CN108607604A - The catalyst and method of alcoholysis makrolon - Google Patents
The catalyst and method of alcoholysis makrolon Download PDFInfo
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- CN108607604A CN108607604A CN201810607391.1A CN201810607391A CN108607604A CN 108607604 A CN108607604 A CN 108607604A CN 201810607391 A CN201810607391 A CN 201810607391A CN 108607604 A CN108607604 A CN 108607604A
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- emimoh
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- makrolon
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- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 30
- 239000004425 Makrolon Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 230000005496 eutectics Effects 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000376 reactant Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 abstract description 105
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000006140 methanolysis reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical class [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 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
- 238000012360 testing method Methods 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 etching apparatus Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0249—Ureas (R2N-C(=O)-NR2)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
Abstract
The invention belongs to the alcoholysis reactions of makrolon, disclose the catalyst and method of catalysis makrolon (PC) alcoholysis recycling bisphenol-A (BPA).Using [EMIMOH] Cl nUrea eutectic solvents as catalyst, alcoholysis reaction occurs this method for reactant makrolon and alcohol, generates bisphenol-A.Catalyst And Method provided by the invention can effectively improve the percent alcoholysis of PC and the yield of BPA, while the synthetic method of the catalyst is simple, and of low cost, dosage is few, be conducive to industrial production.
Description
Technical field
The present invention relates to the alcoholysis reactions of makrolon, more particularly to are catalyzed the catalysis of makrolon alcoholysis recycling bisphenol-A
Agent and method.
Background technology
Makrolon (PC) is the high molecular polymer containing carbonate group in a kind of strand, due to polycarbonate structure
On particularity, it has also become the most fast general engineering plastic of growth rate in five large-engineering plastics.With PC material volume of production and marketing
Swift and violent to increase, generated waste and old PC is also more and more.Although waste and old PC toxicity itself is little, since its is bulky,
It degrades under natural conditions slow, not only takes up space, pollutes environment, but also be also a kind of huge wasting of resources.Therefore, waste and old
The recycling of PC is increasingly subject to the attention of people.Currently, the chemical recycling reported is broadly divided into thermal cracking and chemistry solves
It is poly-.Pyrolysis method is to carry out in the molten state mostly, and reaction needs higher temperature, and high polymer chain rupture is random, raw
At by-product it is more, it is difficult to obtain the target product of high-purity.So compared with pyrolysis method, chemical depolymerization rule is more real
With wherein alcoholysis method is a kind of one of effective way.
Alcoholysis method is mainly and is carried out in the presence of traditional highly basic at present, for example, sources Liu Yao etc. (plastics science and technology, 2014,42
(3):It 74-77) reports and uses sodium hydroxide for catalyst, toluene is solvent, and catalysis CD grade PC Methanolysis recycles bisphenol-A
(BPA), the PC although technique can effectively degrade need to use a large amount of strong alkali as a catalyst, etching apparatus, wastewater flow rate
Greatly, and catalyst cannot recycle.(Journal of Chemical Industry and Engineering, 2011,62 (S2) such as Yang Xuequn:It 85-89) reports using ion
Liquid is catalyst and reaction medium, is catalyzed waste disk Methanolysis, which can effectively recycle accordingly degrading waste CD
Product bisphenol-A, while the technical issues of overcome a large amount of high concentration inorganic acid/highly basic of consumption and reuse cannot be repeated；But
Ionic liquid synthesis step is cumbersome, of high cost and dosage is big, and (ionic liquid and CD quality are than preferably 1:1)；Ionic liquid
Although body is novel green solvent, green is that it does not have apparent vapour pressure, thermal stability good and safe operation
Deng, but the synthesis of ionic liquid, purifying and removal process all use a large amount of volatile organic solvent, ionic liquid to be used as and urge
Agent or solvent eventually some to be lost in environment, different degrees of influence will be caused to environment.Therefore, finding one kind can
The catalyst of biodegradable, the few excellent catalytic effect of dosage alcoholysis makrolon improves prior art drawback, realizes useless
Old makrolon material chemical recovery is utilized and is of great significance.
Invention content
Catalyst amount in order to solve alcoholysis makrolon in the prior art is big, it is of high cost, can not biodegradable, catalysis
Effect need the problem of being improved, and the present invention provides the catalyst of alcoholysis makrolon.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
The catalyst of alcoholysis makrolon, the catalyst are that N- methylimidazoles presoma and urea are prepared
[EMIMOH] Cl-nUrea eutectic solvents, wherein 1≤n≤5, N- methylimidazole presoma are by N- methylimidazoles and 2- chlorine
What ethyl alcohol was prepared.
Preferably, the preparation method of described [EMIMOH] the Cl-nUrea eutectic solvents is：Under nitrogen atmosphere, molar ratio
It is 1:The N- methylimidazoles presoma and urea of n (1≤n≤5) reacts 2h in 80-100 DEG C of heating stirring, until solid mixture
Become transparent supernatant liquid, generates catalyst [EMIMOH] Cl-nUrea eutectic solvents, wherein 1≤n≤5.
Preferably, the preparation method of the N- methylimidazoles presoma is：Molar ratio 1:1 N- methylimidazoles and 2- chloroethenes
Alcohol is heated to reflux, and is stirred to react 48h, and cooled to room temperature filters and heavy with the white after the multiple wash cooling of ethyl acetate
It forms sediment, dry white precipitate obtains N- methylimidazole presomas.
Originally, inventor tests catalyst of a variety of eutectic solvents (DES) as alcoholysis PC, but much to PC alcohol
For solution all without catalytic effect, inventor, which even once abandons, finds suitable eutectic solvent catalyst PC alcoholysis most
First effort, however as the progress of experiment, we have surprisingly found that, acid eutectic solvent imitates PC alcoholysis almost without catalysis
Fruit, and particular kind of alkaline eutectic solvent N- methylimidazoles eutectic solvent has catalytic effect to PC alcoholysis, studies carefully its original
Cause, it may be possible to which, because PC alcoholysis reactions are a nucleophilic substitutions, the alkalinity of nucleopilic reagent is stronger, and nucleophilic substitution more holds
It easily carries out, catalyst of the present invention using alkalinity eutectic solvent [EMIMOH] Cl-nUrea as catalysis PC alcoholysis.The present invention
[EMIMOH] Cl-nUrea, which is further explored, by external spectrum (IR) and semimicro gel permeation chromatography (GPC) is catalyzed PC alcoholysis
Reaction mechanism, pass through IR and GPC and find：With the increase of conversion ratio, the oligomer of small-molecular-weight gradually increases, macromolecule
High polymer gradually decrease, and thus speculate the possibility reaction mechanism of [EMIMOH] Cl-nUrea catalysis PC Methanolysis, DES
Hydrogen bond is formed with methanol, the nucleophilicity of methanol is caused to improve, is conducive to the carbonyl in methanol attack PC chains, the fracture of PC chains is formed
The polymer of different molecular weight with the continuous fracture of PC chains has ultimately generated target product bisphenol-A.
The present invention also provides the method for alcoholysis makrolon, be with [EMIMOH] Cl-nUrea eutectic solvents be catalysis
Alcoholysis reaction occurs for agent, reactant makrolon and alcohol, generates bisphenol-A, it is preferable that the temperature of the alcoholysis reaction is 110-
125 DEG C, time of reaction is 2-4h, and the molar ratio of reactant makrolon and alcohol is 1:2-7, catalyst [EMIMOH] Cl-
The mass ratio of nUrea eutectic solvents and makrolon is 0.025-0.125:1.
It is further preferable that the temperature of the alcoholysis reaction is 120 DEG C, time of reaction is 2h, reactant makrolon and
The molar ratio of alcohol is 1:5, the mass ratio of catalyst [EMIMOH] Cl-nUrea eutectic solvents and makrolon is 0.1:1.
Preferably, the alcohol is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol or isobutanol.The type of Organic Alcohol does not have
There is concrete restriction, can reasonably be selected according to needs of production, makrolon alcoholysis reaction can be selected the most frequently used
Methanol carry out alcoholysis.
Preferably, the method for alcoholysis makrolon further includes post-processing step, this step is to carry out alcoholysis reaction liquid
Filter, filtrate decompression distill to obtain colloidal liquid, are extracted with ethyl acetate and water, and supernatant is evaporated under reduced pressure to obtain bisphenol-A, lower clear liquid
Vacuum distillation, dried recovered [EMIMOH] Cl-nUrea are simultaneously reused.
Compared with the common catalyst of the prior art, the present invention uses environmentally protective, cheap, efficient [EMIMOH] Cl-
NUrea eutectic solvent catalyst is used to be catalyzed the alcoholysis reaction of PC, such eutectic solvent has good catalysis to PC alcoholysis
Effect, catalyst is not only of low cost, it is simple to make, and can also recycle, can make up the deficiency of traditional catalyst；And
And the catalyst have difficult volatilization, fire retardant, nontoxic property, and the eutectic solvent be it is biodegradable, can be to avoid
Ionic liquid as catalyst or solvent eventually some to be lost in environment, different degrees of influence will be caused to environment.
Test result shows that catalyst provided by the invention and method, the yield that PC percent alcoholysis can reach 100%, BPA substantially can reach
98.5-99.8%.By above technical scheme it is found that the present invention uses [EMIMOH] Cl-nUrea eutectic solvents as catalyst
It is catalyzed PC alcoholysis, the percent alcoholysis of PC and the yield of BPA can be effectively improved, while the synthetic method of the catalyst is simple, cost
Cheap, dosage is few, is conducive to industrial production.
Description of the drawings
Fig. 1 is the infrared spectrum of the Methanolysis product and bisphenol-A standard specimen in embodiment 7；
Fig. 2 is [EMIMOH] Cl-2Urea and fresh [EMIMOH] Cl-2Urea after reuse the 4th in embodiment 7
Infrared spectrum；
Fig. 3 is the thermogravimetric spectrogram of [EMIMOH] Cl-2Urea before and after the reuse in embodiment 7.
Specific implementation mode
The invention discloses a kind of catalyst and method of alcoholysis makrolon, those skilled in the art can use for reference herein
Content is suitably modified technological parameter realization.In particular, it should be pointed out that all similar substitutions and modifications are to people in the art
It is it will be apparent that they are considered as including in the present invention for member.The present invention method and application by compared with
Good embodiment is described, related personnel obviously can not depart from the content of present invention, in spirit and scope to as described herein
Methods and applications are modified or suitably change and combine, to realize and apply the technology of the present invention.
In order to enable those skilled in the art to be better understood from the present invention, With reference to embodiment to the present invention
It is described in further detail.
The preparation of embodiment 1 [EMIMOH] Cl-nUrea eutectic solvents
It is 1 that molar ratio is gradually added into there-necked flask for the preparation of N- methylimidazole presomas:1 N- methylimidazoles, 2- chlorine
Ethyl alcohol under nitrogen atmosphere, is heated to reflux, and is stirred to react 48h, cooled to room temperature, and a large amount of white precipitates occurs in drag,
With filtered on buchner funnel white precipitate, it is used in combination ethyl acetate washing multiple, the white precipitate of gained is put into vacuum drying chamber
80 DEG C of dry 8h obtain the N- methylimidazole presomas of white.
It is 1 that the preparation of [EMIMOH] Cl-nUrea eutectic solvents, which takes molar ratio,:2 above-mentioned N- methylimidazoles presoma and
Urea is added in 100ml single port bottles, and under nitrogen atmosphere, 90 DEG C of heating stirrings react 2h, until water white transparency supernatant liquid
Generate [EMIMOH] Cl-2Urea.
The preparation of embodiment 2 [EMIMOH] Cl-nUrea eutectic solvents
It is 1 that molar ratio is gradually added into there-necked flask for the preparation of N- methylimidazole presomas:1 N- methylimidazoles, 2- chlorine
Ethyl alcohol under nitrogen atmosphere, is heated to reflux, and is stirred to react 48h, cooled to room temperature, and a large amount of white precipitates occurs in drag,
With filtered on buchner funnel white precipitate, it is used in combination ethyl acetate washing multiple, the white precipitate of gained is put into vacuum drying chamber
80 DEG C of dry 8h obtain the N- methylimidazole presomas of white.
It is 1 that the preparation of [EMIMOH] Cl-nUrea eutectic solvents, which takes molar ratio,:5 above-mentioned N- methylimidazoles presoma and
Urea is added in 100ml single port bottles, and under nitrogen atmosphere, 90 DEG C of heating stirrings react 2h, until water white transparency supernatant liquid
Generate [EMIMOH] Cl-5Urea.
The influence with comparison PC alcoholysis reactions of embodiment 3 [EMIMOH] Cl-nUrea
In the autoclave with thermometer, [EMIMOH] Cl- in waste and old PC, 0.4g tables of 4g 1 is sequentially added
NUrea, 2.5g methanol, are stirred to react 2h at 120 DEG C, after cooled to room temperature, open kettle and filter unreacted PC residues, filtrate
It is first evaporated under reduced pressure, adds ethyl acetate and deionized water extraction liquid separation, recycled after lower clear liquid vacuum distillation water removal, drying corresponding
[EMIMOH] Cl-nUrea, supernatant obtains corresponding product BPA, the yield and PC of corresponding product BPA after vacuum distillation
Degradation rate is as shown in table 1.
The influence with comparison PC alcoholysis reactions of 1 choline chloride class DES of table
It is shown by 1 data of table, the mol ratio of [EMIMOH] Cl and Urea use 1:1~1:5, PC Methanolysis is reacted
All there is preferable catalytic effect, PC degradation rates are attained by 100%, but the catalytic effect of [EMIMOH] Cl-2Urea is preferable,
BPA yield highers.
The selection of 4 PC alcoholysis reaction conditions of embodiment
4.1 orthogonal experiment
Using [EMIMOH] Cl-2Urea as catalyst, according to the method for orthogonal experiment, select to refer to using PC conversion ratios as quality
Mark, while with reaction temperature, reaction time, catalyst amount, methanol usage for 4 factors, selecting the orthogonal of 4 factor, 3 level
Experimental method (is shown in Table 2), orthogonal to the results are shown in Table 3.
2 orthogonal experiment factor level table of table
3 PC of table Methanolysis Orthogonal experiment results in [EMIMOH] Cl-2urea
It carries out differential analyzing to obtain R1>R2>R3>R4, that is, the factor for influencing PC Methanolysis conversion ratios are followed successively by：Reaction temperature
Degree, reaction time, DES dosages, methanol usage.
The influence that 4.2 reaction temperatures react PC Methanolysis
In reaction time 2h, m ([EMIMOH] Cl-2urea):M (PC)=0.1:1, n (methanol):N (PC)=5:1 item
Under part, influence of the reaction temperature to alcoholysis reaction is investigated, the results are shown in Table 4.
The influence that 4 reaction temperature of table reacts PC Methanolysis
Table 4 shows that with the increase of reaction temperature, PC conversion ratios and BPA yields all significantly increase, when reaction temperature is
At 115 DEG C, the conversion ratio of PC only has 42.2%, and when reaction temperature is increased to 120 DEG C, PC conversion ratios can reach 99.8%,
The yield of thick BPA can reach 98.9%.When temperature increases again, the conversion ratio of PC and the yield of BPA are basically unchanged, and illustrate alcoholysis
Reaction has had reached balance.With the raising of temperature, PC strand chain rupture speed is accelerated, and the rate of PC alcoholysis reactions also just adds
Soon, it has been finally reached the state of reaction balance.But reaction temperature is improved too much, energy consumption, waste of energy, so choosing can be increased
It is preferable reaction temperature to select 120 DEG C.
The influence that 4.3 reaction time reacted PC Methanolysis
In 120 DEG C of reaction temperature, m ([EMIMOH] Cl-2urea):M (PC)=0.1:1, n (methanol):N (PC)=5:1
Under the conditions of, influence of the reaction time to alcoholysis reaction is investigated, the results are shown in Table 5.
The influence that 5 reaction time of table reacts PC Methanolysis
Table 5 show, with the increase in reaction time, PC conversion ratios and BPA yields all significantly increase, when reacted between be
When 1.25h, the conversion ratio of PC only has 24.3%, and when reacted between when increasing to 2h, PC conversion ratios can reach 99.8%, slightly
The yield of BPA can reach 98.9%.When being further added by the time, the conversion ratio of PC and the yield of BPA are basically unchanged, and illustrate that alcoholysis is anti-
Balance should have been had reached.Therefore the preferably reaction time is 2h.
The influence that 4.4 catalyst amounts react PC Methanolysis
In 120 DEG C of reaction temperature, reaction time 2h, n (methanol):N (PC)=5:Under conditions of 1, catalyst use has been investigated
The influence to alcoholysis reaction is measured, the results are shown in Table 6.
The influence that 6 catalyst amount of table reacts PC Methanolysis
Table 6 shows that, with the increase of catalyst amount, PC conversion ratios and BPA yields all significantly increase, when catalyst is used
Measure m ([EMIMOH] Cl-2urea)：M (PC)=0.05:When 1, the conversion ratio of PC only has 56%, and when the dosage of catalyst increases
To m ([EMIMOH] Cl-2urea)：M (PC)=0.1:When 1, PC conversion ratios can reach 99.8%, and the yield of thick BPA can reach
98.9%.When catalyst amount is further added by, the conversion ratio of PC and the yield of BPA are basically unchanged, and illustrate that alcoholysis reaction has reached
Balance is arrived.Therefore preferably catalyst amount is m ([EMIMOH] Cl-2urea)：M (PC)=0.1:1.
The influence that 4.5 methanol usages react PC Methanolysis
In 120 DEG C of reaction temperature, reaction time 2h, m ([EMIMOH] Cl-2urea):Under conditions of m (PC)=0.1, examine
Influence of the methanol usage to alcoholysis reaction is examined, the results are shown in Table 7.
The influence that 7 methanol usage of table reacts PC Methanolysis
It is shown by table 7, with the increase of methanol usage, PC conversion ratios and the variation of BPA yields are small, tend to balance.Work as first
Alcohol dosage n (methanol)：N (PC)=2:When 1, PC conversion ratios have just reached 99%, and when the dosage of methanol increases to n (methanol)：n
(PC)=5:When 1, PC conversion ratios can reach 99.8%, and the yield of thick BPA can reach 98.9%, and there is no to turning for the increase of methanol
The raising of rate and yield cuts much ice, and illustrates in this amount ranges, and PC Methanolysis is reacted in the variation of methanol usage
Influence very little, conversion ratio and yield only improve a bit.And when methanol usage is further added by, the conversion ratio of PC and the receipts of BPA
Rate reduces a bit instead, it is more likely that since methanol usage is excessive, causes the concentration of catalyst to reduce, it is anti-to have slowed down PC alcoholysis
The rate answered, PC conversion ratios and BPA yields decrease, and finally reach equilibrium state.We select n (methanol)：N (PC)=5:
1 is used as preferable methanol usage.
5 PC alcoholysis reactions of embodiment
Using the autoclave with magnetic agitation and thermometer as reaction vessel, 4g (w are sequentially added1) PC, 0.5g catalysis
The isopropanol of agent [EMIMOH] Cl-2Urea, 1.9g closes reaction kettle, and heating stirring is reacted at a temperature of 110 DEG C, and reaction terminates
Afterwards, it is cooled to room temperature.It opens kettle and is separated by filtration unreacted residue 0g (w2), filtrate decompression revolving obtains lurid colloidal fluid
Then body is added ethyl acetate and water dissolution, is transferred to separatory funnel liquid separation, white solid is obtained after supernatant vacuum rotary steam simultaneously
It is dry, obtain product 3.54g (w3), it is bisphenol-A to characterize the product through infrared spectrum, and the decompression of lower clear liquid oil pump removes water and drying,
It is 98.5% to recycle the yield that catalyst [EMIMOH] Cl-2Urea, PC percent alcoholysis are 100%, BPA.
Wherein M (PC) is the molal weight of PC repetitive units；M (BPA) is the molal weight of bisphenol-A.
6 PC alcoholysis reactions of embodiment
In the autoclave with thermometer, 4g waste and old PC, 0.1g [EMIMOH] Cl-2Urea, 5.1g is sequentially added
Ethyl alcohol, is stirred to react 4h at 125 DEG C, after cooled to room temperature, opens kettle and filters unreacted PC residues, filtrate first depressurizes steaming
It evaporates, adds ethyl acetate and deionized water extraction liquid separation, [EMIMOH] Cl- is recycled after lower clear liquid vacuum distillation water removal, drying
2Urea, supernatant obtain product 3.56g after vacuum distillation, and it is bisphenol-A (BPA), PC alcoholysis to characterize the product through infrared spectrum
The yield that rate is 100%, BPA is 99%.
7 PC alcoholysis reactions of embodiment
In the autoclave with thermometer, 4g waste and old PC, 0.4g [EMIMOH] Cl-2Urea, 2.5g is sequentially added
Methanol, is stirred to react 2h at 120 DEG C, after cooled to room temperature, opens kettle and filters unreacted PC residues, filtrate first depressurizes steaming
It evaporates, adds ethyl acetate and deionized water extraction liquid separation, [EMIMOH] Cl- is recycled after lower clear liquid vacuum distillation water removal, drying
2Urea, supernatant obtain product 3.59g after vacuum distillation, and it is bisphenol-A (BPA), PC alcoholysis to characterize the product through infrared spectrum
The yield that rate is 100%, BPA is 99.8%.
The infrared spectrum of PC Methanolysis products therefroms is shown in Fig. 1 with pure bisphenol-A (BPA) spectrogram, the infrared spectrum in Fig. 1
A is standard specimen spectrogram, and infrared spectrum b is alcoholysis product spectrogram, 3346cm-1For the stretching vibration absworption peak of-OH in bisphenol-A,
3027cm-1For the C-H stretching vibration peaks on bisphenol-A phenyl ring, 2964cm-1For-CH3Stretching vibration absworption peak, 1612cm-1、
1510cm-1And 1743cm-1For the skeletal vibration absorption peak of bisphenol-A phenyl ring, 1446cm-1And 1383cm-1For-CH3Bending vibration
Absorption peak, 1237cm-1And 1177cm-1For the stretching vibration absworption peak of the C-O of phenol, 827cm-1Absorption peak can be attributed to benzene
Substituted absorption peak is aligned on ring, it is exactly bisphenol-A that infrared analysis, which demonstrates alcoholysis product,.
Embodiment 8 [EMIMOH] Cl-2Urea is catalyzed the reuse experiment of PC alcoholysis reactions
It is identical as the reaction condition of embodiment 7, it is catalyzed after the catalyst in embodiment 7 is carried out 5 recyclings
Effect carries out catalytic effect experiment, and test result is as shown in table 8.
Table 8 [EMIMOH] Cl-2Urea is catalyzed the reuse experimental result of PC alcoholysis reactions
8 data of table show, [EMIMOH] Cl-2Urea reuses for the first time, PC conversion ratios 100%, BPA yields 98.86%,
It is varied less compared with before reuse, after reuse 5 times, PC conversion ratios and BPA yields are basically unchanged, and illustrate [EMIMOH] Cl-
There is 2Urea good reuse performance, [EMIMOH] Cl-2Urea to be catalyzed the repeatability of PC alcoholysis reactions in PC alcoholysis reactions
Well.
Before and after reuse, the catalytic activity of [EMIMOH] Cl-2Urea is basically unchanged, in order to further verify [EMIMOH] Cl-
2Urea has good reuse performance, [EMIMOH] Cl-2Urea to reuse the 4th and fresh [EMIMOH] Cl-2Urea
Structural characterization is carried out using infrared spectrum, phenogram is shown in that Fig. 2, Fig. 2 phenograms are shown, the phenogram before a reuses, after b reuses
Phenogram, the main characteristic absorption of [EMIMOH] Cl-2Urea and fresh [EMIMOH] Cl-2Urea after reuse the 4th
Peak coincide substantially, and before and after illustrating reuse, structure and the composition of [EMIMOH] Cl-2Urea do not change, further illustrate
[EMIMOH] Cl-2Urea has good reuse performance.
And thermogravimetric analysis has been carried out to the catalyst of [EMIMOH] Cl-2Urea before and after reuse the 4th, verify ChCl
The thermal stability of 2urea, as shown in figure 3, before and after Fig. 3 reuses [EMIMOH] Cl-2Urea thermogravimetric spectrogram, wherein before a reuses
Thermogravimetric spectrogram；B is the thermogravimetric spectrogram after reuse, from figure 3, it can be seen that [EMIMOH] Cl-2Urea decomposition is broadly divided into two
The decomposition temperature in stage, first stage is 175 DEG C or so, this stage is mainly the decomposition of urea, the decomposition temperature of second stage
Degree is 250 DEG C or so, this stage is mainly the decomposition of [EMIMOH] Cl.When temperature is increased to 320 DEG C, the quality of sample with
The raising of temperature gradually goes to zero without significant change.When meaning that reaction temperature is less than 175 DEG C, [EMIMOH] Cl-
2Urea has good thermal stability.The thermogravimetric curve before and after reuse is compared, it is found that two curves essentially coincide, illustrates reuse
The structure of front and back [EMIMOH] Cl-2Urea does not change with composition, and [EMIMOH] Cl-2Urea has good reuse
Energy.
Influences of the different DES of comparative example 1 to PC alcoholysis reactions
Catalyst identical as 7 reaction condition of embodiment, the catalyst of embodiment 7 being modified as successively in table, it is each
The catalytic effect of catalyst is as shown in table 9.Wherein, the preparation method of the eutectic solvent and embodiment 1 of other classes in table 9
It is identical.
Influence of the 9 different types of eutectic solvent of table to PC alcoholysis reactions
It is shown by 9 data of table, there is no catalytic effects to PC Methanolysis by acid DES, and alkalinity DES is to PC Methanolysis
There is catalytic effect.With choline chloride 0.216g in 4gDES ([EMIMOH] Cl-2Urea), the catalytic performance of urea 0.184g, with
Choline chloride, the catalytic performance of urea respectively of same amount are compared, and are properly matched as a result, it has been found that [EMIMOH] Cl and Urea is used
Than formation [EMIMOH] Cl-2Urea to PC Methanolysis have intention less than catalytic effect, and PC conversion ratios and BPA
Yield obtain different degrees of raising；The catalytic effect of [EMIMOH] Cl-2Urea is substantially better than common ionic liquid phase
Than, and even more important is that [EMIMOH] Cl-2Urea preparation methods that the present invention uses are simple, of low cost, [EMIMOH]
Cl-2Urea eutectic solvents be it is biodegradable, can to avoid ionic liquid as catalyst or solvent eventually some want
It is 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 (8)
1. the catalyst of alcoholysis makrolon, which is characterized in that the catalyst is prepared by N- methylimidazoles presoma and urea
Made of [EMIMOH] Cl-nUrea eutectic solvents, wherein 1≤n≤5, N- methylimidazole presoma are by N- methylimidazoles
It is prepared with ethylene chlorhydrin.
2. catalyst as described in claim 1, which is characterized in that the preparation of [EMIMOH] the Cl-nUrea eutectic solvents
Method is：Under nitrogen protection, molar ratio 1:The N- methylimidazoles presoma and urea of n (1≤n≤5) adds at 80-100 DEG C
2h is reacted in thermal agitation, until solid mixture becomes transparent supernatant liquid, generates catalyst [EMIMOH] Cl-nUrea eutectic
Solvent, wherein 1≤n≤5.
3. catalyst as described in claim 1, which is characterized in that the preparation method of the N- methylimidazoles presoma is：It rubs
That ratio 1:1 N- methylimidazoles and ethylene chlorhydrin is heated to reflux, and is stirred to react 48h, and cooled to room temperature filters and uses acetic acid
White precipitate after the multiple wash cooling of ethyl ester, dry white precipitate obtain N- methylimidazole presomas.
4. the method for alcoholysis makrolon, which is characterized in that low with any described [EMIMOH] Cl-nUrea of claim 1-3
Congruent melting solvent is catalyst, and reactant makrolon and alcohol occur alcoholysis reaction, generates bisphenol-A.
5. method as claimed in claim 4, which is characterized in that the temperature of the alcoholysis reaction be 110-125 DEG C, reaction when
Between be 2-4h, the molar ratio of reactant makrolon and alcohol is 1:2-7, catalyst [EMIMOH] Cl-nUrea eutectic solvents with
The mass ratio of makrolon is 0.025-0.125:1.
6. method as claimed in claim 4, which is characterized in that the temperature of the alcoholysis reaction is 120 DEG C, and the time of reaction is
The molar ratio of 2h, reactant makrolon and alcohol is 1:5, catalyst [EMIMOH] Cl-nUrea eutectic solvents and makrolon
Mass ratio be 0.1:1.
7. method as described in claim 4 or 5, which is characterized in that the alcohol is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, just
Butanol or isobutanol.
8. method as claimed in claim 4, which is characterized in that further include post-processing step, this step is by alcoholysis reaction liquid
It being filtered, filtrate decompression distills to obtain colloidal liquid, is extracted with ethyl acetate and water, and supernatant is evaporated under reduced pressure to obtain bisphenol-A,
Lower clear liquid is evaporated under reduced pressure, and dried recovered [EMIMOH] Cl-nUrea is simultaneously reused.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484395A (en) * | 2020-05-20 | 2020-08-04 | 青岛科技大学 | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide |
| CN112979936A (en) * | 2021-02-08 | 2021-06-18 | 中国科学院过程工程研究所 | Method for preparing polycarbonate by using eutectic solvent as catalyst |
| CN114524965A (en) * | 2022-02-20 | 2022-05-24 | 中国科学院山西煤炭化学研究所 | Method for preparing porous material and chemicals from anhydride cured epoxy resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323373A (en) * | 2003-04-22 | 2004-11-18 | Teijin Ltd | Method for depolymerizing aromatic polycarbonate |
| CN101429100A (en) * | 2008-12-09 | 2009-05-13 | 青岛科技大学 | Chemical recovery method for waste polycarbonate material in ionic liquid surrounding |
-
2018
- 2018-06-13 CN CN201810607391.1A patent/CN108607604B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323373A (en) * | 2003-04-22 | 2004-11-18 | Teijin Ltd | Method for depolymerizing aromatic polycarbonate |
| CN101429100A (en) * | 2008-12-09 | 2009-05-13 | 青岛科技大学 | Chemical recovery method for waste polycarbonate material in ionic liquid surrounding |
Non-Patent Citations (1)
| Title |
|---|
| 杨锐: "基于咪唑型低共熔溶剂的合成及其应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484395A (en) * | 2020-05-20 | 2020-08-04 | 青岛科技大学 | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide |
| CN111484395B (en) * | 2020-05-20 | 2022-08-19 | 青岛科技大学 | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide |
| CN112979936A (en) * | 2021-02-08 | 2021-06-18 | 中国科学院过程工程研究所 | Method for preparing polycarbonate by using eutectic solvent as catalyst |
| CN112979936B (en) * | 2021-02-08 | 2022-04-15 | 中国科学院过程工程研究所 | Method for preparing polycarbonate by using eutectic solvent as catalyst |
| CN114524965A (en) * | 2022-02-20 | 2022-05-24 | 中国科学院山西煤炭化学研究所 | Method for preparing porous material and chemicals from anhydride cured epoxy resin |
| CN114524965B (en) * | 2022-02-20 | 2023-11-10 | 中国科学院山西煤炭化学研究所 | Method for preparing epoxy porous material or aromatic glyceryl ether compound by using anhydride cured epoxy resin |
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