CN108837847A - The catalyst and method of alcohol polylactic acid - Google Patents
The catalyst and method of alcohol polylactic acid Download PDFInfo
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- CN108837847A CN108837847A CN201810609405.3A CN201810609405A CN108837847A CN 108837847 A CN108837847 A CN 108837847A CN 201810609405 A CN201810609405 A CN 201810609405A CN 108837847 A CN108837847 A CN 108837847A
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 80
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 230000005496 eutectics Effects 0.000 claims abstract description 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 235000019441 ethanol Nutrition 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 5
- 235000019743 Choline chloride Nutrition 0.000 claims description 5
- 229960003178 choline chloride Drugs 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 abstract description 13
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 abstract description 13
- 229940057867 methyl lactate Drugs 0.000 abstract description 13
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 7
- 238000006140 methanolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910007339 Zn(OAc)2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical group CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the alcoholysis reactions of polylactic acid, disclose the catalyst and method of catalysis polylactic acid (PLA) alcoholysis recycling methyl lactate.This method is with eutectic solvent ChCl-Zn (OAc)2For catalyst, alcoholysis reaction occurs for reactant polylactic acid and alcohol, generates lactate.Catalyst And Method provided by the invention can effectively improve the percent alcoholysis of PLA and the yield of lactate, while the synthetic method of the catalyst is simple, and low in cost, dosage is few, be conducive to industrial production.
Description
Technical field
The present invention relates to the catalyst of alcohol polylactic acid and methods.
Background technique
Polylactic acid (PLA) is the polymer obtained with lactic acid for main polymerizable raw material, and raw material sources are abundant and can be again
It is raw.The production process of polylactic acid is pollution-free, and product can be biodegradable, realizes circulation in nature, therefore is reason
The Green Polymer Material thought.With the extensive use of PLA, the quantity of production and consumption is sharply increased, and is eventually led to waste and old
The accumulation of polylactic acid is growing.Although polylactic acid can be degradable in nature, since degradation cycle is too long, it is degraded
The carbon dioxide generated afterwards can pollute air, therefore aggravation greenhouse effects will not only pay attention to the PRODUCTION TRAITS of PLA, more infuse
The degradation and recycling of weight PLA.
The pyrolysis method of polylactic acid is to carry out in the molten state mostly, and reaction needs higher temperature, and high polymer
Chain rupture is random, and the by-product of generation is more, it is difficult to the target product of high-purity is obtained, so compared with pyrolysis method, chemistry
Depolymerization rule is more practical, and wherein alcoholysis method is a kind of one of effective way, for example S á nchez etc. has studied zinc acetate catalysis PLA
With the alcoholysis reaction of polyethylene terephthalate (PET) mixture, experiment uses infrared spectroscopy (FT-IR), nuclear magnetic resonance
Hydrogen spectrum (1H NMR) and carbon-13 nmr spectra (13C NMR) etc. technologies its product is characterized.Experiment discovery：Compare second
Other solvents such as pure and mild ethylene glycol, alcoholysis reaction is more preferable in methyl alcohol for mixture, and at normal atmospheric pressure, back flow reaction
The yield of 15h, PLA alcoholysis product methyl lactate can reach 65%, but PET hardly reacts, and with this condition, reach from waste and old
The purpose of selective recovery PLA in plastic hybrid.Catalyst PLA and methanol are used ionic liquid as in the prior art
Alcoholysis reaction, catalytic effect is significant, although ionic liquid can recycle catalyst as catalyst, ionic liquid price is high
Expensive, preparation is complicated, is unfavorable for industrial applications, and the synthesis of ionic liquid, purification and recovery process are all using largely waving
Hair property organic solvent, ionic liquid as catalyst or solvent end some to be lost in environment, environment will be caused not
With the influence of degree.Therefore, it is higher to seek a kind of new catalytic efficiency, energy recycling, cost of material is cheap, synthesizes
The catalyst polylactic acid alcoholysis reaction of journey simplicity is of great significance.
Summary of the invention
Catalyst amount in order to solve alcohol polylactic acid in the prior art is big, it is at high cost, can not biodegrade, catalysis
Effect need the problem of being improved, and the present invention provides the catalyst of alcohol polylactic acid.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
The present invention provides the catalyst of alcohol polylactic acid, it is low which is that choline chloride and zinc acetate are prepared
Congruent melting solvent (DES) ChCl-Zn (OAc)2；The eutectic solvent ChCl-Zn (OAc)2Preparation method be：In nitrogen protection
Under, molar ratio 1:1 choline chloride and zinc acetate, heating stirring reacts 2h at 80-100 DEG C, until solid mixture becomes
Transparent supernatant liquid generates eutectic solvent ChCl-Zn (OAc)2。
Originally, inventor tests catalyst of a variety of eutectic solvents as alcoholysis PLA, but much to PLA alcoholysis
All without catalytic effect, inventor or even the initial effort for once abandoning searching suitable catalyst PLA alcoholysis, however with
The progress of test, we have surprisingly found that, acid eutectic solvent to PLA alcoholysis almost without catalytic effect, and specific kind
The alkaline eutectic solvent choline chloride class eutectic solvent ChCl-Zn (OAc) of class2There is catalytic effect to PLA alcoholysis, studies carefully its original
Cause, it may be possible to which, because PLA alcoholysis reaction is a nucleophilic substitution, the alkalinity of nucleopilic reagent is stronger, and nucleophilic substitution is got over
It is easy to carry out.The present invention further explores ChCl-Zn by infrared spectroscopy (IR) and semimicro gel permeation chromatography (GPC)
(OAc)2It is catalyzed the reaction mechanism of PLA alcoholysis, is found by IR and GPC：With the increase of conversion ratio, the oligomer of small-molecular-weight
Gradually increase, the high polymer of macromolecule gradually decreases, and thus speculates eutectic solvent ChCl-Zn (OAc)2It is catalyzed PLA alcohol
The possibility reaction mechanism of solution, ChCl-Zn (OAc)2Hydrogen bond is formed with alcohol, causes the nucleophilicity of alcohol to improve, is conducive to alcohol attack PLA
Chain causes PLA chain to be broken, and forms the polymer of different molecular weight, with the continuous fracture of PLA chain, has ultimately generated target production
Object lactate.
The present invention also provides the methods of alcohol polylactic acid, with above-mentioned eutectic solvent ChCl-Zn (OAc)2For catalyst,
Alcoholysis reaction occurs for reactant polylactic acid and alcohol, generates lactate；The temperature of specific alcoholysis reaction is 110-130 DEG C, reaction
Time be 1-3h, the molar ratio of reactant polylactic acid and alcohol is 1:2-7, catalyst ChCl-Zn (OAc)2With the matter of polylactic acid
Amount is than being 0.06-0.14:1.
Preferably, the temperature of the alcoholysis reaction is 125 DEG C, time of reaction is 3h, reactant polylactic acid and alcohol
Molar ratio is 1:7, catalyst eutectic solvent ChCl-Zn (OAc)2Mass ratio with polylactic acid is 0.06:1.
Preferably, the alcohol is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol or isobutanol；The type of Organic Alcohol
It is not specifically limited, can reasonably be selected according to needs of production, it is the most frequently used to can choose polylactic acid alcoholysis reaction
Methanol carry out alcoholysis.
The present invention also provides the method for alcohol polylactic acid further include post-processing step, this step is to use alcoholysis reaction liquid
Alcohol is transferred in container bottle together, by obtaining product liquid lactate after air-distillation, vacuum distillation, the residual use of the kettle after distillation
Alcohol dissolution is used as catalyst circulation.
Compared with the common catalyst of the prior art, the present invention uses environmentally protective, cheap, efficient ChCl-Zn
(OAc)2Eutectic solvent is used to be catalyzed the alcoholysis reaction of PLA, which has well PLA alcoholysis
Catalytic action, catalyst is not only low in cost, production is simple, can also recycle, can make up traditional catalyst not
Foot；ChCl-Zn (OAc) simultaneously2Eutectic solvent has a difficult volatilization, fire retardant, nontoxic property, and the eutectic solvent be can
It is biodegradable, can to avoid ionic liquid as catalyst or solvent eventually some to be lost in environment, will be to environment
Cause different degrees of influence.Test result shows catalyst provided by the invention and method, and PLA percent alcoholysis can reach substantially
The yield of 93.5-98.9%, lactate can reach 90.8-93.7%.From the above technical scheme, the present invention uses ChCl-
Zn(OAc)2Eutectic solvent is catalyzed PLA alcoholysis, can effectively improve the percent alcoholysis of PLA and the yield of lactate, while this is urged
The synthetic method of agent is simple, low in cost, and dosage is few, is conducive to industrial production.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the PLA Methanolysis product of embodiment 5 and the infrared spectrogram of methyl lactate standard specimen；
Fig. 2 is the gas chromatogram of the PLA Methanolysis reaction product of embodiment 5；
Fig. 3 is ChCl-Zn (OAc) in embodiment 62Reuse Performance comparison diagram；
Fig. 4 is reuse front and back ChCl-Zn (OAc) in embodiment 62Infrared spectrogram.
Specific embodiment
The invention discloses the catalyst of alcohol polylactic acid and methods.Those skilled in the art can use for reference present disclosure,
It is suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications carry out those skilled in the art
Say it is it will be apparent that they are considered as including in the present invention.Method and application of the invention has passed through preferably real
Example is applied to be described, related personnel obviously can not depart from the content of present invention, in spirit and scope to method described herein
It is modified or appropriate changes and combinations with application, carrys out implementation and application the technology of the present invention.
In order to enable those skilled in the art to better understand the present invention, With reference to embodiment to the present invention
It is described in further detail.
Embodiment 1ChCl-Zn (OAc)2The preparation of eutectic solvent
Under nitrogen protection, molar ratio 1:1 choline chloride and zinc acetate, heating stirring reacts 2h at 90 DEG C, until
Solid mixture becomes transparent supernatant liquid, generates eutectic solvent ChCl-Zn (OAc)2。
The selection of embodiment 2PLA alcoholysis reaction condition
With ChCl-Zn (OAc)2It for catalyst, selects methyl lactate yield for standard, is analyzed by Responds Surface Methodology anti-
Between seasonable, the influence of reaction temperature, catalyst amount and methanol usage to experiment, filter out preferable reaction condition.
According in table 1 four empirical factors and three level designs carried out 29 groups of experiments, experimental result is shown in Table 2, to table 2
Experimental data carried out variance analysis, regression model variance analysis the results are shown in Table 3.
1 response surface experiments factor level table of table
2 response surface experiments scheme of table and result
3 regression model variance analysis of table
According to regression coefficient estimated value it is found that each factor contribution ratio is：B>C>A>D, i.e., four factors are to PLA Methanolysis
Reaction influences size：Reaction time>Catalyst amount>Reaction temperature>Methanol usage.
After single factor exploration, optimization obtains ChCl-Zn (OAc)2Being catalyzed the preferable condition that PLA Methanolysis reacts is：T
=125 DEG C, t=3h, m (ChCl-Zn (OAc)2)：M (PLA)=0.06：1, n (PLA):N (methanol)=7：1, with this condition
Product methyl lactate yield reach as high as 93.7%.
Embodiment 3PLA alcoholysis reaction
Prepare a polytetrafluoroethyllining lining and magneton is added, the PLA that quality is 4g is added inward, adding quality is
The ChCl-Zn (OAc) of 0.56g2, it is eventually adding a certain amount of isopropanol, n (PLA):N (isopropanol)=7, is put into band for liner
In the autoclave for having magnetic agitation and thermometer, 2h is reacted at 110 DEG C, after reaction, is cooled to room temperature, after opening kettle
Reaction solution is transferred in single port bottle, it is multiple to wash liner with a small amount of isopropanol, is transferred in single port bottle together, in condition of normal pressure
The unreacted isopropanol of lower distillation, then be evaporated under reduced pressure and collect product liquid (quality 6.66g), the product is through INFRARED SPECTRUM chart
Levying the product is isopropyl lactate；Kettle residual (mass of residue 0.82g) after distillation is dissolved with isopropanol, can be directly as catalysis
Agent recycling；PLA percent alcoholysis is 93.5%, and the yield of isopropyl lactate is 90.8%.
Wherein, M (PLA) represents the molal weight of PLA repetitive unit, and M (lactate) represents the molal weight of lactate.
Embodiment 4PLA alcoholysis reaction
Prepare a polytetrafluoroethyllining lining and magneton is added, the PLA that quality is 4g is added inward, adding quality is
The ChCl-Zn (OAc) of 0.24g2, it is eventually adding a certain amount of ethyl alcohol n (PLA):N (ethyl alcohol)=2；Liner is put into magnetic force
In the autoclave of stirring and thermometer, 2.5h being reacted at 120 DEG C, after reaction, is cooled to room temperature, opening will be anti-after kettle
Liquid is answered to be transferred in single port bottle, it is multiple with a small amount of ethanol washing liner, it is transferred in single port bottle, distills in atmospheric conditions together
Unreacted ethyl alcohol, then be evaporated under reduced pressure, it is lactic acid second that distillating liquid product (quality 6g), which characterizes the product through infrared spectrum,
Ester；Remaining kettle residual (quality 0.45g) will be distilled to be dissolved with ethyl alcohol, it can be directly as catalyst recycling；PLA alcoholysis
Rate is 94.8%, and the yield of ethyl lactate is 91.5%.
Embodiment 5PLA alcoholysis reaction
Prepare a polytetrafluoroethyllining lining and magneton is added, the PLA that quality is 4g is added inward, adding quality is
The ChCl-Zn (OAc) of 0.24g2, it is eventually adding a certain amount of methanol, n (PLA):N (methanol)=1:7；Liner is put into and is had
In the autoclave of magnetic agitation and thermometer, 3h is reacted at 125 DEG C, after reaction, is cooled to room temperature, and is incited somebody to action after opening kettle
Reaction solution is transferred in single port bottle, and it is multiple to wash liner with a small amount of methanol, is transferred in single port bottle, is steamed together in atmospheric conditions
Unreacted methanol is evaporated, then is evaporated under reduced pressure to obtain product liquid (quality 5.43g), the infrared spectrum and cream of the product liquid
The infrared spectrum of sour methyl esters standard specimen as shown in Figure 1, PLA Methanolysis reaction product gas chromatogram；Residual (the matter of kettle after distillation
Amount is 0.3g) it is dissolved with methanol, it can be directly as catalyst recycling；PLA percent alcoholysis is that the yield of 98.5%, BPA is
93.7%.
In Fig. 1, a is standard specimen infrared spectrogram, and b is alcoholysis product infrared spectrogram, 3445cm-1Place belongs to stretching for O-H
Contracting vibration absorption peak, 2986cm-1、2957cm-1The stretching vibration absworption peak of place ownership C-H, 1743cm-1It is the flexible vibration of C=O
The raw peak of movable property, 1372cm-1It is-CH3Bending vibration absorption peak, 1223cm-1、1132cm-1It is absorbed for the stretching vibration of C-O
Peak, it is exactly methyl lactate that infrared analysis, which demonstrates alcoholysis product, and the infrared spectrum of product and methyl lactate standard specimen is compared,
It was found that two curves substantially completely coincide, show that PLA Methanolysis product is exactly methyl lactate.
Fig. 2 data show that a is the gas chromatogram of standard specimen, and b is the gas phase spectrogram of product, under identical testing conditions,
Compared with the gas chromatogram of methyl lactate standard specimen, go out peak position and the retention time of product are coincide substantially with standard specimen, thus may be used
Determine that reaction product is methyl lactate.The purity that methyl lactate is obtained according to spectrogram is 100%.
6 catalyst ChCl-Zn (OAc) of embodiment2Recycling
To catalyst ChCl-Zn (OAc)2It is recycled, the reaction item of the reaction condition and embodiment 5 that recycle
Part is identical, successively come evaluate catalyst PLA Methanolysis experiment repeatability, the results are shown in Table 4.
Repetition experiment of the table 4 under preferable reaction condition
4 data of table show, the catalyst ChCl-Zn (OAc) that preparation method provided by the invention obtains2It is catalyzed PLA methanol
The repeatability of alcoholysis experiment is good.
To ChCl-Zn (OAc)2Reuse performance investigated, as a result see Fig. 3.ChCl-Zn as can be seen from Figure 3
(OAc)2For the first time, PLA conversion ratio 98.3%, methyl lactate yield 93.5% varies less compared with before reuse for reuse；Reuse
After 5 times, PLA conversion ratio and methyl lactate yield can also maintain higher value, illustrate ChCl-Zn (OAc)2In PLA methanol
There is good reuse performance in alcoholysis reaction, before and after reuse, ChCl-Zn (OAc)2Catalytic activity be basically unchanged.
In order to further verify DES with good reuse performance, to reuse 5 times ChCl-Zn (OAc)2With it is fresh
ChCl-Zn(OAc)2Structural characterization is carried out, characterization structure is shown in Fig. 4, the infrared spectrogram before a reuse, infrared after b reuse 5 times
Spectrogram passes through reuse 5 times ChCl-Zn (OAc)2With fresh ChCl-Zn (OAc)2Infrared spectrum compare, find
The ChCl-Zn (OAc) that reuse is 5 times2With fresh ChCl-Zn (OAc)2Main feature absorption peak coincide substantially, before illustrating reuse
Afterwards, ChCl-Zn (OAc)2Structure does not change with composition, further illustrates ChCl-Zn (OAc)2With good reuse
Performance.
The selection of 1 catalyst type of comparative example
Catalyst identical as 5 reaction condition of embodiment, the catalyst of embodiment 5 being successively modified as in table, it is each
The catalytic effect of catalyst is as shown in table 5.Wherein, the preparation of the choline chloride class DES of other classes in table 5 and embodiment 1
Method is identical.
Influence of the different choline chloride class eutectic solvents of table 5 to PLA alcoholysis reaction
5 data of table show that under identical reaction conditions, different catalyst is to have difference to the degradation catalytic effect of PLA
Different.ChCl-C2H2O4·2H2O, ChCl-2 acetamide, ChCl-PTSA, ChCl- succinic acid, ChCl- adipic acid, ChCl- benzene
Formic acid does not have catalytic effect to PLA；And ChCl-2ZnCl2、ChCl-2Urea、ChCl-2CuCl2·2H2O、ChCl-Zn
(OAc)2、ChCl-2MnCl2·4H2O has a degree of catalytic effect to the degradation of polylactic acid, wherein especially with ChCl-
2CuCl2·2H2O and ChCl-Zn (OAc)2Catalytic effect is preferable, but when reuse, eutectic solvent ChCl-2CuCl2·
2H2O generates a large amount of flocculent deposits after adding water, and the structure of catalyst changes, and can not recycle, therefore provided by the invention
ChCl-Zn(OAc)2As catalyst PLA, its catalytic effect is best.And the ChCl-Zn (OAc) that the present invention uses2Preparation
Method is simple, low in cost, eutectic solvent ChCl-Zn (OAc)2Be it is biodegradable, can be to avoid ionic liquid conduct
Catalyst or solvent eventually some to be lost in environment, different degrees of influence will be caused to environment.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. the catalyst of alcohol polylactic acid, which is characterized in that it is low that the catalyst is that choline chloride and zinc acetate are prepared
Congruent melting solvent C hCl-Zn (OAc)2。
2. catalyst as described in claim 1, which is characterized in that the eutectic solvent ChCl-Zn (OAc)2Preparation method
For：Under nitrogen protection, molar ratio 1:1 choline chloride and zinc acetate, heating stirring reacts 2h at 80-100 DEG C, until solid
Body mixture becomes transparent supernatant liquid, generates eutectic solvent ChCl-Zn (OAc)2。
3. the method for alcohol polylactic acid, which is characterized in that with eutectic solvent ChCl-Zn (OAc) of any of claims 1 or 22
For catalyst, alcoholysis reaction occurs for reactant polylactic acid and alcohol, generates lactate.
4. method as claimed in claim 3, which is characterized in that the temperature of the alcoholysis reaction be 110-130 DEG C, reaction when
Between be 1-3h, the molar ratio of reactant polylactic acid and alcohol is 1:2-7, catalyst ChCl-Zn (OAc)2With the mass ratio of polylactic acid
For 0.06-0.14:1.
5. method as claimed in claim 4, which is characterized in that the temperature of the alcoholysis reaction is 125 DEG C, and the time of reaction is
The molar ratio of 3h, reactant polylactic acid and alcohol is 1:7, catalyst eutectic solvent ChCl-Zn (OAc)2With the quality of polylactic acid
Than being 0.06:1.
6. the method as claimed in claim 3 or 4, which is characterized in that the alcohol is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, just
Butanol or isobutanol.
7. method as claimed in claim 3, which is characterized in that further include post-processing step, this step is by alcoholysis reaction liquid
It is transferred in container bottle together with alcohol, by product liquid lactate is obtained after air-distillation, vacuum distillation, the kettle after distillation is residual
Alcohol dissolution is used to use as catalyst circulation.
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| CN112962308A (en) * | 2021-02-08 | 2021-06-15 | 安徽工程大学 | Processing technology and application of hydrophilic polylactic acid fiber |
| CN113754535A (en) * | 2021-09-08 | 2021-12-07 | 中国科学院青岛生物能源与过程研究所 | Method for catalyzing and depolymerizing polylactic acid and analogue thereof by magnesium catalysis system |
| CN115043725A (en) * | 2022-08-04 | 2022-09-13 | 东莞理工学院 | Method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109678703A (en) * | 2019-01-29 | 2019-04-26 | 河南工业大学 | A kind of synthetic method of monoglyceride |
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| CN112962308A (en) * | 2021-02-08 | 2021-06-15 | 安徽工程大学 | Processing technology and application of hydrophilic polylactic acid fiber |
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| CN113754535A (en) * | 2021-09-08 | 2021-12-07 | 中国科学院青岛生物能源与过程研究所 | Method for catalyzing and depolymerizing polylactic acid and analogue thereof by magnesium catalysis system |
| CN115043725A (en) * | 2022-08-04 | 2022-09-13 | 东莞理工学院 | Method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid |
| CN115043725B (en) * | 2022-08-04 | 2024-02-09 | 湖北福星生物科技有限公司 | Method for preparing 2-bromopropionate compound and lactate compound by degrading polylactic acid |
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