CN1631870A - Gentle depolymerization process for waste polytrimethylene terephthalate - Google Patents
Gentle depolymerization process for waste polytrimethylene terephthalate Download PDFInfo
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- CN1631870A CN1631870A CNA2004100645578A CN200410064557A CN1631870A CN 1631870 A CN1631870 A CN 1631870A CN A2004100645578 A CNA2004100645578 A CN A2004100645578A CN 200410064557 A CN200410064557 A CN 200410064557A CN 1631870 A CN1631870 A CN 1631870A
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- waste material
- trimethylene terephthalate
- poly
- methyl alcohol
- gentle
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
A friendly method for depolymerizing benzenedicarbon propylene glycol ester uses methanol as depolymerizing agent,the mess ratio benzenedicarbon propylene glycol ester and polyethylene propylene glycol ester methanol is 1:1-20; in the reaction, the temperature is 150-300deg.C and the pressure is generated by methanol itself, for 0.1-10.0 hours, the waste of benzenedicarbon propylene glycol ester is depolymerized to be dimethyl phthalate (DMT) and 1,3-propylene glycol (PDO). It has simple technical process, can generate monomer product DMT and PDO.
Description
Technical field
The invention belongs to a kind of depolymerization and handle the method for waste and old polyester, relate to the method that the Poly(Trimethylene Terephthalate) waste material is handled in a kind of depolymerization specifically.
Background technology
Poly(Trimethylene Terephthalate) (PTT) is a kind of trevira of excellent performance, had the rigidity of polyethylene terephthalate (PET) concurrently, the flexibility that polybutylene terephthalate (PBT) arranged again, and its rebound resilience is equivalent to nylon, dimensional stability and dyeability all are better than PET and PBT, therefore can be widely used in fields such as weaving, engineering plastics.Along with constantly perfect, the decline of production cost of PTT technology, the developing of application market, its production and consumption will hold out broad prospects; A large amount of production and use must bring the accumulation of a large amount of waste materials to handle.How scrap stock, the waste product in the process for producing, and the waste materials such as waste products after using, saved resource, reduced environmental pollution and become the problem that presses for solution at recycle effectively.
The recovery method of at present relevant new polyester material PTT has alkaline water solution, supercritical methanol method to handle.The alkaline water solution is to use glycols, is solvent as ethylene glycol, glycol ether etc., realizes that in strongly basic medium (as NaOH, KOH) reaction product is disodium terephthalate salt and 1, ammediol; Disodium terephthalate salt generates terephthalic acid with neutralizations such as hydrochloric acid more then.The alkaline water solution directly uses strongly basic medium to participate in reaction, and is very high to the requirement of equipment, and post-reaction treatment need use the acidic medium neutralization, and aftertreatment is cumbersome.The supercritical methanol depolymerization, temperature of reaction requires must be more than 260 ℃, and reaction pressure requires greater than 8MPa, and reaction product is dimethyl terephthalate (DMT) and propylene glycol; But the shortcoming of this technology is that the supercritical reaction operational condition is relatively harsher, processing unit requires height.
Summary of the invention
The object of the invention is to provide a kind of method of gentle depolymerization PTT waste material, and this technological process is simple, mild condition, directed dimethyl terephthalate (DMT) and the propylene glycol of generating.
The present invention is achieved in that with waste and old PTT be raw material, and methyl alcohol is as reaction solvent, depolymerization PTT under the state of hot methanol, and obtaining product is dimethyl terephthalate (DMT) (DMT) and 1, ammediol (PDO).
Concrete steps of the present invention are as follows:
(1) will be ground into the particle of 5.0-50 millimeter through Poly(Trimethylene Terephthalate) (PTT) waste material that washs, drying is removed impurity, stand-by;
(2) particle that step (1) is obtained and methyl alcohol are by weight 1: (1-20), join in the autoclave that has whipping appts;
(3) feed inert gas replacement and go out the interior oxygen of reaction system;
(4) then reaction system is warming up between 150-300 ℃, working pressure is a methyl alcohol self-generating pressure, and the reaction times is 0.1-10 hour;
(5) after question response is finished,, be drying to obtain the solid product dimethyl terephthalate (DMT) with reaction system cooling, crystallization, filtration, methanol wash; Filtrate can get 1 through rectifying separation, ammediol (PDO) and methyl alcohol, and wherein methyl alcohol is also reusable.
The catalyzer that in (2) step, can also add 0.1-10wt% for the content that improves DMT in the reaction product.
Aforesaid PTT waste material and methyl alcohol weight ratio preferably 1: (2-10).
Preferably 180-300 ℃ of aforesaid service temperature.
Preferably 0.2-2.0 hour aforesaid operating time.
Aforesaid catalyzer can be zinc acetate (ZnAc
2), manganese acetate (MnAc
2), Cobaltous diacetate (CoAc
2) or plumbic acetate (PbAc
2).
Aforesaid rare gas element is nitrogen or argon gas.
The present invention compared with prior art has the following advantages:
1. the present invention realizes in the medium of hot methanol, the operational condition gentleness, and depolymerization process and aftertreatment technology are simple.
2. this technological process, orientable generation monomeric products is DMT and PDO.
3. the PDO by the present technique gained can be used for reacting again with DMT through further purifying, synthetic new polyester; Methyl alcohol is reusable, directly is used as the solvent of depolymerization reaction.
4. present technique can be used catalyzer, and catalyzer can not need to reclaim, and directly reuses in methyl alcohol, continues to participate in the reaction of depolymerization PTT.
Embodiment
Embodiment 1
In the autoclave that devices such as stirring, temperature control are installed, add and to remove impurity through washing, drying, get PTT particle 9.02 grams and the 90.42 gram methyl alcohol that it are ground into the 5.0-20 millimeter, remaining oxygen in the nitrogen replacement reaction system, reaction is after 2 hours under 240 ℃, the condition of 3.8MPa, cooling, crystallization, filtration, methanol wash are weighed as 8.50 grams after the gained solid product drying.The content of monomer DMT is 93.2% in the solid product, and terephthalic acid dipropylene glycol ester (BHPT) and oligopolymer contain 6.4%, and contained insolubles is 0.4%; The content of PDO is 2.89 grams in the filtrate, and the degree of depolymerizaton of PTT polyester can reach 98.5%.
Embodiment 2
The depolymerization appointed condition is pressed embodiment 1, adds the 15.03 gram PTT particles and the 90.60 gram methyl alcohol that are ground into the 10-30 millimeter in the autoclave.Depolymerization reaction is after carrying out 1 hour under 300 ℃, 4.8MPa, and cooling, crystallization, filtration, methanol wash are weighed as 13.21 grams after the gained solid product drying.The content of monomer DMT is 95.8% in the solid product, and BHPT and oligopolymer contain 4.2%; The content of PDO is 5.19 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 99.5%.
Embodiment 3
The depolymerization appointed condition is pressed embodiment 1, adds the 22.02 gram PTT particles and the 88.40 gram methyl alcohol that are ground into the 5.0-10 millimeter in the autoclave.Depolymerization reaction uses 5%ZnAc in 260 ℃, 3.8MPa
2Be catalyzer, after reaction was carried out 3 hours, cooling, crystallization, filtration, methanol wash were weighed as 18.25 grams after the gained solid product drying.The content of monomer DMT is 85.9% in the solid product, and BHPT and oligopolymer are 12.8%, and contained insolubles is 1.3%; The content of PDO is 7.07 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 96.5%.
Embodiment 4
The depolymerization appointed condition is pressed embodiment 1, adds the PTT particle and the 90.8 gram methyl alcohol of 9.02 grams that are ground into the 10-15 millimeter in the autoclave.Depolymerization reaction uses 8%CoAc in 180 ℃, 1.5MPa
2Be catalyzer, carry out 5 hours after, cooling, crystallization, filtration, methanol wash, be weighed as after the gained solid product drying 8.35 the gram.The selectivity of monomer DMT is 74.5% in the solid product, and the content of impurity such as BHPT and oligopolymer is 21.3%, and contained insolubles is 4.2%; The content of PDO is 2.45 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 95.7%.
Embodiment 5
The depolymerization appointed condition is pressed embodiment 1, adds the PTT particle and the 90.04 gram methyl alcohol of 15.02 grams that are ground into the 5.0-15 millimeter in the autoclave.Depolymerization reaction uses 0.1%MnAc in 280 ℃, 4.4MPa
2After carrying out 1 hour under the catalyzer, cooling, crystallization, filtration, methanol wash are weighed as 13.5 grams after the gained solid product drying.The content of DMT is 97.3% in the solid product, and BHPT and oligopolymer are 1.5%, and contained insolubles is 1.2%; The content of PDO is 5.15 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 98.3%.
Embodiment 6
The depolymerization appointed condition is pressed embodiment 1, adds the PTT particle and the 90.20 gram methyl alcohol of 15.01 grams that are ground into the 5.0-40 millimeter in the autoclave.Depolymerization reaction uses 2%PbAc in 220 ℃, 2.8MPa
2After carrying out 2 hours under the catalyzer, cooling, crystallization, filtration, methanol wash are weighed as 13.2 grams after the gained solid product drying.The content of DMT is 85.5% in the solid product, and BHPT and oligopolymer are 10.2%, and contained insolubles is 4.3%; The content of PDO is 4.65 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 96.5%.
Embodiment 7
The depolymerization appointed condition is pressed embodiment 1, adds 11.02 grams that are ground into the 20-50 millimeter in the autoclave and removes pretreated PTT particle and 90.39 gram methyl alcohol such as impurity through washing, drying.Heat up, stir, boost, undertaken by the step of embodiment 1, depolymerization reaction is after carrying out 20 minutes under 260 ℃, 4.2MPa, and cooling, crystallization, filtration, methanol wash are weighed as 9.2 grams after the gained solid product drying.The content of DMT is 72.4% in the solid product, and BHPT and oligopolymer are 16.3%, and contained insolubles is 11.3%, and the content of PDO is 5.65 grams in the filtrate, and the degree of depolymerizaton of PTT can reach 90.3%.
Claims (7)
1, a kind of method of gentle depolymerization Poly(Trimethylene Terephthalate) waste material is characterized in that comprising the steps:
(1) will be ground into the particle of 5.0-50 millimeter through the Poly(Trimethylene Terephthalate) waste material that washs, drying is removed impurity, stand-by;
(2) particle that step (1) is obtained and methyl alcohol are by weight 1: 1-20 joins in the autoclave that has whipping appts;
(3) feed inert gas replacement and go out the interior oxygen of reaction system;
(4) then reaction system is warming up between 150-300 ℃, working pressure is a methyl alcohol self-generating pressure, and the reaction times is 0.1-10 hour;
(5) after question response is finished,, be drying to obtain the solid product dimethyl terephthalate (DMT) with reaction system cooling, crystallization, filtration, methanol wash; Filtrate can get 1 through rectifying separation, ammediol (PDO) and methyl alcohol, and wherein methyl alcohol is also reusable.
2, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 is characterized in that also adding the catalyzer of 0.1-10wt% in (2) step.
3, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 or 2 is characterized in that described Poly(Trimethylene Terephthalate) waste material and methyl alcohol weight ratio are 1: 2-10.
4, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 or 2 is characterized in that described service temperature is 180-300 ℃.
5, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 or 2 is characterized in that the described operating time is 0.2-2.0 hour.
6, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 or 2 is characterized in that described catalyzer is zinc acetate, manganese acetate, Cobaltous diacetate or plumbic acetate.
7, the method for a kind of gentle depolymerization Poly(Trimethylene Terephthalate) waste material as claimed in claim 1 or 2 is characterized in that described rare gas element is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100645578A CN1260205C (en) | 2004-11-19 | 2004-11-19 | Gentle depolymerization process for waste polytrimethylene terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100645578A CN1260205C (en) | 2004-11-19 | 2004-11-19 | Gentle depolymerization process for waste polytrimethylene terephthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1631870A true CN1631870A (en) | 2005-06-29 |
| CN1260205C CN1260205C (en) | 2006-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100645578A Expired - Fee Related CN1260205C (en) | 2004-11-19 | 2004-11-19 | Gentle depolymerization process for waste polytrimethylene terephthalate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045858A (en) * | 2015-08-18 | 2016-10-26 | 江苏景宏新材料科技有限公司 | Method for preparing dimethyl terephthalate from waste PETG film through normal-pressure alcoholysis |
| CN109134244A (en) * | 2018-09-26 | 2019-01-04 | 东华大学 | A kind of biodegrading process of waste and old polyester |
| CN113718365A (en) * | 2021-08-02 | 2021-11-30 | 浙江佳人新材料有限公司 | Preparation method of cool regenerated PTT fiber |
| CN113897698A (en) * | 2021-10-12 | 2022-01-07 | 浙江理工大学桐乡研究院有限公司 | Preparation method of antibacterial regenerated PTT fiber |
| CN116120525A (en) * | 2021-11-12 | 2023-05-16 | 中国科学院福建物质结构研究所 | Polymer compound capable of being circularly degraded and recycled and synthesis and depolymerization recycling method thereof |
-
2004
- 2004-11-19 CN CNB2004100645578A patent/CN1260205C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045858A (en) * | 2015-08-18 | 2016-10-26 | 江苏景宏新材料科技有限公司 | Method for preparing dimethyl terephthalate from waste PETG film through normal-pressure alcoholysis |
| CN109134244A (en) * | 2018-09-26 | 2019-01-04 | 东华大学 | A kind of biodegrading process of waste and old polyester |
| CN113718365A (en) * | 2021-08-02 | 2021-11-30 | 浙江佳人新材料有限公司 | Preparation method of cool regenerated PTT fiber |
| CN113897698A (en) * | 2021-10-12 | 2022-01-07 | 浙江理工大学桐乡研究院有限公司 | Preparation method of antibacterial regenerated PTT fiber |
| CN116120525A (en) * | 2021-11-12 | 2023-05-16 | 中国科学院福建物质结构研究所 | Polymer compound capable of being circularly degraded and recycled and synthesis and depolymerization recycling method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1260205C (en) | 2006-06-21 |
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Granted publication date: 20060621 Termination date: 20131119 |