CN110003009A - A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate - Google Patents
A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate Download PDFInfo
- Publication number
- CN110003009A CN110003009A CN201910348086.XA CN201910348086A CN110003009A CN 110003009 A CN110003009 A CN 110003009A CN 201910348086 A CN201910348086 A CN 201910348086A CN 110003009 A CN110003009 A CN 110003009A
- Authority
- CN
- China
- Prior art keywords
- oac
- bmim
- sba
- catalyst
- ionic liquid
- 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.)
- Withdrawn
Links
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 26
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 title claims abstract description 24
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 title claims abstract description 24
- 229940057867 methyl lactate Drugs 0.000 title claims abstract description 24
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 title description 30
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 27
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910007339 Zn(OAc)2 Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 235000011056 potassium acetate Nutrition 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000006140 methanolysis reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 240000001414 Eucalyptus viminalis Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses one kind with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is the method that methyl lactate is recycled in catalyst alcoholysis useless poly-lactic acid material (abbreviation PLA), comprising the following steps: m in mass ratioPLA:mCatalyst=1:0.002~0.1, molar ratio nPLA: nMethanol=1:1~10, by PLA, methanol and catalyst [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is added in reaction kettle, alcoholysis reaction is carried out at 90~130 DEG C, reaction terminates that catalyst is recovered by filtration, the unreacted methanol of revolving recycling, is evaporated under reduced pressure and collects product methyl lactate, the conversion ratio of PLA is up to 100%, the yield of product methyl lactate is up to 95% or more, purity is up to 99%, the immobilized ionic liquid of catalyst [Bmim] [OAc]-Zn (OAc)2/ SBA-15 can direct reuse.
Description
Technical field
The invention belongs to waste biomass sill high level conversion technical fields, and in particular to a kind of immobilized ionic liquid
Catalyst [Bmim] [OAc]-Zn (OAc)2The method that/SBA-15 is catalyzed useless polylactic acid (PLA) Methanolysis recycling methyl lactate.
Background technique
As the continuous rise and the mankind of population increase, oil crisis and petrochemical industry based raw material price are to environment and health
The problems such as pay attention to day by day so that the development and utilization of renewable resource increasingly attracts attention.Polylactic acid (PLA)
As a kind of high molecular material of function admirable, there is good biocompatibility, biodegradability, environmentally friendly and good
The advantages that mechanical property got well, be the potential substitute of the petrochemical-based polymers such as polyester, polystyrene, can be applied to industry, agriculture
The fields such as industry, packaging and biomedicine.With the scarcity of petroleum resources and the development of PLA production technology, PLA material is in daily life
Usage amount can increase year by year in work, then a new problem will be become by how handling discarded PLA.Although PLA can be certainly
It degrades under the conditions of so, but degradation cycle is too long, waste is stacked or landfill also can occupied space, pollution environment;In addition, degradation produces
Object carbon dioxide and water are because can not directly carry out cycling and reutilization and a kind of wasting of resources.Therefore, constantly reinforcing PLA system
While standby technical research, the attention of people is also increasingly subject to the recovery and utilization technology research of useless PLA.
Due to the characteristics such as degradable of PLA, it is difficult to pass through as other plastics melting and moulds again, is granulated and the methods of moulds again
Carry out physiochemical mutagens.And the monomer of PLA is all the industrial chemicals or intermediate that added value is higher, widely used, so by it
Burn the method for recovering energy and being also not preferred.And use chemical recycling can be by PLA material in hot or chemical reagent effect
Lower carry out depolymerization, generates corresponding small molecule product, to realize recycling for resource.The chemical recycling reported at present
Mainly there are thermal depolymerization and chemical depolymerization, thermal depolymerization method causes thermal depolymerization product complicated, it is difficult to obtain high-purity since temperature is higher
Product.Therefore, compared with thermal depolymerization, chemical depolymerization method is more effective.Chemical depolymerization method reported in the literature mainly has hydrolysis, alcohol
Solution and enzymatic degradation, wherein alcoholysis method is important one of chemical depolymerization method, in this way, can be raw by useless PLA alcoholysis
At corresponding lactic acid alkyl ester product.
Since PLA is difficult to dissolve in methyl alcohol, need its alcoholysis reaction in high temperature or a large amount of classical acid or base catalysis
Under the conditions of carry out.Currently, the relevant report about alcoholysis method depolymerization PLA is fewer, such as Brake (US Patent
Etc. 5264617) PLA alcoholysis reaction is catalyzed with sulfuric acid, p-methyl benzenesulfonic acid and methane sulfonic acid etc..Ishihara(JP
2009029757 A 20090212) etc. using zinc carbonate or zinc polycarboxylate as catalyst, react 3.0h at 60~100 DEG C of temperature,
PLA alcoholysis obtains methyl lactate, and yield is only 65%, and product has optical isomer.It is traditional the shortcomings that report method
Acid base catalysator is difficult to recycle or reuse, and corrosion equipment need to neutralize and wash and lead to that wastewater flow rate is big, pollution environment.This
Seminar reports ionic liquid 1- alkyl -3- methylimidazole acetate (CN 2012101469065), liquid Lewis acid (CN
2015102531419) be catalyst, can effectively be catalyzed PLA alcoholysis and recycle corresponding product, but liquid catalyst separation it is difficult,
It is difficult to recycle.Ionic liquid dosage it is big (ionic liquid and PLA mass ratio are generally 0.02~1:1, preferably 0.05~0.5:
1;), although liquid Lewis acid dosage is little, all contain transition metal salt, causes product colour pollution, purity not high.Cause
This, introduces new idea and method to improve prior art drawback, and it is important to realize that useless poly-lactic acid material chemical recycling has
Meaning.
Summary of the invention
For shortcoming existing for the art, the purpose of the present invention is to propose to a kind of immobilized ionic liquids of application
Body [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is the method for catalyst Methanolysis PLA, and recycling obtains methyl lactate.It realizes
The technical solution of the present invention is as follows:
By the PLA of certain mass, [Bmim] [OAc]-Zn (OAc)2/ SBA-15 and methanol are added in reaction kettle, one
Determine that useless PLA is carried out alcoholysis reaction under temperature and pressure, reaction terminates that catalyst, the unreacted first of revolving recycling is recovered by filtration
Product methyl lactate is collected in alcohol, vacuum distillation, and catalyst after drying can direct reuse.
Temperature of the present invention is 90~130 DEG C, and the mass ratio of useless PLA and catalyst is 1:0.001~0.1, preferably
It is 1:0.005~0.05, the molar ratio of give up PLA and methanol is 1:1~10, preferably 1:4~6, the reaction time is 1.0~
4.0h, preferably 2.0~3.0h.
Used catalyst [Bmim] [OAc]-Zn (OAc) of the present invention2/ SBA-15 is own product, the specific steps are as follows:
(1) preparation of [Bmim] [Cl]
Refined N- methylimidazole is placed in 250mL three-necked flask, 1- chlorine normal butane, the 1- chlorine are added dropwise under ice bath
The molar ratio of normal butane and N- methylimidazole is 1.2~2.0:1, after a period of time is stirred at room temperature, N2The lower 70 DEG C of reflux of atmosphere are anti-
It after answering a period of time, is transferred in separatory funnel, is repeatedly washed to product and be in neutrality on a small quantity with ethyl acetate, after liquid separation, lower layer
Liquid obtains white solid [Bmim] [Cl] after revolving, vacuum drying, cooling, and reaction equation is as follows:
(2) preparation of [Bmim] [OAc]
A certain amount of commercial solid potassium acetate is placed in 100mL single port bottle, the dehydrated alcohol of certain volume is added, is stirred
It makes it dissolve to form transparent, homogeneous phase solution, step (1) homemade [Bmim] [Cl] then is added, [Bmim] [Cl] and second
The molar ratio of sour potassium is 1:1.2;N2Reaction a period of time is stirred at room temperature under atmosphere, after filtering, adds a certain amount of potassium acetate, institute
The molar ratio for stating potassium acetate and [Bmim] [Cl] is 1.5:1, is stirred for reaction 6.0h, after being filtered, rotating precipitation, filter at room temperature
Liquid is washed through anhydrous ether, and after placing 12h using filter, revolving, low temperature, colourless, the preferable liquid of mobility is obtained by filtration
[Bmim] [OAc], reaction equation is as follows:
(3)[Bmim][OAc]-Zn(OAc)2Preparation
In the single port bottle equipped with magnetic agitation, 4.0g step (2) homemade [Bmim] [OAc] is pressed with anhydrous zinc acetate
Molar ratio (3~1): 1 feeds intake, N2Lower 60 DEG C of atmosphere are stirred to react 6h, and product is placed in a vacuum drying oven dry a period of time, obtains
To colourless viscous liquid [Bmim] [OAc]-Zn (OAc)2, reaction equation is as follows:
(4) preparation of SBA-15
4g P123 is added in 250mL beaker, 30g water and 120g 2mol/L hydrochloric acid solution is added, stirs at room temperature
It dissolves P123 thoroughly, is slowly added to 8.5g ethyl orthosilicate (TEOS), after reaction for 24 hours is vigorously stirred at 40 DEG C, be transferred to water
Thermal response kettle, 100 DEG C crystallization 3 days.Cooling, drying at room temperature, roasting, crushing, activates after 6h to obtain carrier S BA- at 180 DEG C at filtering
15。
(5)[Bmim][OAc]-Zn(OAc)2The preparation of/SBA-15
Weigh 2.0g carrier S BA-15 to be added in the flask containing 60mL dehydrated alcohol, in mass ratio 1:(1~3) it is added
Ionic liquid [Bmim] [OAc]-Zn (OAc)2, preferably 1:1.5~2, N2For 24 hours, reaction terminates back flow reaction under atmosphere, cold
But, filter, washed using toluene, methanol, 80 DEG C of dry 8h obtain immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/
SBA-15.It is characterized in that N content is 2.19%, specific surface area 230m2/ g, Kong Rongwei 0.28cm3/ g, aperture 4.5nm.
Invention effect
Method proposed by the present invention provides one kind with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/SBA-
15 methods for recycling methyl lactate for the useless PLA material Methanolysis of catalyst, the product purity that this method obtains are up to
99% or more, catalyst recovery process is simple, and performance is stablized, and may be reused.The conversion ratio 100% of raw material PLA, product are received
For rate up to 95% or more, the methyl lactate of recycling is a kind of important industrial chemicals, be can get using method of the invention fabulous
Economic benefit and environmental benefit.
The present invention overcomes catalytic erosion equipment existing in the prior art, pollution environment, repeat performance difference or
Liquid catalyst dosage is big, separation is difficult, be difficult to recycle and the disadvantages of product yield is lower, catalyst passes through simple filtration
Realize separation and recycling, and performance is stablized, and may be reused.
Detailed description of the invention
Fig. 1 is [Bmim] [OAc]-Zn (OAc)2The infrared spectroscopy of/SBA-15.
Fig. 2 is [Bmim] [OAc]-Zn (OAc)2The scanning electron microscope of/SBA-15.
Fig. 3 is the infrared spectrogram of product methyl lactate made from embodiment 1.
Specific embodiment
Combined with specific embodiments below, the present invention is described further: those skilled in the art institute it should be understood that, implement
Example is only used to illustrate rather than for limiting the scope of the invention.In embodiment, unless otherwise instructed, means used are equal
For the means of this field routine.
Embodiment 1:
The preparation of catalyst:
(1) preparation of [Bmim] [Cl]
Refined 0.5mol N- methylimidazole is placed in 250mL three neck round bottom flask, 0.6mol is added dropwise under ice-water bath
1- chlorine normal butane, drop finish be stirred at room temperature reaction 1.0h after, in N2Under atmosphere, after 70 DEG C of heating stirring back flow reaction 72h, while hot will
Colorless viscous shape liquid is transferred in 250mL separatory funnel, unreacted to remove with ethyl acetate (30mL × 3) washed product
1- chlorine normal butane, topples over ethyl acetate layer, and lower layer's thick liquid is transferred in 250mL single-necked flask, and rotation is depressurized at 55 DEG C
Remaining ethyl acetate is evaporated off, then dries 4.0h under vacuum conditions, obtains 81.3g white solid [Bmim] after cooling
[Cl], yield 93.2%.
(2) preparation of [Bmim] [OAc]
0.06mol solid potassium acetate is placed in 100mL single-necked flask, the dehydrated alcohol of certain volume is added, stirring makes
Its dissolution forms transparent, homogeneous salting liquid, and 0.05mol [Bmim] [Cl] then is added in single port bottle.Under nitrogen atmosphere,
After room temperature is stirred to react for 24 hours strongly, white depositions are removed by filtration, then 0.025mol potassium acetate is added into filtrate, at room temperature
It is stirred for reaction 6.0h, to react away [Bmim] [Cl] that has not exchanged, is filtered to remove and generates potassium chloride and excessive potassium acetate.
Filtrate is depressurized to rotary evaporation at 55 DEG C and removes alcohol solvent, the washing of 10mL anhydrous ether is then added thereto again, is precipitated
Filtrate, is depressurized rotary evaporation 1.0h by responseless potassium acetate precipitating at 55 DEG C after filtering, residue is placed cold in refrigerator
But and after standing 12h, it is removed by filtration the salt of precipitation again, obtains that 8.67g is colourless, the preferable liquid of mobility [Bmim] [OAc],
Yield 87.5%.
(3)[Bmim][OAc]-Zn(OAc)2Preparation
4.0g [Bmim] [OAc] and anhydrous zinc acetate are fed intake according to molar ratio 2:1 in the flask equipped with magnetic agitation,
N2Lower 60 DEG C of atmosphere are stirred to react 6h, and products therefrom is placed in a vacuum drying oven dry 12h, obtains colourless viscous liquid [Bmim]
[OAc]-Zn(OAc)2, yield 87.4%.
(4) preparation of SBA-15
4g P123 is added in 250mL beaker, 30g water and 120g 2mol/L hydrochloric acid solution is added, at room temperature magnetic force
Stirring dissolves P123 thoroughly.It is slowly added to 8.5g ethyl orthosilicate (TEOS), is vigorously stirred reaction at 40 DEG C of water bath with thermostatic control
24h.Reaction terminates, and stops stirring, and white gum mixture is transferred to hydrothermal reaction kettle, 100 DEG C crystallization 3 days.It is cooling, mistake
Filter, drying at room temperature obtain SBA-15 original powder.Finally by product, 550 DEG C of roasting 6h remove surfactant in Muffle furnace, obtain
SBA-15 finished product.
(5)[Bmim][OAc]-Zn(OAc)2The preparation of/SBA-15
SBA-15 is activated to moisture and impurity that 6h removes adsorption at 180 DEG C.Then after weighing activation
2.0gSBA-15 is added in the flask containing 60mL dehydrated alcohol, and 3.0g ionic liquid [Bmim] [OAc]-Zn is added
(OAc)2, N2Protect lower back flow reaction for 24 hours.Reaction terminates, cooling, filtering, is washed using toluene, methanol, 80 DEG C of dry 8h are obtained
To solid [OAc]-Zn (OAc)2/SBA-15.It is characterized in that N content is 2.19%, specific surface area 230m2/ g, Kong Rongwei
0.28cm3/ g, aperture 4.5nm.
[Bmim][OAc]-Zn(OAc)2The IR of/SBA-15 is characterized: equipment is that U.S. Nicolet company 510P FT-IR is red
External spectrum instrument, the result is shown in Figure 1.In the IR spectrogram of SBA-15,1632cm-1Place is the stretching vibration absworption peak of Si-OH,
1082cm-1、806cm-1It is respectively belonging to [SiO4] asymmetry and symmetrical stretching vibration, 464cm-1Place's characteristic peak belongs to
[SiO4] deformation vibration;In [Bmim] [OAc]-Zn (OAc)2IR spectrogram in, 3147cm-1Place is that the C-H on aromatic ring is flexible
Vibration absorption peak, 2962cm-1、2936cm-1Place is the stretching vibration absworption peak of alkyl chain, 1388cm-1、1618cm-1Place is C=O
Asymmetry and symmetrical stretching vibration absorption peak;And [Bmim] [OAc]-Zn (OAc)2Retain simultaneously in the IR spectrogram of/SBA-15
Features above peak, shows that ionic liquid successfully loads on SBA-15.
[Bmim][OAc]-Zn(OAc)2The SEM of/SBA-15 characterizes (Fig. 2): equipment is the JSM- of Japan Electronics Corporation
6390 scanning electron microscope, are as a result shown in Fig. 2.Found out by Fig. 2 (a), a large amount of corynebacterium SBA-15 flock together to form the rope made of hemp
Shape structure, is found out by Fig. 2 (b), [Bmim] [OAc]-Zn (OAc)2Load the pattern of SBA-15 is not made a significant impact,
But carrier surface relative coarseness, and the agglomeration of rodlike SBA-15 is more obvious, further demonstrates that ionic liquid [Bmim]
[OAc]-Zn(OAc)2It is successfully carried on the surface SBA-15.
Alcoholysis reaction experiment:
4g is given up PLA, 0.04g solid catalyst [Bmim] [OAc]-Zn (OAc)2/ SBA-15 and 8.88g methanol is added
Into the 75mL autoclave with magnetic agitation and thermometer, 2.0h is stirred to react at 110 DEG C, it is after reaction, cooling
To room temperature, solid catalyst being recovered by filtration and is reused through the dry catalyst as next secondary response, filtrate is transferred to flask,
Excessive methanol is recycled in air-distillation, continues the conversion ratio 100% that product methyl lactate 5.53g, PLA are collected in vacuum distillation, produces
Product yield 95.8%, gas chromatograph results are shown in Table, and as shown in Table 1, in retention time t=5.052min, appearance is product,
Purity is 99.26%.
1 PLA Methanolysis product chromatographic peak result of table
From the figure 3, it may be seen that the infrared spectrum of product methyl lactate (b) and standard specimen (a) that embodiment 1 obtains is almost the same,
3432cm-1It is nearby the stretching vibration absworption peak of-OH, 2987cm-1、2957cm-1It is nearby the stretching vibration absworption peak of C-H,
1742cm-1It is nearby the stretching vibration absworption peak of-C=O, 1223cm-1、1132cm-1For the stretching vibration absworption peak of C-O.
Embodiment 2:
Reaction temperature is only changed to 120 DEG C with embodiment 1 by experiment condition and step, and the conversion ratio 100% of PLA obtains
Methyl lactate 5.56g, yield 96.2%.
Embodiment 3:
Experiment condition and step are with embodiment 1, only by 0.04g catalyst [Bmim] [OAc]-Zn (OAc)2/ SBA is changed to
The conversion ratio 100% of 0.06g, PLA obtain methyl lactate 5.57g, yield 96.4%.
Embodiment 4:
Reaction time 2.0h is only changed to reaction time 3.0h, the conversion of PLA with embodiment 1 by experiment condition and step
Rate 100% obtains methyl lactate 5.55g, yield 96.1%.
Embodiment 5:
8.88g methanol is only changed to 10.66g methanol, the conversion ratio of PLA with embodiment 1 by experiment condition and step
100%, obtain methyl lactate 5.52g, yield 95.6%.
Embodiment 6-10:
Catalyst is only changed to the catalyst recycled in embodiment 1 with embodiment 1 by experiment condition and step, is carried out 5 times
Repeat reuse experiment.The repetition reuse of catalyst the results are shown in Table 2.
Table 2 [Bmim] [OAc]-Zn (OAc)2The reuse result of/SBA
Claims (5)
1. one kind is with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is the useless poly-lactic acid material of catalyst alcoholysis
The method for recycling methyl lactate, comprising the following steps: m in mass ratioPLA:mCatalyst=1:0.001~0.1, molar ratio nPLA:nMethanol
=1:1~10, by PLA, methanol and catalyst [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is added in reaction kettle, 90~
1.0~4.0h of alcoholysis reaction is carried out at 130 DEG C, reaction terminates that catalyst is recovered by filtration, the unreacted methanol of revolving recycling, subtracts
Product methyl lactate is collected in pressure distillation, and catalyst can direct reuse.
2. as described in claim 1 with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is catalyst alcoholysis
The method of useless poly-lactic acid material recycling methyl lactate, which is characterized in that used catalyst [Bmim] [OAc]-Zn (OAc)2/SBA-
15 be own product, using SBA-15 as carrier, by infusion process by ionic liquid [Bmim] [OAc]-Zn (OAc)2Load to SBA-
On 15, through the following steps that being prepared:
It weighs a certain amount of carrier S BA-15 to be added in the flask containing 60mL dehydrated alcohol, be added ionic liquid [Bmim]
[OAc]-Zn(OAc)2(mass ratio with SBA-15 is 1:1~3), N2It flows back under atmosphere for 24 hours, reaction terminates, and cooling, filtering makes
It is washed with toluene, methanol, 80 DEG C of dry 8h obtain immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/SBA-15。
3. as claimed in claim 2 with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is catalyst alcoholysis
The method of useless poly-lactic acid material recycling methyl lactate, which is characterized in that the carrier S BA-15 through the following steps that preparation and
:
4g P123 is added in 250mL beaker, 30g water and 120g2mol/L hydrochloric acid solution is added, stirring makes P123 at room temperature
Thoroughly dissolution, is slowly added to 8.5g ethyl orthosilicate (TEOS), after reaction for 24 hours is vigorously stirred at 40 DEG C, is transferred to hydro-thermal reaction
Kettle, 100 DEG C crystallization 3 days.Cooling, drying at room temperature, roasting, crushing, activates after 6h to obtain carrier S BA-15 at 180 DEG C at filtering.
4. as claimed in claim 2 with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is catalyst alcoholysis
The method of useless poly-lactic acid material recycling methyl lactate, which is characterized in that ionic liquid [Bmim] [the OAc]-Zn (OAc)2It is
It is prepared by following steps:
(1) preparation of [Bmim] [Cl]
Refined N- methylimidazole is placed in 250mL three-necked flask, 1- chlorine normal butane is added dropwise under ice bath (with N- methylimidazole
Molar ratio be 1.2~2.0:1), after a period of time is stirred at room temperature, N2The lower 70 DEG C of back flow reactions of atmosphere for a period of time after, transfer
It into separatory funnel, is washed with the ethyl acetate of certain volume to product and is in neutrality, after liquid separation, lower liquid is through revolving, vacuum
White solid [Bmim] [Cl] is obtained after dry, cooling, reaction equation is as follows:
(2) preparation of [Bmim] [OAc]
A certain amount of commercial solid potassium acetate is placed in single port bottle, the dehydrated alcohol of certain volume is added, stirs to dissolve
Transparent, homogeneous phase solution is formed, a certain amount of homemade [Bmim] [Cl] (molar ratio with potassium acetate is 1:1.2) is then added.N2
After reaction a period of time is stirred at room temperature under atmosphere, after filtering, a certain amount of potassium acetate (molar ratio with [Bmim] [Cl] is added
For 1:5), it is stirred for reaction 6.0h at room temperature, after being filtered, rotating precipitation, filtrate is washed through anhydrous ether, using filter, rotation
It steams, after low temperature placement 12h, colourless, the preferable liquid of mobility [Bmim] [OAc] is obtained by filtration, reaction equation is as follows:
(3)[Bmim][OAc]-Zn(OAc)2Preparation
In the single port bottle equipped with magnetic agitation, by homemade [Bmim] [OAc] and commercially available anhydrous zinc acetate 1:1 in molar ratio
~3:1 feeds intake, N2Lower 60 DEG C of atmosphere are stirred to react 6h, and product is placed in a vacuum drying oven dry a period of time, obtain colourless viscous
Thick liquid [Bmim] [OAc]-Zn (OAc)2, reaction equation is as follows:
5. as described in claim 1 with immobilized ionic liquid [Bmim] [OAc]-Zn (OAc)2/ SBA-15 is catalyst alcoholysis
The method of useless poly-lactic acid material recycling methyl lactate, which is characterized in that used catalyst [Bmim] [OAc]-Zn (OAc)2/SBA-
N content is 2.19% in 15, specific surface area 230m2/ g, Kong Rongwei 0.28cm3/ g, aperture 4.5nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910348086.XA CN110003009A (en) | 2019-04-28 | 2019-04-28 | A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910348086.XA CN110003009A (en) | 2019-04-28 | 2019-04-28 | A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110003009A true CN110003009A (en) | 2019-07-12 |
Family
ID=67174697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910348086.XA Withdrawn CN110003009A (en) | 2019-04-28 | 2019-04-28 | A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110003009A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110357770A (en) * | 2019-07-23 | 2019-10-22 | 复旦大学 | A kind of method that glycol selectivity catalyzed conversion prepares lactic acid |
-
2019
- 2019-04-28 CN CN201910348086.XA patent/CN110003009A/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110357770A (en) * | 2019-07-23 | 2019-10-22 | 复旦大学 | A kind of method that glycol selectivity catalyzed conversion prepares lactic acid |
CN110357770B (en) * | 2019-07-23 | 2021-10-26 | 复旦大学 | Method for preparing lactic acid through selective catalytic conversion of ethylene glycol |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102659590B (en) | Alcoholysis recovery method of waster polylactic acid in ionic liquid environment | |
CN107382718B (en) | The method of the mesoporous alkaline molecular sieve catalyzed alcoholysis polylactic acid of CaO/MCF | |
CN111217710B (en) | Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation | |
CN101613461A (en) | The method of preparing fluorine-containing epoxy resin by phase transfer catalyst | |
CN113736068B (en) | Pyridine and thiazole dual-functionalized conjugated microporous polymer and preparation method and application thereof | |
CN115678030B (en) | Mechanochemical method for preparing metal-organic framework material | |
CN107188802A (en) | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type | |
CN111217700A (en) | Method for catalyzing alcoholysis of polyethylene terephthalate by using non-metal choline ionic liquid | |
CN110003009A (en) | A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate | |
CN113244940B (en) | Solid base catalyst for synthesizing dimethyl carbonate, preparation method thereof and preparation method of dimethyl carbonate | |
CN102532591B (en) | Method for depolymerizing waste polyester bottle | |
CN102491890A (en) | Preparation method of dibenzoylmethane and application of dibenzoylmethane in molding processing of thermoplastic resin | |
CN102614919B (en) | Sulfonated cross-linked chitosan resin type solid acid catalyst and preparation method thereof | |
CN111484395B (en) | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide | |
CN102433223A (en) | Method for preparing conjugate linoleate by using vegetable oil | |
CN105732687A (en) | Methyltris(methylethylketoxime)silane preparation method | |
CN109942419A (en) | A kind of method of immobilized ionic liquid-catalyzed useless polylactic acid alcoholysis recycling methyl lactate | |
CN105037249A (en) | Preparation method of liquid monoester and diester mixed type hindered amine light stabilizer | |
CN114849714B (en) | Preparation method of solid base catalyst for alcoholysis of PET | |
CN101450895A (en) | Preparation method of trifluoro-phenylacetic acid | |
CN1927800A (en) | Synthesis process of 2,4,6-trimethyl benzoic acid | |
CN101434539A (en) | Preparation of benzyl acetate | |
CN101851154B (en) | Improved method for producing 2-alkylene alicyclic ketone | |
CN101117588A (en) | Method for preparing biological diesel fuel by high-acid-value grease | |
CN101054330A (en) | Synthesis method for biphenyl compound |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190712 |
|
WW01 | Invention patent application withdrawn after publication |