CN108947798A - A kind of method of degradation polymer - Google Patents

A kind of method of degradation polymer Download PDF

Info

Publication number
CN108947798A
CN108947798A CN201810597098.1A CN201810597098A CN108947798A CN 108947798 A CN108947798 A CN 108947798A CN 201810597098 A CN201810597098 A CN 201810597098A CN 108947798 A CN108947798 A CN 108947798A
Authority
CN
China
Prior art keywords
polymer
acid
degradation
degradation polymer
sulfonamide
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
CN201810597098.1A
Other languages
Chinese (zh)
Other versions
CN108947798B (en
Inventor
李智
刘华
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.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
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 University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN201810597098.1A priority Critical patent/CN108947798B/en
Priority to CN202110199167.5A priority patent/CN112961045A/en
Publication of CN108947798A publication Critical patent/CN108947798A/en
Application granted granted Critical
Publication of CN108947798B publication Critical patent/CN108947798B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The present invention provides a kind of methods of degradation polymer characterized by comprising by polymer, sulfonamide, lewis acid catalyst mixes and depolymerization；The polymer includes the polyester repetitive unit that dicarboxylic acids and diol copolymer are formed.In the resulting catabolite of the present invention, contained dicarboxylic acid monomer can be used for synthesizing again for polyester；The small molecule aminoalcohol derivative obtained through subsequent transformation can then be converted into the amino alcohol compared with high added value by conventional method, or be directly used in other purposes as chemical raw material, be advantageously implemented the maximization of economic benefit of polymer degradation.

Description

A kind of method of degradation polymer
Technical field
The present invention relates to a kind of methods of degradation polymer, belong to organic chemistry filed.
Background technique
Polyester is the polymer general name as obtained by polyalcohol and polyacid polycondensation, is that one kind has excellent performance, is widely used Engineering plastics may be made as polyester fiber and polyester film.The specific kind of polyester has: polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), poly- 2,6- naphthalene diacid second diester (PEN), and The polyester-based fibers of a variety of modifications, wherein the most widely used is PET polyester.
PET polyester is a kind of excellent crystalline thermoplastic polyester's material, be widely used in food packaging, weaving, film, Synthetic fibers etc..It is fast with PET polyester output and consumption figure however since it is difficult to be degraded by microorganisms in the environment Speed increases, and the handling problems of waste PET polyester become increasingly conspicuous.Recycling waste PET polyester can not only reduce environmental pollution, And the cycling and reutilization of resource may be implemented.The recovery method of PET polyester mainly has physics and chemical method, wherein chemistry drop The monomer or intermediate that solution obtains can be used as raw material and prepare high performance polyester material again, be able to achieve the highly efficient regeneration of resource It utilizes.
The chemical degradation method of PET polyester mainly has alcoholysis method, Hydrolyze method and amine-decomposing method at present.Alcoholysis method be with methanol, PET polyester is degraded to terephthalate (DMT, BHET) as alcoholysis agent, by different technique by the various alcohol such as ethylene glycol And ethylene glycol.The product purity that alcoholysis method obtains is higher, and condition is relatively mild, industrial continuous production easy to accomplish, example Such as the low pressure methanol alcoholysis process of E.I.Du Pont Company's PET polyester.This technique first fragmentates the cutting of PET polyester, and then investment contains In the reaction vessel for melting DMT, and the temperature of reactor is controlled at 220 DEG C, PET polyester is promoted to be completely dissolved in the solution； Obtained solution is poured into reactor, then temperature is within the scope of 260~300 DEG C and is in 0.34~0.65MPa with pressure Methanol in range is blown into reactor, and depolymerization reaction occurs with the PET polyester liquid in reactor.In addition there are Eastman Three sections of continuity method methanol depolymerization PET polyester process etc. that Kodak Company uses.Alcoholysis method research is more, and technique is more mature, leads to Often it is related to 200 DEG C or more of high temperature or the control of various mesohighs.Hydrolyze method is to take water as a solvent to be catalyzed PET polyester Degradation, is depolymerized to monomers terephthalic acid (TPA) and ethylene glycol, gained TPA monomer can be directly used for the reproduction of PET polyester. Neutral hydrolysis usually carries out within the temperature range of 245~300 DEG C, and pressure is normally controlled between 1~4MPa, Japanese Kobe The technique of the supercritical water hydrolysis PET of Steel company exploitation also belongs to such.Alkaline water solution is usually in sodium hydroxide and hydrogen Carried out in the aqueous solution of potassium oxide, usual conditions be within the temperature range of 200~250 DEG C, control reaction pressure 1.4~ Between 2MPa, react 3~5 hours.The principal product that this method obtains is para-phthalic sodium or potassium terephthalate and second two The terephthalic acid (TPA) of high-purity can be obtained by being acidified for alcohol, but its generated waste liquid subsequent processing is more complicated, be easy Pollute environment.Amine-decomposing method is PET polyester benzenedicarboxamide corresponding with the progress aminolysis reaction generation of different types of amine, but by It is more compared with slow and by-product in the aminolysis reaction of PET, so the amine-decomposing method of PET realizes industrialized production not yet so far.
The research of PET polyester degradation is numerous, also there is more mature technique, but is limited to by various conditions, and chemistry is passed through Method, which recycles PET polyester, still has very big room for promotion.In addition, the product of PET polyester degradation at present is only limitted to benzene Dicarboxylic acid derivatives and ethylene glycol, and the recycling of cheap ethylene glycol is often ignored by people, and the warp of PET degradation is virtually reduced Ji benefit.In addition, having emerged in large numbers the various polyester materials with different structure and function in recent years with the continuous development of polyester industrial Material, the industrialized production and use of these functional polyesters will necessarily also face the recycling problem of waste material.
To sum up, develop a kind of novel, general polyester polymer biodegrading process tool with higher economic value added It is significant.
Summary of the invention
The object of the present invention is to provide a kind of methods by the polymer degradation containing polyester unit.
Applicant is surprisingly, it has been found that polyol carboxylate is common with lewis acid catalyst in sulfamide compound Under effect, substitution reaction can occur for the alcoxyl key of ester group, obtain carboxylic acid and aminoalcohol derivative.Such as applicant has been filed on Patent application (application number: 201810429499.6, denomination of invention " a method of prepare aminoalcohol derivative "), it is open in Appearance is incorporated herein by reference in its entirety for all purposes.Therefore, containing feature polyol carboxylate functional group Polymer theoretical on similar reaction can also occur, as a result will lead to polymer polyatomic alcohol backbone breaking, be degraded to polyacid Monomer and small molecule aminoalcohol derivative.
In order to achieve the above object, the present invention provides a kind of methods of degradation polymer, comprising: by polymer, sulphonyl Amine and lewis acid catalyst mixing and depolymerization；The polymer includes the polyester weight that dicarboxylic acids and diol copolymer are formed Multiple unit.
Preferably, the polymer includes following repetitive unit:
Wherein, R1For aromatic group or the alkyl chain of C1-C6；R2For the alkyl of H or C1-C6, n is 1 to 6；Preferably, institute State R1Aromatic group be full carbon aromatic group or miscellaneous aromatic group, most preferably phenyl ring, naphthalene nucleus or furan nucleus；The R1Alkane Base chain is the alkyl chain of C1-C6, most preferably C2 and C4 alkyl；R2For H or methyl, n is 1 or 2.
Preferably, the dicarboxylic acids is selected from terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,5- furans two At least one of formic acid, 2,6-naphthalenedicarboxylic acid and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid；Dihydric alcohol be selected from ethylene glycol, 1,3-PD and At least one of 1,2-PD.
Preferably, the sulfonamide are as follows:
Wherein, R3Alkyl for C1-C6, the aryl comprising substituent group, and the substituent group is selected from hydrogen, halogen, C1-C6 Alkyl, the halogenated alkyl of C1-C6, the alkoxy of C1-C6, the alkylamino of C1-C6, the alkylthio group of C1-C6, C2-C6 acyl group, The aryl is phenyl or naphthyl；R4Selected from hydrogen, the alkyl of C1-C6, the acyl group of C2-C6, comprising the benzoyl group of substituent group, wherein The substituent group is same to be selected from above-mentioned R3The range of the substituent group of middle aryl；R3、R4Cyclic structure can be collectively constituted.
Preferably, the amine residues of the sulfonamide contain N-H key.
Preferably, the sulfonamide is o-benzoic sulfimide, para toluene sulfonamide or N- methyl tolysulfonyl Amine.
Most preferably, the sulfonamide is o-benzoic sulfimide, popular name saccharin.The feedstock property is stablized, inexpensively It is easy to get.
Preferably, the lewis acid catalyst, preferably fluoroform sulphonate, the especially following various valence states of metal Fluoroform sulphonate: Li, Na, Mg, Ca, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Bi etc..Its In most preferably trifluoromethanesulfonic acid hafnium, trifluoromethanesulfonic acid aluminium, trifluoromethanesulfonic acid iron, trifluoromethanesulfonic acid zirconium or trifluoromethanesulfonic acid scandium.
The depolymerization product of this method is small-molecule mixture, including dibasic carboxylic acid monomers, dicarboxylic acids sulfoamido alcohol list Ester and bis- (sulfoamido alcohol) diester of dicarboxylic acids:
Wherein, R1、R2、R3、R4, n range be same as above.
Preferably, the method for the degradation polymer further includes carrying out the ester functional group in gained depolymerization product into one Alkaline condition hydrolysis and acidification separation and Extraction are walked, dicarboxylic acids and sulfoamido alcohol are obtained.Preferably, the sulfonamide It is 1%~200mol%, most preferably on the basis of the amount of substance of the inventory to contain the repetitive unit in polymer 100mo1%.
Preferably, the lewis acidic inventory is using the amount of the substance in polymer containing the repetitive unit as base Standard is 0.1~20.0mol%, most preferably 5.0mol%.
Preferably, the depolymerization carries out in a solvent.
Preferably, the solvent be non-polar organic solvent, preferred fragrance hydro carbons solvent, chlorinated solvents, esters solvent, Most preferably from one of toluene, dimethylbenzene and chlorobenzene or a variety of.
Preferably, the depolymerization reaction carries out at a temperature of 100~180 DEG C, wherein most preferably 150 DEG C.
Core of the invention technical solution is: using fluoroform sulphonate as catalyst, with such as o-benzoyl sulphonyl Asia The sulfonamide of amine etc. carries out depolymerization to the polymer containing polyol ester functional group in a heated condition, obtains corresponding dicarboxylic acids list Body and aminoalcohol derivative.
Its depolymerization mechanism is activation of the polyol carboxylate by catalyst, the alcoxyl key in main chain by sulfonamide with The mode of nucleophilic displacement of fluorine disconnects, and one side carboxylic acid is left away as leaving group, generates free carboxy acid；Another aspect sulfoamido generation It is connected for alkoxy with polyhydric alcohol residue, obtains aminoalcohol derivative.When polymer is degraded, the main chain of polymer is all Carboxylate function is likely to that cleavage reaction occurs；But after a substitution reaction occurs for any one residue of dihydric alcohol, this Second of substitution reaction will not occur again for residue, therefore the residue will still retain a carboxylate.Accordingly, it is considered to solution Poly- randomness and continuity will obtain incomplete depolymerization in depolymehzation process, produce among the polyester with sulfoamido alcohol residue Object, and finally obtained small-molecule mixture includes dicarboxylic acid monomer, the unilateral carboxylic that bilateral carboxyl is all used as leaving group to obtain As leaving group, another side carboxyl retains the dicarboxylic acids sulfoamido alcohol monoesters of carboxylate to base and bilateral carboxyl is all protected Stay bis- (sulfoamido alcohol) diester of the dicarboxylic acids of carboxylate.
Mild condition of the present invention, without the complex conditions such as high temperature and pressure, high conversion rate, products therefrom separation is simple.In addition, Degrading polyester by this method can be while obtaining reusable dicarboxylic acids, also by simple and regular subsequent transformation Obtain the aminoalcohol derivative that added value is had more than the product glycol of other depolymerization methods, more economic benefit.
PET polyester raw material used in the embodiment of the present invention is colourless commercial mineral water bottle, and PEN polyester raw material is commercialization Japanese Supreme Being people Teonex TN-8065S plastic grains, PEF polyester raw material be reference literature (applied chemistry, 2012,29,751- 756；CN102190785A it) voluntarily synthesizes and characterizes.
Operation of the present invention is simple: polymer, sulfonamide, catalyst being mixed, solvent, heating stirring is added to having reacted Entirely.Products therefrom separation is simple: solvent being evaporated off after completion of the reaction, obtained solid is handled with dilute alkaline aqueous solution, keeps depolymerization resulting Dicarboxylic acids P1 and dicarboxylic acids sulfoamido alcohol monoesters P2 are converted to salt and enter water phase, and the insoluble solids in system are binary carboxylic Bis- (sulfoamido alcohol) the diester P3 of acid, are filtered to obtain the final product；The solid being precipitated after water phase is acidified is P1, and P2 is then remained dissolved in In water.
In the resulting depolymerization product of the present invention, P2 and P3 are small molecule, can be after by conventional methods such as hydrolysis or alcoholysis It is continuous to be converted into P1 and sulfoamido alcohol.Therefore, the present invention after catalytic degradation can not post-treated separation product, but Alkaline condition hydrolysis and acidification separation and Extraction are carried out in system immediately, obtains final depolymerization product P1 and sulfoamido alcohol.Institute Sulfoamido alcohol is different according to structure and property, separation and purification operation slightly has difference: if its not carboxy-containing acid group, is dissolved in In organic phase, liquid separation extraction be can be obtained；If it contains carboxylic acid group, water phase is dissolved in the form of sodium salt together with P1 In, the solid that is precipitated is P1 after water phase acidification, it can be purified through filtering, and the molten still solution of sulfoamido alcohol is in filtrate, Product can be obtained by organic solvent extraction.
Polymer Degradation and Transformation containing polyester repetitive unit can be dicarboxylic acids and sulfoamido alcohol, conversion ratio by the present invention Height, product is single, and separates simple.Dicarboxylic acids can be directly used for synthesizing again for polyester, and sulfoamido alcohol can then pass through conventional side Method is converted into the amino alcohol compared with high added value, or is directly used in other chemical conversions as chemicals, is conducive to reality The maximization of economic benefit of existing polyester degradation.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Table 1~3 is that the response parameter variation of its depolymerization is investigated using PET polyester as template raw material to depolymerization product P3-A's The influence of yield.Embodiment 14-19 is operating process of the PET polyester to dicarboxylic acids and sulfoamido alcohol of degrading, embodiment 20,21 Respectively degradation PEN and PEF polyester to dicarboxylic acids and sulfoamido alcohol operating process.It is total that depolymerization product all passes through liquid nuclear-magnetism Vibration characterizes its structure.
The present invention is a kind of novel polymer biodegrading process, and core technology is the polyol ester of Louis acid catalysis The nucleophilic substitution of the sulfonamide such as alcoxyl key and saccharin, depolymerization product are dicarboxylic acids P1, dicarboxylic acids sulfoamido alcohol monoesters P2 and bis- (sulfoamido alcohol) the diester P3 of dicarboxylic acids.In view of in current polyester polymer, PET's using and recycling the most Extensively, therefore we test using PET polyester as raw material first.We select the PET empty bottle of commercially available mineral water, are cut into Fragment, and investigate the response parameter of PET fragment degradation.It is verified through many experiments, the depolymerization product in the depolymerization reaction is main For P1-A and P3-A, and P2-A and the intermediate product of incomplete depolymerization are less.Therefore, the yield of core degradation product P3-A can For discussing the efficiency of PET degradation.Primarily look at the influence that different fluoroform sulphonates degrades to PET as catalyst.
Embodiment 1-4
A kind of biodegrading process of PET polyester, specific steps are as follows:
Sequentially add 96mg PET polyester chips in 5mL reaction flask, 91.5mg saccharin, different trifluoro methylsulphur in table 1 Phosphate catalyst and 0.5mL chlorobenzene make solvent.Reaction bottle closure is heated to 150 DEG C, the condition for being 150 DEG C in steady temperature Under, stirring carries out depolymerization reaction 24 hours.Solvent is removed after completion of the reaction, then the hydroxide of 15mL 0.5M is added into system Sodium water solution, stirring are filtered after ten minutes, and obtained solid is bis- (sulfoamido alcohol) the diester P3-A of dicarboxylic acids.1H NMR (500MHz, DMSO) δ 8.29 (d, J=7.7Hz, 2H), 8.13 (d, J=7.5Hz, 2H), 8.09-8.03 (m, 6H), 8.00 (t, J=7.5Hz, 2H), 4.61 (t, J=4.9Hz, 4H), 4.16 (t, J=4.8Hz, 4H)13C NMR (126MHz, DMSO) δ 165.3,159.2,137.2,136.3,135.7,133.9,129.9,126.7,125.6,122.1,62.6,38.4.HR-MS (ESI-TOF) calculated value C26H21N2O10S2 +[M+H]+: 585.0632, measured value 585.0617.
Table 1: experiment parameter of the different fluoroform sulphonates as catalyst
For embodiment 1-4, using the trifluoromethanesulfonic acid salt catalyst of different activities, the activity of polyester degradation has biggish Difference.When using trifluoromethanesulfonic acid hafnium as catalyst, the yield highest of catabolite P3-A, not degradable obtained by the reaction Proportion of products is minimum (< 5%).
It is tested below using 5mol% trifluoromethanesulfonic acid hafnium as catalyst, saccharin inventory is to contain polyester weight in polymer 100mol% is added on the basis of the amount of the substance of multiple unit, under conditions of steady temperature is 150 DEG C, reacts 24 hours, investigates Influence using different solvents to monomer yield.
Embodiment 5-9
A kind of biodegrading process of PET polyester, specific steps are as follows:
Sequentially add 96mg PET polyester chips in 5mL reaction flask, 91.5mg saccharin, 17.8mg trifluoromethanesulfonic acid hafnium, And different solvents described in table 2.Reaction bottle closure be heated to 150 DEG C, steady temperature be 150 DEG C under conditions of, stir into Row depolymerization reaction 24 hours.Solvent is removed after completion of the reaction, then the sodium hydrate aqueous solution of 15mL 0.5M is added into system, Stirring is filtered after ten minutes, and obtained solid is catabolite P3-A.
Table 2: solvent and the experiment parameter of concentration variation
It is concluded that under equal conditions from embodiment 5-9, when the reaction is using chlorobenzene as solvent, products therefrom P3-A's Yield highest, oligoester substitution product content are minimum.However consider the environment friendly of solvent, our selection toluene are made molten Agent, while filtering out when the concentration containing polyester repetitive unit in reaction system is 0.5M, polyester being capable of degradable Cheng Dan Body, and the yield highest of catabolite P3-A.
Finally, we are using trifluoromethanesulfonic acid hafnium as catalyst, using toluene as solvent, polyester will be contained in system and repeat list The concentration of member is adjusted to 0.5M, under conditions of steady temperature is 150 DEG C, investigates the inventory variation of substrate and catalyst and anti- Answer influence of the time change to product yield.
Embodiment 10-13
A kind of biodegrading process of PET polyester, specific steps are as follows:
Sequentially add the PET polyester chips such as 3 ingredient proportion of table in 5mL reaction flask, saccharin, trifluoromethanesulfonic acid hafnium, with And 2mL toluene.Reaction bottle closure is heated to 150 DEG C, and under conditions of steady temperature is 150 DEG C, stirring carries out depolymerization reaction phase Between seasonable.Solvent is removed after completion of the reaction, then the sodium hydrate aqueous solution of 15mL0.5M is added into system, and stirring is after ten minutes Filtering, obtained solid is catabolite P3-A.
Table 3: the experiment parameter of the variation of the inventory of substrate and catalyst and reaction time variation
From above embodiments, we are obtained, the reaction is using 5mol% trifluoromethanesulfonic acid hafnium as catalyst, in polymer Equivalent saccharin is put on the basis of the amount of substance containing polyester repetitive unit, under conditions of steady temperature is 150 DEG C, reaction 12~24 hours, polyester degradation was more complete, and the yield of products therefrom P3-A is close；And the amount of catalyst is down to 2mol% When, system is then degraded not exclusively, and the yield of product P3-A is lower.
It is obtained from above-mentioned all embodiments, the optimization degradation condition of this method are as follows: with 5mol% trifluoromethanesulfonic acid hafnium work For catalyst, equivalent raw material PET polyester repetitive unit and saccharin are put into, using toluene as solvent, concentration 0.5M, system exists It is stirred to react under 150 DEG C of steady temperature 24 hours, polyester fully degraded can be made, mainly obtain catabolite terephthalic acid (TPA) P1-A and bis- (sulfoamido alcohol) the diester P3-A of dicarboxylic acids.
In the last handling process of reaction, it has been found that P3-A has fraction in alkali process and is hydrolyzed, with carboxylic acid sodium The form of salt enters water phase, so that the separation yield of product may be more slightly lower than practical conversion yields；Meanwhile a small amount of dicarboxylic acids Sulfoamido alcohol monoesters P2-A can also enter water phase in the form of sodium salt, increase and extract isolated workload.So it is contemplated that Catabolite P2-A and P3-A are further hydrolyzed to terephthalic acid (TPA) and sulfonamide ethyl alcohol directly in system, improved to benzene two The yield of formic acid, while simplifying operation.The catabolite of PET polyester is further hydrolyzed and is also had the advantage that, the first step Issuable a small amount of not exclusively depolymerization, the polyester with sulfoamido alcohol residue, can also be hydrolyzed to phase in degradation process With catabolite terephthalic acid (TPA) and sulfonamide ethyl alcohol, thus to the greatest extent the terephthalic acid (TPA) in recycled PET polyester and Ethylene glycol segment.
After the completion of object degradation to be polymerized, aqueous alkali is directly added into system by the way of basic hydrolysis for we, It is stirred to react the corresponding time under relevant temperature, the degradation of mixture generated in system is further hydrolyzed to terephthalic acid (TPA) P1-A With sulfonamide ethyl alcohol P4-A.This method is not required to purification intermediate product, and easy to operate, resulting two final catabolites are easy to point From: organic phase is removed by liquid separation, and resulting solid is P1-A after water phase is acidified, and filtering can purify；And P4-A dissolves In filtrate, product can be obtained with organic solvent such as ethyl acetate extraction.
Embodiment 14:
192mg PET polyester chips, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL are added in the reaction flask of 15mL Toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 4mL is added into system The sodium hydrate aqueous solution of 6M, sealing are heated to 60 DEG C, and reaction 3 hours is hydrolyzed in stirring.To after completion of the reaction, by reaction solution It is transferred in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified with the hydrochloric acid of 1M To pH~4,160mg terephthalic acid (TPA) P1-A solid, separation yield 97% are filtered to obtain.1H NMR (500MHz, DMSO) δ 13.31 (s, 2H), 8.05 (s, 4H) filtrates are extracted with 20mL ethyl acetate, remove ethyl acetate up to 220mg sulfonamide ethyl alcohol P4-A, Separation yield 90%.1H NMR (500MHz, DMSO) δ 13.72 (s, 1H), 8.01-7.83 (m, 1H), 7.81-7.60 (m, 3H), 7.02 (s, 1H), 4.77 (s, 1H), 3.40 (t, J=5.9Hz, 2H), 2.89 (d, J=3.7Hz, 2H)13C NMR (126MHz, DMSO) 169.4 δ, 138.0,133.4,133.1,131.3,129.9,129.0,60.1,45.7.HR-MS (ESI-TOF) are calculated Value C9H10NO5S-[M-H]-: 244.0285, measured value 244.0281.
Embodiment 15:
192mg PET polyester chips, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL are added in the reaction flask of 15mL Toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 4mL is added into system The potassium hydroxide aqueous solution of 6M, sealing are heated to 60 DEG C, and reaction 5 hours is hydrolyzed in stirring.To after completion of the reaction, by reaction solution It is transferred in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified with the hydrochloric acid of 1M To pH~4,157mg terephthalic acid (TPA) P1-A solid, separation yield 95% are filtered to obtain.Filtrate is extracted with 20mL ethyl acetate, is removed Go ethyl acetate up to 212mg sulfonamide ethyl alcohol P4-A, separation yield 87%.
Embodiment 16:
192mg PET polyester chips, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL are added in the reaction flask of 15mL Toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 4mL is added into system The lithium hydroxide aqueous solution of 6M, sealing are heated to 60 DEG C, and reaction 5 hours is hydrolyzed in stirring.To after completion of the reaction, by reaction solution It is transferred in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified with the hydrochloric acid of 1M To pH~4,162mg terephthalic acid (TPA) P1-A solid, separation yield 98% are filtered to obtain.Filtrate is extracted with 20mL ethyl acetate, is removed Go ethyl acetate up to 205mg sulfonamide ethyl alcohol P4-A, separation yield 84%.
Embodiment 17:
192mg PET polyester chips, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL are added in the reaction flask of 15mL Toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 6mL is added into system The sodium hydrate aqueous solution of 1M, sealing are heated to 100 DEG C, and reaction 5 hours is hydrolyzed in stirring.To after completion of the reaction, react Liquid is transferred in the separatory funnel of 125mL, and 20mL water and 20mL ethyl acetate, liquid separation is added.The hydrochloric acid acid of gained water phase 1M Change to pH~4, filters to obtain 153mg terephthalic acid (TPA) P1-A solid, separation yield 93%.Filtrate is extracted with 20mL ethyl acetate, Ethyl acetate is removed up to 196mg sulfonamide ethyl alcohol P4-A, separation yield 80%.
Embodiment 18:
192mg PET polyester chips, 185mgN- methyl para toluene sulfonamide, 35mg tri- are added in the reaction flask of 15mL Fluorine methanesulfonic acid hafnium and 2mL toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, The sodium hydrate aqueous solution of 4mL 6M is added into system, sealing is heated to 60 DEG C, and reaction 5 hours is hydrolyzed in stirring.To anti- After answering, reaction solution is transferred in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water PH~4 mutually are acidified to the hydrochloric acid of 1M, filter to obtain 158mg terephthalic acid (TPA) P1-A solid, separation yield 96%.Gained organic phase Solvent is removed under reduced pressure, then purifies to obtain 128mg sulfonamide ethyl alcohol P4-B, separation yield 56%.1H NMR (400MHz, CDCl3)δ 7.69 (d, J=8.0Hz, 2H), 7.34 (d, J=7.8Hz, 2H), 3.76 (t, J=5.2Hz, 2H), 3.15 (t, J=5.3Hz, 2H), 2.82 (s, 3H), 2.43 (s, 3H)13C NMR (101MHz, CDCl3) δ 143.5,134.1,129.8,127.5,60.3, 52.5,36.1,21.5.
Embodiment 19:
192mg PET polyester chips, 171mg para toluene sulfonamide, 35mg trifluoro methylsulphur are added in the reaction flask of 15mL Sour hafnium and 2mL toluene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, to system The middle sodium hydrate aqueous solution that 4mL 6M is added, sealing are heated to 60 DEG C, stir 5 hours.To which after completion of the reaction, reaction solution is turned It moves in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified to the hydrochloric acid of 1M 162mg terephthalic acid (TPA) P1-A solid, separation yield 98% are filtered to obtain in pH~4.Solvent is removed under reduced pressure in gained organic phase, then Purify to obtain 133mg sulfonamide ethyl alcohol P4-C, separation yield 62%.1H NMR (400MHz, CDCl3) δ 7.75 (d, J=8.3Hz, 2H), 7.30 (d, J=8.1Hz, 2H), 3.68 (t, J=4.8Hz, 2H), 3.07 (t, J=4.9Hz, 2H), 2.42 (s, 3H)13C NMR (101MHz, CDCl3) δ 143.6,136.6,129.8,127.1,61.3,45.2,21.5.
Embodiment 20:
242mg PBN polyester granulate, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL are added in the reaction flask of 15mL Chlorobenzene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 4mL is added into system The sodium hydrate aqueous solution of 6M, sealing are heated to 80 DEG C, and reaction 5 hours is hydrolyzed in stirring.To after completion of the reaction, by reaction solution It is transferred in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified with the hydrochloric acid of 1M To pH~4,207mg 2,6-naphthalenedicarboxylic acid P1-B solid, separation yield 96% are filtered to obtain.Filtrate is extracted with 20mL ethyl acetate, Ethyl acetate is removed up to 203mg sulfonamide ethyl alcohol P4-A, separation yield 83%.
Embodiment 21:
182mg PEF polyester, 183mg saccharin, 35mg trifluoromethanesulfonic acid hafnium and 2mL chlorine are added in the reaction flask of 15mL Benzene.Reaction bottle closure is heated to 150 DEG C, and stirring carries out depolymerization reaction 24 hours.It is cooled to room temperature, 4mL 6M is added into system Sodium hydrate aqueous solution, sealing is heated to 60 DEG C, and reaction 5 hours is hydrolyzed in stirring.To which after completion of the reaction, reaction solution is turned It moves in the separatory funnel of 125mL, 20mL water and 20mL ethyl acetate, liquid separation is added.Gained water phase is acidified to the hydrochloric acid of 1M 143mg 2,5-furandicarboxylic acid P1-C solid, separation yield 92% are filtered to obtain in pH~4.Filtrate is extracted with 20mL ethyl acetate, Ethyl acetate is removed up to 192mg sulfonamide ethyl alcohol P4-A, separation yield 78%.

Claims (13)

1. a kind of method of degradation polymer characterized by comprising by polymer, sulfonamide and lewis acid catalyst Mix simultaneously depolymerization；The polymer includes the polyester repetitive unit that dicarboxylic acids and diol copolymer are formed.
2. the method for degradation polymer as described in claim 1, which is characterized in that the depolymerization product is small molecule mixing Object, including dibasic carboxylic acid monomers, dicarboxylic acids sulfoamido alcohol monoesters and bis- (sulfoamido alcohol) diester of dicarboxylic acids.
3. the method for degradation polymer as described in claim 1, which is characterized in that the two of the repetitive unit of the polymer First carboxylic acid is selected from terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 1, At least one of 4- naphthalenedicarboxylic acid；Dihydric alcohol is selected from least one of ethylene glycol, 1,3-PD and 1,2-PD.
4. the method for degradation polymer as described in claim 1, which is characterized in that the lewis acid catalyst is trifluoro Mesylate.
5. the method for degradation polymer as claimed in claim 4, which is characterized in that the trifluoromethanesulfonic acid salt catalyst is Sc(OTf)3, Fe (OTf)3, Al (OTf)3, Zr (OTf)4Or Hf (OTf)4。
6. the method for degradation polymer as described in claim 1, which is characterized in that the amine residues of the sulfonamide contain N-H key.
7. the method for degradation polymer as claimed in claim 6, which is characterized in that the sulfonamide is o-benzoyl sulphonyl Imines, para toluene sulfonamide, N- methyl para toluene sulfonamide.
8. the method for degradation polymer as described in claim 1, which is characterized in that the method for the degradation polymer is also wrapped It includes and further alkaline condition hydrolysis and acidification separation and Extraction is carried out to the ester functional group in gained depolymerization product, obtain binary carboxylic Acid and sulfoamido alcohol.
9. the method for degradation polymer as described in claim 1, which is characterized in that the lewis acidic inventory is with poly- It is 0.1~20.0mol% on the basis of the amount for closing the substance in object containing the repetitive unit.
10. the method for degradation polymer as described in claim 1, which is characterized in that the sulfonamide inventory is to polymerize It is 1%~200mol% on the basis of the amount of substance in object containing the repetitive unit.
11. the method for degradation polymer as described in claim 1, which is characterized in that the depolymerization reaction uses nonpolarity Organic solvent.
12. the method for degradation polymer as claimed in claim 11, which is characterized in that the solvent is selected from toluene, diformazan One of benzene and chlorobenzene are a variety of.
13. the method for degradation polymer as described in claim 1, which is characterized in that the temperature of the depolymerization reaction is 100 ~180 DEG C.
CN201810597098.1A 2018-05-30 2018-05-30 Method for degrading polymer Active CN108947798B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201810597098.1A CN108947798B (en) 2018-05-30 2018-05-30 Method for degrading polymer
CN202110199167.5A CN112961045A (en) 2018-05-30 2018-05-30 Method for degrading polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810597098.1A CN108947798B (en) 2018-05-30 2018-05-30 Method for degrading polymer

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN202110199167.5A Division CN112961045A (en) 2018-05-30 2018-05-30 Method for degrading polymer

Publications (2)

Publication Number Publication Date
CN108947798A true CN108947798A (en) 2018-12-07
CN108947798B CN108947798B (en) 2021-03-02

Family

ID=64488123

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201810597098.1A Active CN108947798B (en) 2018-05-30 2018-05-30 Method for degrading polymer
CN202110199167.5A Pending CN112961045A (en) 2018-05-30 2018-05-30 Method for degrading polymer

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202110199167.5A Pending CN112961045A (en) 2018-05-30 2018-05-30 Method for degrading polymer

Country Status (1)

Country Link
CN (2) CN108947798B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114377726A (en) * 2021-08-05 2022-04-22 清华大学 Plastic hydrolysis method using binuclear metal complex catalyst
WO2022171029A1 (en) * 2021-02-10 2022-08-18 上海科技大学 Polyester degradation method
CN115103830A (en) * 2019-12-19 2022-09-23 伊士曼化工公司 Method for producing dimethyl terephthalate by polyester methanol decomposition depolymerization system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070176A (en) * 1974-10-08 1978-01-24 Sumitomo Chemical Company, Limited Method for controlling the growth of plants
US6706755B2 (en) * 2001-06-13 2004-03-16 Allergan, Inc. Cyclopentane heptan(ene) acyl sulfonamide, 2-alkyl or 2-arylalkyl, or 2-heteroarylalkenyl derivatives as therapeutic agents
CN1665773A (en) * 2002-07-09 2005-09-07 隆萨股份公司 Process for the preparation of i n /i -monosubstituted beta-amino alcohols
CN105085272A (en) * 2015-08-28 2015-11-25 王帅 Synthesis method for aryl or heteroaryl ester compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070176A (en) * 1974-10-08 1978-01-24 Sumitomo Chemical Company, Limited Method for controlling the growth of plants
US6706755B2 (en) * 2001-06-13 2004-03-16 Allergan, Inc. Cyclopentane heptan(ene) acyl sulfonamide, 2-alkyl or 2-arylalkyl, or 2-heteroarylalkenyl derivatives as therapeutic agents
CN1665773A (en) * 2002-07-09 2005-09-07 隆萨股份公司 Process for the preparation of i n /i -monosubstituted beta-amino alcohols
CN105085272A (en) * 2015-08-28 2015-11-25 王帅 Synthesis method for aryl or heteroaryl ester compound

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIANG, HANBING等: "Palladium-catalyzed cascade metallo-ene/Suzuki coupling reaction of allenamides", 《ROYAL SOCIETY OF CHEMISTRY》 *
PARUL GOEL等: "Discovery and Biological Evaluation of Potent and Selective N‑ Methylene Saccharin-Derived Inhibitors for Rhomboid Intramembrane Proteases", 《BIOCHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115103830A (en) * 2019-12-19 2022-09-23 伊士曼化工公司 Method for producing dimethyl terephthalate by polyester methanol decomposition depolymerization system
WO2022171029A1 (en) * 2021-02-10 2022-08-18 上海科技大学 Polyester degradation method
CN114377726A (en) * 2021-08-05 2022-04-22 清华大学 Plastic hydrolysis method using binuclear metal complex catalyst

Also Published As

Publication number Publication date
CN112961045A (en) 2021-06-15
CN108947798B (en) 2021-03-02

Similar Documents

Publication Publication Date Title
CN108947798A (en) A kind of method of degradation polymer
JP2008088096A (en) Method for producing bis-(2-hydroxyethyl) terephthalate and method for producing polyethylene terephthalate
CN105873895A (en) Method for forming an aromatic diacid and/or an aromatic diacid precursor from a polyester-containing feedstock
CN115678030B (en) Mechanochemical method for preparing metal-organic framework material
CN102924266A (en) Method for preparing phthalic acid by xylol co-oxidation catalyst system
CN112876359B (en) Preparation method of dimethyl 2, 6-naphthalene dicarboxylate
EP0204119B1 (en) Process for producing 2,6-naphthalenedicarboxylic acid
JP4330918B2 (en) How to recycle polyester waste
CN103965039A (en) Method for synthesizing 2,6-naphthalenedicarboxylic acid
JP2013177331A (en) Method for recovering triethylamine and acetone from waste liquid produced in manufacture of naphthalenedicarboxylic acid
JP2002060369A (en) Method for recycling polyester waste
JP2000034341A (en) Polycondensation for polyester using lithium titanyloxalate catalyst
JPH01180851A (en) Production of 2,6-naphthalenedicarboxylic acid
CN113549035B (en) Process for preparing 2, 5-furandicarboxylic acid from furfural
KR20240003511A (en) Hybrid Chemical Depolymerization of Polymer Containing Ester Bonds using a Mixture of Alcohol and Carbonyl Compound
TW574208B (en) Process for removing titanium oxide or iron oxide red from depolymerization products from with ethylene glycol solvolysis of polyesters containing titanium oxide or iron oxide red
JP4390968B2 (en) Polyester production method
JP2005105091A (en) Polyalkylene terephthalate waste-treated mass and treating method therefor
JP4496045B2 (en) Polyester production method
JP2002167354A (en) Terephthalic acid component
CN112645811A (en) Method for preparing 2,6-naphthalene dicarboxylic acid by oxidizing 2, 6-diisopropyl naphthalene
CN1915959A (en) New method for synthesizing p-isopropyl benzoic acid
JP4397718B2 (en) Method for producing 2,6-naphthalenedicarboxylic acid
JP4669272B2 (en) Method for producing polyethylene terephthalate using bis- (2-hydroxyethyl) terephthalate as a raw material
JP2002161064A (en) Terephthalic acid composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant