CN105037593A - CO2-responding monomer and polymer thereof - Google Patents
CO2-responding monomer and polymer thereof Download PDFInfo
- Publication number
- CN105037593A CN105037593A CN201510192007.2A CN201510192007A CN105037593A CN 105037593 A CN105037593 A CN 105037593A CN 201510192007 A CN201510192007 A CN 201510192007A CN 105037593 A CN105037593 A CN 105037593A
- Authority
- CN
- China
- Prior art keywords
- monomer
- compound
- solvent
- response
- chain
- 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.)
- Pending
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
- Y02P20/141—Feedstock
Abstract
The invention relates to a CO2-responding monomer and a polymer thereof. The CO2-responding monomer is prepared by means of direct reaction between p-vinylphenylamine and acetal, and then with alternately feeding of CO2 and N2, the monomer is subjected to hydrophilicity/hydrophobicity transformation, wherein the solution electrical conductivity of the monomer is changed periodically, thereby proving that the monomer is significant in CO2-responding performance. The monomer is mild in preparation conditions, is high in yield and is simple in operation and allows free radical polymerization. A prepared CO2-responding polymer prepared from the monomer has potential application value in the fields of controlled-release drugs, bio-sensors, energy resource and environment protection, oil exploitation, emulsion polymerization and the like.
Description
Technical field
The present invention relates to a kind of CO
2response monomer and polymkeric substance prepared therefrom, belong to intelligent polymer Material Field.
Background technology
Intelligent macromolecule material is that one can perception environmental change, and is realized the novel material of instruction and execution by self judgment and conclusion.At present, based on temperature response, pH response, oxidation-reduction reaction and light stimulus response intelligent macromolecule existed system and deep research.But temperature and light can be confined to some specific site of action, pH, oxidation-reduction reaction then can because introducing acid, alkali, redox agent and cause stimulating the defects such as residual.CO
2as a kind of greenhouse gases, not only cheap and easy to get, and be a kind of biomass cells meta-bolites, there is good biocompatibility and membrane permeability, it can be used as the stimulation mode of intelligent primitive not only simple to operate, with low cost, and new pollution can not be brought to system.Therefore, in recent years, a kind of novel based on CO
2the polymkeric substance of micro-tapping response becomes the focus of research, and it has in fields such as drug controlled release, biosensor, energy environment protection, oil production, letex polymerizations and has huge potential using value.
At present, the CO reported
2the synthesis of micro-tapping responsive polymer mainly contains two kinds of methods.One, is first polymerized, and then modifies CO
2response functional group.As the report that Zhou (Macromolecules2009,42,7146-7154) and Guo (Chem.Commun., 2011,47,9348-9350) etc. do.Its two, first synthesize CO
2response monomer, then carries out polyreaction.This method more meets the actual requirement of Macroscopic single crystal technique, simple to operate, is conducive to large-scale production.The acrylamido CO reported
2response monomer (Angew.Chem.Int.Ed.2011,50,4923-4927; Langmuir2012,28,5940-5946) synthetic route is longer, and owing to wherein relating to the reaction of diamines, therefore the control ratio of its synthesis condition is more difficult.And based on CO prepared by traditional temperature-responsive monomer
2responsive polymer (ACSMacroLett.2012,1,57-61) is limited by again the limitation of response temperature.Therefore, be necessary to study a kind of novel, synthetic route is shorter, the simple CO of synthesis technique
2response monomer, and be polymerized under suitable conditions, thus obtain CO easily
2responsive polymer.
Summary of the invention
The present invention adopts vinyl amine and aldolization, obtains a kind of CO
2response monomer, and carried out radical polymerization, obtain based on this CO
2the polymkeric substance of stimuli responsive type monomer.
Tool of the present invention has the following advantages:
1. synthesize CO
2the reaction conditions of response monomer is gentle, and productive rate is high, simple to operate;
2. the CO synthesized by
2response monomer is alternately passing into CO
2and N
2under condition, the transformation of hydrophilic, hydrophobic property can be realized;
3. the CO synthesized by
2response monomer shows the reversible change of obvious specific conductivity, illustrates that it has obvious CO
2response performance;
4. obtained CO
2response monomer can carry out conventional free radical polymerization and controllable free-radical polymerisation.
Accompanying drawing explanation
The CO of Fig. 1 embodiment of the present invention
2the conductance profile of stimulating responsive monomer.
Fig. 2 .CO
2response monomer is by the photo of hydrophilic, hydrophobic sex reversal.
Embodiment
The present invention is achieved by the following measures:
A kind of CO
2the monomer of response and polymerization process thereof, is characterized in that: compound (a) is a kind of to vinyl phenyl amine, and Gabriel reaction method can be adopted efficiently to prepare; Compound (b) is a kind of acetal; The two direct reaction can obtain CO
2response monomer (c).C () is carried out radical polymerization and can be obtained based on this CO in solvent (d)
2the polymkeric substance (e) of response monomer.Chemical equation is:
Detailed process is as follows:
In reaction vessel, add compound (b) by consumption, then add a certain amount of organic solvent dissolution or not solubilizing agent, logical N
2deoxygenation.Then compound (a) is added, at N
2under protection, 40 ~ 80 DEG C of stirring reaction 0.5 ~ 2h.React rear underpressure distillation except desolventizing and by product, obtain CO
2response monomer (c).
In reaction vessel, add CO by consumption
2response monomer (c), then adds a certain amount of solvent (d) and chain-transfer agent (requiring to determine dosage according to molecular weight design), initiator (0.2 ~ 1 times of equivalent of chain-transfer agent consumption), logical N under normal temperature
20.5 ~ 1h deoxygenation.Then, 70 DEG C of stirred in water bath reaction 24 ~ 48h are put into.After having reacted, aftertreatment obtains based on this CO
2the polymkeric substance of response monomer.
Solvent (d) in Raolical polymerizable is acid solvent, can be the mixed solvent that Glacial acetic acid or Glacial acetic acid and other organic solvents are formed.Chain-transfer agent is the general chain-transfer agent of reversible addion-fragmentation chain transfer radical polymerization (RAFT), also can not add chain-transfer agent, namely carries out traditional radical polymerization.Initiator is general initiator, as AIBN, V501, V50, V70 etc.
Embodiment 1
In reaction vessel, add compound (b) (4-vinyl benzyl amine), logical N
2deoxygenation.Then compound (a) (N,N-dimethylacetamide dimethylacetal) is added, N
2under protection, 65 DEG C of stirring reaction 1.5h.After having reacted, normal temperature underpressure distillation, except desolventizing and by product, obtains CO
2response monomer (c).
In reaction vessel, add CO
2response monomer (c), then a certain amount of solvent (d) Glacial acetic acid is added, monomer concentration controls at 0.5M), and chain-transfer agent (2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid, according to molecular weight design require determine consumption), initiator (AIBN, 0.5 times of equivalent of chain-transfer agent consumption), logical N under normal temperature
20.5 ~ 1h deoxygenation.Then, 70 DEG C of stirred in water bath reaction 24h are put into.After having reacted, neutralize alkalescence with saturated sodium bicarbonate aqueous solution, precipitate in acetone, obtain CO
2responsive polymer.
Embodiment 2
In reaction vessel, add compound (b) (4-vinyl benzyl amine), logical N
2deoxygenation.Then compound (a) (N,N-dimethylacetamide dimethylacetal) is added, N
2under protection, 65 DEG C of stirring reaction 1.5h.After having reacted, normal temperature underpressure distillation, except desolventizing and by product, obtains CO
2response monomer (c).
In reaction vessel, add CO
2response monomer (c), then a certain amount of solvent (d) (Glacial acetic acid is added, monomer concentration controls at 0.5M), and chain-transfer agent (4-cyano group-4-[(dodecyl sulfanyl thiocarbonyl group) sulfanyl] valeric acid, require to determine consumption according to molecular weight design), initiator (V501,0.5 times of equivalent of chain-transfer agent consumption), logical N under normal temperature
20.5h deoxygenation.Then, 70 DEG C of stirred in water bath reaction 24h are put into.After having reacted, neutralize alkalescence with saturated sodium bicarbonate aqueous solution, precipitate in acetone, obtain CO
2responsive polymer.
Embodiment 3
In reaction vessel, add compound (b) (4-vinyl benzyl amine), logical N
2deoxygenation.Then compound (a) (N,N-dimethylacetamide dimethylacetal) is added, N
2under protection, 65 DEG C of stirring reaction 1.5h.After having reacted, normal temperature underpressure distillation, except desolventizing and by product, obtains CO
2response monomer (c).
In reaction vessel, add CO
2response monomer (c), then adds a certain amount of solvent (d) (Glacial acetic acid, monomer concentration controls at 0.5M), initiator (AIBN requires to determine consumption according to molecular weight design), logical N under normal temperature
20.5h deoxygenation.Then, 70 DEG C of stirred in water bath reaction 24h are put into.After having reacted, neutralize alkalescence with saturated sodium bicarbonate aqueous solution, precipitate in acetone, obtain CO
2responsive polymer.
Embodiment 4
In reaction vessel, add compound (b) (4-vinyl aniline), logical N
2deoxygenation.Then compound (a) (N,N-dimethylacetamide dimethylacetal) is added, N
2under protection, 65 DEG C of stirring reaction 1.5h.After having reacted, normal temperature underpressure distillation, except desolventizing and by product, obtains CO
2response monomer (c).
In reaction vessel, add CO
2response monomer (c), then a certain amount of solvent (d) (Glacial acetic acid is added, monomer concentration controls at 0.5M), and chain-transfer agent (4-cyano group-4-[(dodecyl sulfanyl thiocarbonyl group) sulfanyl] valeric acid, require to determine consumption according to molecular weight design), initiator (V501,0.5 times of equivalent of chain-transfer agent consumption), logical N under normal temperature
20.5h deoxygenation.Then, 70 DEG C of stirred in water bath reaction 24h are put into.After having reacted, neutralize alkalescence with saturated sodium bicarbonate aqueous solution, precipitate in acetone, obtain CO
2responsive polymer.
Claims (9)
1. a CO
2response monomer and polymkeric substance prepared therefrom, is characterized in that: compound (a) is a kind of to vinyl phenyl amine, and compound (b) is a kind of acetal, and the two direct reaction can obtain CO
2response monomer (c), (c) carries out radical polymerization and can obtain based on this CO in solvent (d)
2the polymkeric substance (e) of response type monomer.
2. compound (a) according to claim 1 is a kind of amine with vinyl phenyl, and Gabriel reaction method can be adopted efficiently to prepare, and its general structure is:
3. compound (b) according to claim 1 is a kind of acetal, and its general structure is:
4. CO according to claim 1
2response monomer (c) is the amidine of a kind of band to vinyl phenyl, and its general structure is:
5. according to claim 1 based on this CO
2the polymkeric substance (e) of response type monomer, its general structure is:
6. compound (a) according to claim 1 and compound (b) react, generate compound (c), it is characterized in that: in reaction vessel, compound (b) is added by consumption, then add a certain amount of organic solvent dissolution or not solubilizing agent also can, logical N
2deoxygenation, then adds compound (a), N
2under protection, 40 ~ 80 DEG C of stirring reaction 0.5 ~ 2h, have reacted rear underpressure distillation except desolventizing and by product, have obtained CO
2response monomer (c).
7. reaction according to claim 8, is characterized in that: can not use solvent or use acetonitrile, the one in methylene dichloride, chloroform, dimethyl formamide (DMF), tetrahydrofuran (THF) (THF) organic solvent.
8. (c) according to claim 1 carries out radical polymerization and can obtain CO in solvent (d)
2responsive polymer (e), is characterized in that: in reaction vessel, adds CO by consumption
2response monomer (c), then adds a certain amount of solvent (d), and requires to determine that dosage adds chain-transfer agent, initiator initiator according to molecular weight design, and initiator amount is 0.2 ~ 1 times of equivalent of chain-transfer agent consumption, logical N under normal temperature
2, continue 0.5 ~ 1h deoxygenation, then put into 70 DEG C of stirred in water bath reaction 24 ~ 48h; After having reacted, aftertreatment obtains based on this CO
2the polymkeric substance of response monomer, solvent (d) is acid solvent, is the mixed solvent that Glacial acetic acid or Glacial acetic acid and other organic solvents are formed.
9. radical polymerization according to claim 10, it is characterized in that: chain-transfer agent is the general chain-transfer agent of reversible addion-fragmentation chain transfer radical polymerization (RAFT), also chain-transfer agent can not be added, carry out radical polymerization, radical polymerization initiator used is AIBN, one in V501, V50, V70.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510192007.2A CN105037593A (en) | 2014-04-18 | 2015-04-15 | CO2-responding monomer and polymer thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410156384 | 2014-04-18 | ||
| CN201510192007.2A CN105037593A (en) | 2014-04-18 | 2015-04-15 | CO2-responding monomer and polymer thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105037593A true CN105037593A (en) | 2015-11-11 |
Family
ID=54444596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510192007.2A Pending CN105037593A (en) | 2014-04-18 | 2015-04-15 | CO2-responding monomer and polymer thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037593A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632786A (en) * | 2016-10-10 | 2017-05-10 | 长春工业大学 | Method for preparing large-particle monodispersed high-stable polymer emulsion by CO2 induced in-situ charge neutrality technology |
| CN107099005A (en) * | 2017-05-07 | 2017-08-29 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN111285433A (en) * | 2020-03-06 | 2020-06-16 | 中国科学院生态环境研究中心 | CO (carbon monoxide)2Method for treating emulsified oil wastewater by atmosphere response material |
-
2015
- 2015-04-15 CN CN201510192007.2A patent/CN105037593A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632786A (en) * | 2016-10-10 | 2017-05-10 | 长春工业大学 | Method for preparing large-particle monodispersed high-stable polymer emulsion by CO2 induced in-situ charge neutrality technology |
| CN107099005A (en) * | 2017-05-07 | 2017-08-29 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN107099005B (en) * | 2017-05-07 | 2019-04-02 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN111285433A (en) * | 2020-03-06 | 2020-06-16 | 中国科学院生态环境研究中心 | CO (carbon monoxide)2Method for treating emulsified oil wastewater by atmosphere response material |
| CN111285433B (en) * | 2020-03-06 | 2021-09-21 | 中国科学院生态环境研究中心 | CO (carbon monoxide)2Method for treating emulsified oil wastewater by atmosphere response material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102031101B (en) | Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof | |
| CN103087257B (en) | Preparation method for pH and temperature dual-sensitive ion micro-hydrogel | |
| CN102659979B (en) | Preparation method of double-hydrophilic temperature response polymer | |
| CN101434684B (en) | Amphipath block copolymers, congeries material thereof, preparation method and application | |
| CN105037593A (en) | CO2-responding monomer and polymer thereof | |
| CN101935373B (en) | Preparation method of multi-sensitivity photosensitive polyamphoteric electrolyte micelle | |
| CN101798503A (en) | Novel polymeric oil-displacing agent for improving recovery ratio and application thereof | |
| CN105566516B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN104262555A (en) | Block polymer with multi-response property for temperature and carbon dioxide and preparation method thereof | |
| CN103265492B (en) | Chlorinated 1-vinyl-3-carboxymethyl imidazole polymerizable acidic ionic liquid and synthetic method thereof | |
| CN110305267A (en) | A kind of high-intensitive response type hydrogel and preparation method thereof based on block copolymer | |
| CN102703042A (en) | Alkali-proof polymer-type profile control agent and preparation method thereof | |
| CN105237678A (en) | Partially hydrolyzed acrylamide water-soluble polymer with utlralong hydrophobic long chain, preparation method therefor and application thereof | |
| CN105566560B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN103936947B (en) | A kind of preparation method of dual photosynthesis-carbon dioxide response block copolymer | |
| CN101712736A (en) | Method for preparing fast responsive temperature-sensitive hydrogel by adopting frontal polymerization technology | |
| CN106046251A (en) | Temperature-resistant and salt-tolerant polymeric filtrate loss reducer for water-based drilling fluid and method for preparing temperature-resistant and salt-tolerant polymeric filtrate loss reducer | |
| CN101220263A (en) | Water-based fracturing fluid gelatinizer and producing method thereof | |
| NO20083754L (en) | Continuous process for the preparation of vinyl chloride (co) polymers | |
| Liu et al. | A CO2-switchable amidine monomer: synthesis and characterization | |
| CN102993057B (en) | Synthesis method of 1,6-bis(cyano-guanidino) hexane | |
| CN104371043A (en) | Thioxanthone acetylfluorene photoinitiator and preparation method thereof | |
| CN104086702A (en) | Benzene-ring-containing modified acrylamide water-soluble amphoteric polymer and preparation method thereof | |
| CN104152131A (en) | Polymeric oil-displacing agent containing sulfite structure and synthetic method thereof | |
| CN103382239B (en) | Method for modified preparation of high-oil-absorption gel through human hair keratin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151111 |