CN104479145B - A kind of method of ion liquid dissolving acrylic resin - Google Patents
A kind of method of ion liquid dissolving acrylic resin Download PDFInfo
- Publication number
- CN104479145B CN104479145B CN201410801155.5A CN201410801155A CN104479145B CN 104479145 B CN104479145 B CN 104479145B CN 201410801155 A CN201410801155 A CN 201410801155A CN 104479145 B CN104479145 B CN 104479145B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- acrylic resin
- ion
- liquid
- hours
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of method of ion liquid dissolving acrylic resin, ionic liquid used is glyoxaline ion liquid.Anion in ionic liquid is bromide ion, acetate ion, hydroxide ion or hexafluorophosphoricacid acid ions, and the group connect on imidazoles is ethyl, propyl group or butyl.Method used is to dissolve by heating, and the temperature of dissolving is 50~200 DEG C.This method is simple to operate, can effectively dissolve acrylic resin, and the method uses the more popular ion liquid solvent of Recent study, environment-protecting and non-poisonous, non-volatile, can be repeated several times use, and the acrylic resin of dissolving may also pass through extraction recovery.It is demonstrated experimentally that the acrylic resin after ionic liquid thermosol, its molecular weight reduces, and illustrates that ionic liquid while acrylic resin is dissolved, also plays the role of depolymerization to acrylic resin.
Description
Technical field
The present invention relates to the dissolving recycling field of acrylic resin, and in particular to acrylic resin is in ionic liquid
Dissolving, depolymerization and recovery method and technique.
Background technology
Ionic liquid, also known as ionic liquid at room temperature or room temperature molten salt, usually by volume is relatively large, structure is not right
The relatively small nothing of the organic cation (such as alkyl imidazolium ion, alkyl pyridinium ions, alkyl quaternary ammonium ion) and volume of title
Machine or organic anion (such as Br-, PF6–、CH3COO-, OH -) form ionic compound.
Compared with traditional organic solvent, ionic liquid has the characteristics of traditional organic solvent is incomparable and superior
Property.Ionic liquid is not only environmentally friendly solvent first, and will not be caused damage in separating-purifying because of volatilization, reduces
Reaction cost.Secondly ionic liquid has good thermal stability, and liquid is kept having within the scope of larger temperature, non-volatile, most
Ionic liquid can still keep stable liquid condition at 300 DEG C, thus to some because temperature is too high can not be in organic solvent
For the reaction of middle progress, ionic liquid is the first choice as solvent, while ionic liquid can dissolve gas chromatography, inorganic
Thing, it is the good solvent of many chemical degradation reactions.In addition, most of ionic liquids can be reduced into recycling
This takes into account environmental protection again.
By to introducing other functionalization groups in ionic liquid structure, forming the ion for going for multiple fields
Liquid.Basic group such as is introduced on 1- alkyl -3- methylimidazole rings, now ionic liquid has the work(of alkali ionic liquid
Energy.Due to " controllability " of ionic liquid structure, people ionic liquid is carried out as needed functional compound into and ion
Exchange, the different ionic liquid of many functions can be obtained.
Now, industrial expansion, the living standard of people is improved, but industrial expansion also brings serious pollution,
Compared to by serious pollution drive it is economical develop rapidly, people are more willing to exchange for " blue mountains and green waters " with green industry.With people
To the requirement more and more higher of environmental protection, those heavy-polluted factories, the chemical products of strong toxicity will be eliminated, and people are more willing to connect
By environment-protecting and non-poisonous chemical products.In this case, the appearance of ionic liquid, the requirement of people, ionic liquid are met
It will be promoted in future, or even replace traditional organic solvent.
The content of the invention
The present invention is in order to overcome the above-mentioned deficiency of prior art, there is provided a kind of with ion liquid dissolving acrylic resin
Method, the needs that non-toxic product is developed in requirement and factory of the people to environmental protection are met, simple to operate, recyclable repetition makes
With being a new environment-protecting and non-poisonous solvent.
To achieve these goals, the used following scheme of the present invention is achieved：
A kind of method with ion liquid dissolving acrylic resin, it is characterised in that the ionic liquid be imidazoles from
Sub- liquid, glyoxaline ion liquid include cation and anion, and the anion is bromide ion, acetate ion, hydroxyl
Ion or hexafluorophosphoricacid acid ions, the group connect on cation imidazoles is ethyl, propyl group or butyl；
The method of the dissolving is according to 1 ~ 20 by ionic liquid and acrylic resin：1 mass ratio mixing, mixture exist
50~200 DEG C of heated at constant temperature 0.5 ~ 12 hour, reaction terminates, and naturally cools to room temperature.
The preparation method of the ionic liquid comprises the following steps：
S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and halogenated hydrocarbons, first plus N- methylimidazoles are into container, then inward
Halogenated hydrocarbons is slowly added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；
S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, is subtracted
Pressure distillation is steamed, and repeats backflow with being evaporated under reduced pressure twice；
S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can obtain halo ionic liquid.
The salt of other corresponding anions is added in obtained halo ionic liquid, by ion exchange, and is purified available
The ionic liquid of corresponding anion.
Ionic liquid and granular acrylic resin are added in container, constant temperature dissolves 6 hours at an established temperature
Or more, so that it may reach dissolving purpose, by stirring in course of dissolution, can effectively shorten dissolution time.
1 can be used by having dissolved the ionic liquid of acrylic resin:：After the ethyl acetate extraction of 1 volume ratio, acetic acid is isolated
Ethyl ester, remaining ionic liquid are reusable.
Compared with prior art, the invention has the advantages that.
The ionic liquid pollution of the present invention is small, nontoxic, environmentally friendly, simple to operate, keeps liquid at relatively high temperatures and does not wave
Hair, can be repeated several times use after use, cost-effective.
Embodiment
Below by specific embodiment to the further specific descriptions of the present invention.If experimental method is without special used in following
Illustrate, be the existing conventional method of the art, used dispensing or material, be to pass through business unless otherwise specified
The available dispensing of industry approach or material.Described above is only the preferred embodiment of the present invention, it is noted that for this technology
For the those of ordinary skill in field, under the premise without departing from the principles of the invention, some improvement can also be made, these improvement
Also it should be regarded as protection scope of the present invention.
Embodiment 1
The preparation method of ionic liquid comprises the following steps：
S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and bromoethane, first plus N- methylimidazoles are into container, then inward
Bromoethane is slowly added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；
S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, is subtracted
Pressure distillation is steamed, and repeats backflow with being evaporated under reduced pressure twice；
S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can 1-ethyl-3-methyllimidazolium bromide from
Sub- liquid.
The method of ion liquid dissolving acrylic resin：Take 5.00g 1-ethyl-3-methyllimidazolium bromides ionic liquid with
0.5000g particulate propylene acid resins, isothermal reaction 12 hours at 50 DEG C, acrylic resin 0.0200g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 95%.
Embodiment 2
The preparation method of ionic liquid comprises the following steps：
S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and N-Propyl Bromide, first plus N- methylimidazoles are into container, then inward
N-Propyl Bromide is slowly added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；
S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, is subtracted
Pressure distillation is steamed, and repeats backflow with being evaporated under reduced pressure twice；
S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can bromination 1- propyl group -3- methylimidazoles from
Sub- liquid.
The method of ion liquid dissolving acrylic resin：Take 5.00g brominations 1- propyl group -3- methylimidazoles ionic liquid with
0.5000g particulate propylene acid resins, isothermal reaction 10 hours at 80 DEG C, acrylic resin 0.0200g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 93%.
Embodiment 3
The preparation method of ionic liquid is as follows：
S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and NBB, first plus N- methylimidazoles are into container, then inward
NBB is slowly added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；
S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, is subtracted
Pressure distillation is steamed, and repeats backflow with being evaporated under reduced pressure twice；
S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can 1-butyl-3-methylimidazolium bromide from
Sub- liquid.
The method of ion liquid dissolving acrylic resin：Take 5.00g 1-butyl-3-methylimidazolium bromides ionic liquid with
0.5000g particulate propylene acid resins, isothermal reaction 11 hours at 120 DEG C, acrylic resin 0.0250g is dissolved, with acetic acid second
After ester extraction, the ionic liquid rate of recovery is 95%.
Embodiment 4
The preparation method of ionic liquid is as follows：
S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and NBB, first plus N- methylimidazoles are into container, then inward
NBB is slowly added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；
S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, is subtracted
Pressure distillation is steamed, and repeats backflow with being evaporated under reduced pressure twice；
S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can 1-butyl-3-methylimidazolium bromide from
Sub- liquid；
S4. hydrogen-oxygen is made by ion-exchange reactions with sodium hydroxide and 1-butyl-3-methylimidazolium bromide ionic liquid
Change 1- butyl -3- methylimidazole ionic liquids.
The method of ion liquid dissolving acrylic resin：Take 5.00g hydroxides 1- butyl -3- methylimidazoles ionic liquid with
0.5000g particulate propylene acid resins, isothermal reaction 6 hours at 180 DEG C, acrylic resin 0.4300g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 94%.
Embodiment 5
According to the synthetic method of ionic liquid described in embodiment 4, with sodium hydroxide and 1-butyl-3-methylimidazolium bromide from
Hydroxide 1- butyl -3- methylimidazole ionic liquids are made by ion-exchange reactions in sub- liquid, take 5.00g ionic liquids with
0.5000g particulate propylene acid resins, isothermal reaction 6 hours at 150 DEG C, acrylic resin 0.4000g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 94%.
Embodiment 6
According to the synthetic method of ionic liquid described in embodiment 4, with sodium hydroxide and bromination 1- propyl group -3- methylimidazoles from
Hydroxide 1- butyl -3- methylimidazole ionic liquids are made by ion-exchange reactions in sub- liquid, take 5.00g ionic liquids with
0.5000g particulate propylene acid resins, isothermal reaction 13 hours at 50 DEG C, acrylic resin 0.3000g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 92%.
Embodiment 7
According to the synthetic method of ionic liquid described in embodiment 4, with sodium hydroxide and 1-ethyl-3-methyllimidazolium bromide from
Hydroxide 1- butyl -3- methylimidazole ionic liquids are made by ion-exchange reactions in sub- liquid, take 5.00g ionic liquids with
1.0000g particulate propylene acid resins, isothermal reaction 1 hour at 180 DEG C, acrylic resin 0.8500g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 94%.
Embodiment 8
According to the synthetic method of ionic liquid described in embodiment 4, with sodium hydroxide and 1-butyl-3-methylimidazolium bromide from
Hydroxide 1- butyl -3- methylimidazole ionic liquids are made by ion-exchange reactions in sub- liquid, take 5.00g ionic liquids with
2.5000g particulate propylene acid resins, isothermal reaction 8 hours at 90 DEG C, acrylic resin 2.1100g is dissolved, uses ethyl acetate
After extraction, the ionic liquid rate of recovery is 93%.
Embodiment 9
According to the synthetic method of ionic liquid described in embodiment 4, with Potassium Hexafluorophosphate and bromination 1- propyl group -3- methylimidazoles
Hexafluorophosphoric acid 1- propyl group -3- methylimidazole ionic liquids are made by ion-exchange reactions in ionic liquid, take 5.00g ionic liquids
With 0.5000g particulate propylene acid resins, isothermal reaction 3 hours at 100 DEG C, acrylic resin 0.0300g is dissolved, with acetic acid second
After ester extraction, the ionic liquid rate of recovery is 96%.
Embodiment 10
According to the synthetic method of ionic liquid described in embodiment 4, with Potassium Hexafluorophosphate and bromination 1- propyl group -3- methylimidazoles
Hexafluorophosphoric acid 1- propyl group -3- methylimidazole ionic liquids are made by ion-exchange reactions in ionic liquid, take 5.00g ionic liquids
With 0.5000g particulate propylene acid resins, isothermal reaction 10 hours at 150 DEG C, acrylic resin 0.0500g is dissolved, uses acetic acid
After ethyl ester extraction, the ionic liquid rate of recovery is 96%.
Claims (2)
- A kind of 1. method with ion liquid dissolving acrylic resin, it is characterised in that the ionic liquid is imidazole-like ionic Liquid, glyoxaline ion liquid include cation and anion, the anion be bromide ion, acetate ion, hydroxyl from Son or hexafluorophosphoricacid acid ions, the group connect on cation imidazoles is ethyl, propyl group or butyl；The method of the dissolving is according to 1 ~ 20 by ionic liquid and acrylic resin：1 mass ratio mixing, mixture 50~ 200 DEG C of heated at constant temperature 0.5 ~ 12 hour, reaction terminates, and naturally cools to room temperature；The acrylic resin is by acrylic acid, methyl A kind of thermoplastic resin made of acrylic acid and its derivative polymerization.
- 2. according to the method for claim 1, it is characterised in that the preparation method of the ionic liquid comprises the following steps：S1. it is 1 to take mol ratio:1.1 N- methylimidazoles and halogenated hydrocarbons, first plus N- methylimidazoles are slow into container, then inward Halogenated hydrocarbons is added dropwise, in the case where temperature is 50 DEG C, condensing reflux, stirs 36 hours or more；S2. again by volume ratio be 2：1 ethyl acetate：Acetonitrile solution is added in S1 resulting solutions, is flowed back two hours, and decompression is steamed Steaming is evaporated, repeats backflow with being evaporated under reduced pressure twice；S3. step S2 products therefroms dry 24 hours at a temperature of 120 DEG C, you can obtain halo ionic liquid；The salt of other corresponding anions is added in obtained halo ionic liquid, by ion exchange, and purifies and can obtain accordingly The ionic liquid of anion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410801155.5A CN104479145B (en) | 2014-12-22 | 2014-12-22 | A kind of method of ion liquid dissolving acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410801155.5A CN104479145B (en) | 2014-12-22 | 2014-12-22 | A kind of method of ion liquid dissolving acrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104479145A CN104479145A (en) | 2015-04-01 |
| CN104479145B true CN104479145B (en) | 2018-03-09 |
Family
ID=52753760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410801155.5A Active CN104479145B (en) | 2014-12-22 | 2014-12-22 | A kind of method of ion liquid dissolving acrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104479145B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7888412B2 (en) * | 2004-03-26 | 2011-02-15 | Board Of Trustees Of The University Of Alabama | Polymer dissolution and blend formation in ionic liquids |
-
2014
- 2014-12-22 CN CN201410801155.5A patent/CN104479145B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104479145A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wheeler et al. | Ionic liquids as catalytic green solvents for nucleophilic displacement reactions | |
| CN105037062A (en) | Alcohol-based ternary deep-eutectic solvent and preparation method thereof | |
| CN105384707B (en) | A kind of preparation method of α amino acetophenones light trigger | |
| CN104119211A (en) | Method for preparing alpha-monobrominated ketone and alpha, alpha-dibrominated ketone compounds by selectively brominating ketone compounds | |
| Mason et al. | Microwave-assisted aqueous krapcho decarboxylation | |
| CN106083751A (en) | A kind of preparation method of s-triazine ultraviolet absorber UV 1577 | |
| CN104788342A (en) | Method for preparing aromatic nitrile compound from aromatic methanol | |
| Grolleau et al. | Clean and efficient iodination of thiophene derivatives | |
| CN103130843A (en) | Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester | |
| CN103539704A (en) | Method for preparing diuron | |
| Kumar et al. | Environmentally-Benign and Rapid Bromination of Industrially-Important Aromatics Using an Aqueous CaBr2− Br2 System as an Instant and Renewable Brominating Reagent | |
| CN103923015A (en) | Two selective ionic liquids and synthesis method thereof | |
| CN104479145B (en) | A kind of method of ion liquid dissolving acrylic resin | |
| CN102898337A (en) | Method for producing granular flame retardant tetrabromobisphenol S ether | |
| CN103333198A (en) | Unsaturated acyloxy silane and preparation method thereof | |
| CN102344346B (en) | Method for synthetizing tetrabromobisphenol A diallyl ether in water phase | |
| JP2010520896A (en) | Method of absorbing methyl acrolein with ionic liquid | |
| CN103965094B (en) | The synthetic method of the N-methyl-4-bromo-phthalimide of amino-5- | |
| CN101684067B (en) | Clean production method of antioxidant 1790 intermediate | |
| CN106187758A (en) | A kind of synthetic method of the different monooctyl ester of tetrabromobenzoic acid | |
| CN103351311B (en) | A kind of synthetic method of diphenatril | |
| CN103232396B (en) | Three selective ionic liquids and synthesizing method thereof | |
| CN105175281A (en) | Preparation method of Clocythrin pesticide | |
| CN103553866B (en) | A kind of method preparing adjacent two/trihalogenated benzene | |
| CN103204762B (en) | The preparation method of 4-bromo-4-iodine biphenyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230928 Address after: Room 2302, No.1 Yinfeng 1st Street, Nansha Street, Nansha District, Guangzhou City, Guangdong Province, 511466 Patentee after: Guangdong youbei Technology Co.,Ltd. Address before: 510006 No. 100 West Ring Road, University of Guangdong, Guangzhou Patentee before: GUANGDONG University OF TECHNOLOGY |