CN101250285A - Method for degrading bis-hydroxyethyl terephthalate - Google Patents

Method for degrading bis-hydroxyethyl terephthalate Download PDF

Info

Publication number
CN101250285A
CN101250285A CNA2007101757042A CN200710175704A CN101250285A CN 101250285 A CN101250285 A CN 101250285A CN A2007101757042 A CNA2007101757042 A CN A2007101757042A CN 200710175704 A CN200710175704 A CN 200710175704A CN 101250285 A CN101250285 A CN 101250285A
Authority
CN
China
Prior art keywords
polyethylene terephthalate
degrading
pet
coo
charged ion
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.)
Granted
Application number
CNA2007101757042A
Other languages
Chinese (zh)
Other versions
CN101250285B (en
Inventor
李增喜
王慧
张锁江
刘彦轻
张香平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN2007101757042A priority Critical patent/CN101250285B/en
Publication of CN101250285A publication Critical patent/CN101250285A/en
Application granted granted Critical
Publication of CN101250285B publication Critical patent/CN101250285B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Abstract

The invention relates to a process for degrading polyethylene glycol terephthalate (PET) through utilizing ion liquid, which is characterized in that degrading polyethylene glycol terephthalate with ion liquid, and reacting under the condition of no adding any catalyst. The process degrades PET polyester through utilizing ion liquid which has the solvent function, and has the advantages of difficult volatilization of ion liquid, environment-friendly and mild reaction conditions and the like.

Description

A kind of method of the polyethylene terephthalate of degrading
Technical field:
The present invention relates to a kind of ionic liquid that utilizes, do not use the method for catalyst degradation polyethylene terephthalate.
Background technology:
Polyethylene terephthalate (PET) is a kind of thermoplastic macromolecule material of excellent property, because of it has good physical and chemical performance, be widely used in fields such as food product pack, beverage, film, medicine, sensitive film, finishing material, electrically insulating material, fiber, sheet base.Along with the swift and violent increase of polyester material volume of production and marketing, the amount of the waste and old polyester material that is produced will get more and more.2004, China PET polyester yearly capacity was about 6,000,000 tons, and its consumption is still increasing with the speed in every year 11%, wherein has every year millions of tons of polyester to become waste material approximately.Though the toxicity of these polyester waste materials own is little, because its light weight, bulky, and is difficult under the natural condition and degrades, thereby not only can cause very big influence, and can cause the huge wasting of resources environment.As the important channel of turning waste into wealth and solving ecological environmental pollution, the recovery and utilization technology of waste and old polyester more and more is subjected to the attention of countries in the world.
Traditional chemical recovery PET polyester is produced monomer and is mainly contained following several method: methyl alcohol alcoholysis, glycolysis and hydrolysis.Though adopting chemical recovery method can be monomer or industrial chemicals with the PET polyester depolymerization of giving up, realize the recycle of PET polyester waste material, still there are many unfavorable factors in aforesaid method, as: the organic solvent of using in the degradation process is volatile, contaminate environment; Severe reaction conditions needs High Temperature High Pressure usually; The glycolysis product is complicated, and many oligomers are wherein arranged; Acid-base solution meeting etching apparatus in the hydrolytic process, contaminate environment.So the present invention is a purpose with the depolymerizing agent environmentally friendly, that reaction conditions is gentle of exploitation degraded PET polyester.
Summary of the invention:
Research and utilization ionic liquid of the present invention, degraded PET polyester under the reaction conditions that does not add any catalyzer, gentleness.
The molecular weight of used polyethylene terephthalate is 6.2～6.8 * 10 4G/mol.
Used ion liquid positively charged ion is selected from a kind of in glyoxaline cation (1), pyridylium (2), season phosphine positively charged ion (3), the quaternary ammonium cation (4), and structure is as follows:
Figure S2007101757042D00021
Negatively charged ion is selected from Cl -, Br -, I -, AlCl 4 -, AlBr 4 -, AlI 4 -, CF 3COO -, CH 3COO -, CF 3SO 3 -, SCN -, (CF 3SO 2) 2N -, (CF 3SO 2) 3C -, o-C 6H 4(OH) (COO -) in a kind of.Wherein, the substituting group on (1), (2), (3) and (4) is selected from a kind of in alkane, halohydrocarbon, hydroxyl, aromatic hydrocarbons, the heterocycle hydro carbons, can be identical, also can be different, and the carbon number of aliphatic chain organic substituent group is between 1～14.
Because ionic liquid has good solubility, and volatilization hardly, so this method has reaction conditions gentleness, advantages of environment protection.
The temperature of reaction of ionic liquid degraded polyethylene terephthalate is 50 ℃ to 250 ℃, preferred 120 ℃ to 200 ℃.
Ionic liquid degraded polyethylene terephthalate does not have particular requirement to reaction pressure.
The time of ionic liquid degraded polyethylene terephthalate is 6 hours to 24 hours.
Embodiment:
The present invention illustrates with following embodiment, but the invention is not restricted to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g1-butyl-3-Methylimidazole villaumite ([bmim] Cl) successively.Control reaction temperature is 180 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of the PET that do not degrade.Draw with this understanding, the degradation rate of PET polyester is 49.54%.
Embodiment 2
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g1-butyl-3-Methylimidazole bromine salt ([bmim] Br) successively.Control reaction temperature is 180 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of undegradable PET.Draw with this understanding, the degradation rate of PET polyester is 6.96%.
Embodiment 3
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g1-ethyl-3-Methylimidazole bromine salt ([emim] Br) successively.Control reaction temperature is 180 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of undegradable PET.Draw with this understanding, the degradation rate of PET polyester is 2.90%.
Embodiment 4
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g1-butyl-3-Methylimidazole trifluoroacetate ([bmim] CF successively 3COO).Control reaction temperature is 120 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of undegradable PET.Draw with this understanding, the degradation rate of PET polyester is 7.63%.
Embodiment 5
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g1-butyl-3-Methylimidazole chloro-aluminate ([bmim] AlCl successively 4).Control reaction temperature is 150 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of undegradable PET.Draw with this understanding, the degradation rate of PET polyester is 29.90%.
Embodiment 6
Implementation method: in the 50ml there-necked flask, add 5.0gPET particle, 20.0g β hydroxyethyl trimethyl ammonium salicylic acid salt ([N successively + 111(CH 2) 2OH] C 6H 4(OH) (COO)).Control reaction temperature is 180 ℃, and pressure is 1atm, and 8 hours postcooling of condensing reflux reaction are isolated undegradable PET particle to room temperature, thorough washing, drying, weigh the quality of undegradable PET.Draw with this understanding, the degradation rate of PET polyester is 53.80%.
Embodiment 7
With embodiment 1, control reaction temperature is 200 ℃, and then the degradation rate of PET polyester is 64.58% 200 ℃ the time.

Claims (6)

1. the method for the polyethylene terephthalate of degrading is characterized in that with the ionic liquid being depolymerizing agent, descends in the condition that does not add any catalyzer and separates polyethylene terephthalate.
2. method according to claim 1, the molecular weight that it is characterized in that used polyethylene terephthalate is 6.2～6.8 * 10 4G/mol.
3. method according to claim 1, used ion liquid positively charged ion are selected from a kind of in glyoxaline cation (1), pyridylium (2), season phosphine positively charged ion (3), the quaternary ammonium cation (4), and structure is as follows:
Figure S2007101757042C00011
Its negatively charged ion is selected from Cl -, Br -, I -, AlCl 4 -, AlBr 4 -, AlI 4 -, CF 3COO -, CH 3COO -, CF 3SO 3 -, SCN -, (CF 3SO 2) 2N -, (CF 3SO 2) 3C -, o-C 6H 4(OH) a kind of in (COO).
4. according to claim 3 described methods, it is characterized in that substituting group on (1), (2), (3) and (4) is selected from a kind of in alkane, halohydrocarbon, hydroxyl, aromatic hydrocarbons, the heterocycle hydro carbons, can be identical, also can be different, wherein the carbon number of aliphatic chain organic substituent group is between 1～14.
5. method according to claim 1, the temperature of the polyethylene terephthalate that it is characterized in that degrading is 50 ℃ to 250 ℃, preferred 120 ℃ to 200 ℃.
6. method according to claim 1, the polyethylene terephthalate time that it is characterized in that degrading is 6 hours to 24 hours.
CN2007101757042A 2007-10-10 2007-10-10 Method for degrading bis-hydroxyethyl terephthalate Active CN101250285B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007101757042A CN101250285B (en) 2007-10-10 2007-10-10 Method for degrading bis-hydroxyethyl terephthalate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007101757042A CN101250285B (en) 2007-10-10 2007-10-10 Method for degrading bis-hydroxyethyl terephthalate

Publications (2)

Publication Number Publication Date
CN101250285A true CN101250285A (en) 2008-08-27
CN101250285B CN101250285B (en) 2011-04-20

Family

ID=39953897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007101757042A Active CN101250285B (en) 2007-10-10 2007-10-10 Method for degrading bis-hydroxyethyl terephthalate

Country Status (1)

Country Link
CN (1) CN101250285B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153443A (en) * 2011-02-23 2011-08-17 合肥工业大学 Method for degrading polyethylene terephthalate
CN102516594A (en) * 2011-11-04 2012-06-27 中国科学院长春应用化学研究所 Recovery method of thermosetting epoxy resin or composite material thereof
CN106065068A (en) * 2016-07-27 2016-11-02 安徽泰达新材料股份有限公司 Pure polyester used for powder coating and preparation method thereof
JP2018508642A (en) * 2014-12-23 2018-03-29 イオニカ・テクノロジーズ・ベー・フェー Improved reusable capture complex
CN108690217A (en) * 2017-04-07 2018-10-23 波音公司 Carbon fiber recycles composition and method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100487059C (en) * 2005-01-20 2009-05-13 中国科学院过程工程研究所 Method for preparing degradable material using stalk
EP1994060A1 (en) * 2006-03-08 2008-11-26 Basf Se Method for breaking down cellulose
DE102006011075A1 (en) * 2006-03-08 2007-09-13 Basf Ag Process for breaking down cellulose in solution

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153443A (en) * 2011-02-23 2011-08-17 合肥工业大学 Method for degrading polyethylene terephthalate
CN102153443B (en) * 2011-02-23 2013-07-31 合肥工业大学 Method for degrading polyethylene terephthalate
CN102516594A (en) * 2011-11-04 2012-06-27 中国科学院长春应用化学研究所 Recovery method of thermosetting epoxy resin or composite material thereof
JP2018508642A (en) * 2014-12-23 2018-03-29 イオニカ・テクノロジーズ・ベー・フェー Improved reusable capture complex
CN106065068A (en) * 2016-07-27 2016-11-02 安徽泰达新材料股份有限公司 Pure polyester used for powder coating and preparation method thereof
CN106065068B (en) * 2016-07-27 2017-10-27 安徽泰达新材料股份有限公司 Powdery paints pure polyester and preparation method thereof
CN108690217A (en) * 2017-04-07 2018-10-23 波音公司 Carbon fiber recycles composition and method
US11377535B2 (en) 2017-04-07 2022-07-05 The Boeing Company Carbon fiber recovery compositions and methods
CN108690217B (en) * 2017-04-07 2022-07-15 波音公司 Carbon fiber recycling composition and method

Also Published As

Publication number Publication date
CN101250285B (en) 2011-04-20

Similar Documents

Publication Publication Date Title
Quartinello et al. Synergistic chemo‐enzymatic hydrolysis of poly (ethylene terephthalate) from textile waste
CN101250285B (en) Method for degrading bis-hydroxyethyl terephthalate
CN101407445B (en) Waste polyester material recovery method with ion liquid as reaction medium and catalyst
Xi et al. Study on depolymerization of waste polyethylene terephthalate into monomer of bis (2-hydroxyethyl terephthalate)
CN101429100B (en) Chemical recovery method for waste polycarbonate material in ionic liquid surrounding
CN102584569B (en) Method for preparing diphenolic acid in ionic liquid
Zhu et al. Glycolysis recycling of rigid waste polyurethane foam from refrigerators
Zhang et al. Hydrolysis of poly (ethylene terephthalate) waste bottles in the presence of dual functional phase transfer catalysts
Kumar et al. An efficient one pot method for synthesis of carboxylic acids from nitriles using recyclable ionic liquid [bmim] HSO4
CN102659590A (en) Alcoholysis recovery method of waster polylactic acid in ionic liquid environment
CN103951564B (en) A kind of method of multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate
CN112851502B (en) Method for catalyzing waste PET polyester to carry out methanol alcoholysis by using choline and terephthalic acid non-metallic ionic liquid
CN103360260B (en) Preparation technology of ethylene glycol terephthalate and preparation method of polyester
Yue et al. Metal-containing ionic liquids: highly effective catalysts for degradation of poly (ethylene terephthalate)
Großeheilmann et al. Preparation of Poly (ionic liquid) s‐Supported Recyclable Organocatalysts for the Asymmetric Nitroaldol (Henry) Reaction
Liu et al. Butanol alcoholysis reaction of polyethylene terephthalate using acidic ionic liquid as catalyst
CN105483389A (en) Leaching method for indium in waste liquid crystal panel and leaching agent
CN105618139B (en) A kind of ligocellulose degradation's method based on molybdenum multi-metal oxygen hydrochlorate
CN114656684A (en) Method for preparing high-purity recycled PET (polyethylene terephthalate) polyester by using waste PET polyester
CN104860797A (en) Isopropyl ether-isopropyl alcohol azeotrope distillation separation method based on choline chloride deep eutectic solvent
CN102796002B (en) Method for catalytically alcoholizing polyethylene terephthalate
CN102153443B (en) Method for degrading polyethylene terephthalate
CN102976922A (en) Novel method for recovering calcium lactate by hydrolysis of waste polylactic acid material
Dilip Cradle to grave: How green are ionic liquids?
Rai et al. Ionic liquid mediated efficient reduction of nitroarenes using stannous chloride under sonication

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