 60～160ppm is a benchmark with the content of zinc in the modified copolyester gross weight;
The addition of described titanium compound is to be that 3～80ppm is a benchmark with the content of titanium in the modified copolyester gross weight;
The addition of described germanium compound is to be that 80～180ppm is a benchmark with the content of germanium in the modified copolyester gross weight;
The addition of described cobalt compound is to be that 10～80ppm is a benchmark with the content of cobalt in the modified copolyester gross weight;
The addition of the organic compound of described phosphorus is to be that 10～70ppm is a benchmark with the content of phosphorus in the modified copolyester gross weight.
2. the preparation method of modified copolyester for non-fiber according to claim 1 is characterized in that: described zn cpds is a kind of in zinc acetate, zinc nitrate, the zinc lactate.
3. the preparation method of modified copolyester for non-fiber according to claim 1 is characterized in that: described titanium compound is a kind of in organic titanate titanium ethylene glycolate, tetrabutyl titanate, the titanium isopropylate.
4. the preparation method of modified copolyester for non-fiber according to claim 1, it is characterized in that: described germanium compound is a germanium oxide.
5. the preparation method of modified copolyester for non-fiber according to claim 1 is characterized in that: described cobalt compound is a kind of in Cobaltous diacetate tetrahydrate, cobaltous phosphate, the Xiao Suangu.
6. the preparation method of modified copolyester for non-fiber according to claim 1, it is characterized in that: the organic compound of described phosphorus is trialkylphosphate or Triphenyl phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101278053A CN100572417C (en) | 2005-12-06 | 2005-12-06 | The preparation method of modified copolyester for non-fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101278053A CN100572417C (en) | 2005-12-06 | 2005-12-06 | The preparation method of modified copolyester for non-fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1807486A CN1807486A (en) | 2006-07-26 |
| CN100572417C true CN100572417C (en) | 2009-12-23 |
Family
ID=36839593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101278053A Active CN100572417C (en) | 2005-12-06 | 2005-12-06 | The preparation method of modified copolyester for non-fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100572417C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250255B (en) * | 2008-03-28 | 2010-09-29 | 中国石油天然气股份有限公司 | Method for preparing synthetic terephthalic acid-1,3-trimethylene glycol ester |
| CN101875757B (en) * | 2009-04-30 | 2012-05-30 | 中国石油天然气股份有限公司 | Preparation method of polyethylene terephthalate/polyterephthalic glycol-1,4-cyclohexanedimethanol ester alloy |
| CN103992467B (en) * | 2013-02-20 | 2017-03-01 | 乐天化学株式会社 | For the resin combination preparing thermoplastic polyester and the polyester resin prepared by said composition |
| CN105111423B (en) * | 2015-09-15 | 2017-07-14 | 彭春海 | A kind of polymer waterborne polyester and preparation method thereof |
| CN112608454A (en) * | 2020-11-06 | 2021-04-06 | 珠海华润化学材料科技有限公司 | Basic production formula for preparing non-crystalline copolyester PETG by using recycled PET plastic and process method thereof |
-
2005
- 2005-12-06 CN CNB2005101278053A patent/CN100572417C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 从废聚酯合成多组分共聚酯的研究. 祝根平.浙江大学硕士学位论文. 2004 |
| 从废聚酯合成多组分共聚酯的研究. 祝根平.浙江大学硕士学位论文. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1807486A (en) | 2006-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101864068B (en) | Preparation method of polybutylene terephthalate/adipate butanediol copolyester | |
| EP2894182B1 (en) | Method for continuously preparing biodegradable aliphatic/aromatic polyester copolymer | |
| JP4529485B2 (en) | Polyester polymerization catalyst, method for producing the same, and method for producing polyester using the same | |
| US8344093B2 (en) | Production method of aliphatic polyester | |
| KR101769560B1 (en) | Polyester resin copolymerized with lactic acid and isosorbide and preparing method thereof | |
| JP2014525505A (en) | Aliphatic-aromatic copolyesters, compositions, and methods of making copolyesters | |
| CN100572417C (en) | The preparation method of modified copolyester for non-fiber | |
| US3528946A (en) | Acetylacetonates as polycondensation catalysts in transesterification method of preparing polyesters | |
| CN105849150A (en) | Composition for producing biodegradable polyester resin, and production method for biodegradable polyester resin | |
| CN102604053B (en) | Method for preparing biomass polyester | |
| CN100386361C (en) | Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis | |
| JP5200531B2 (en) | Method for producing aliphatic polyester | |
| JP2012144744A (en) | Method for producing aliphatic polyester | |
| KR20140076356A (en) | Method for continuous production of biodegradable aliphatic/aromatic polyester copolymer | |
| CN107778462B (en) | Method for preparing thermoplastic biodegradable plastic | |
| CN116102720A (en) | Poly (terephthalic acid) -carbonic acid-butanediol copolyester and preparation method thereof | |
| CN102167803B (en) | Preparation method of polyethylene terephthalate-1,3-propanediol copolyester | |
| KR101992393B1 (en) | Method for continuous production of biodegradable aliphatic polyester | |
| KR102236319B1 (en) | A preparation method of High molecular weight aliphatic carbonate and aromatic ester copolymer resin | |
| US11254785B2 (en) | Process for preparing polyesters by using an additive | |
| CN109456467A (en) | Improve the preparation method of flexible polycyclohexylene's diformazan alcohol ester resin | |
| JP2008019391A (en) | Catalyst for polyester polycondensation, its preparation method and method of producing polyester | |
| CN113801312B (en) | Composite catalyst containing organic semiconductor and application thereof | |
| JP2018145413A (en) | Production method of aliphatic aromatic polyester | |
| JP2014133824A (en) | Method for producing aliphatic polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |