CN105837744A - Preparation method of double sensitive polymer hydrogel based on crown ether - Google Patents
Preparation method of double sensitive polymer hydrogel based on crown ether Download PDFInfo
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- CN105837744A CN105837744A CN201610409739.7A CN201610409739A CN105837744A CN 105837744 A CN105837744 A CN 105837744A CN 201610409739 A CN201610409739 A CN 201610409739A CN 105837744 A CN105837744 A CN 105837744A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
Abstract
The invention discloses a preparation method of double sensitive polymer hydrogel based on crown ether. The crown ether is introduced on a main chain of the hydrogel by a simple synthetic route; a polymer material which simultaneously responds to the temperature and environment ions is constructed by using an ion recognition function of the crown ether. Compared with the current intelligent hydrogel which only can generate response to one external stimulus, the preparation method disclosed by the invention has unique advantages and broader application prospect, and can be widely applied to the fields such as flexible executing elements, micromechanics, drug release slow-release systems and separating membrane parasite materials. In addition, the preparation method disclosed by the invention has the advantages of simplicity, short reaction time, high industrial degree and remarkable practical value.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to a kind of Dual Sensitive macromolecule hydrogel based on crown ether
Preparation method.
Background technology
Hydrogel be a kind of can be swelling and keep large quantity of moisture and undissolvable cross linked polymer in water.Water with
The form such as bonding water, irreducible water and Free water is present among macromolecule network and loses flowability, and makes hydrogel soft and energy
Keep certain shape.The response condition stimulated to external world according to hydrogel can be divided into conventional hydrogels and intelligent aqueous gel capable two big
Class.Conventional hydrogels is insensitive to the change of environment (such as temperature or pH value etc.), and intelligent aqueous gel capable is frequently referred to again environmental sensitivity
Hydrogel, refers to self energy sensing external environment (such as temperature, pH value, optical, electrical, pressure etc.) small change or stimulation, and energy
Produce a family macromolecule hydrogel of corresponding physical arrangement and chemical property.This can be with extraneous positive energy exchange and information
And the characteristic responded, make intelligent aqueous gel capable at flexibly direct writing element, micromechanics, drug delivery system, separation film, biological material
The aspects such as material have huge application prospect.
Current intelligent aqueous gel capable the most only produces response, if one can be developed simultaneously to temperature to a kind of outside stimulus
With the macromolecular material that environment ion produces response, it will have advantage and the application prospect of uniqueness.
Summary of the invention
Goal of the invention: in order to overcome prior art exists hydrogel be only to single outside stimulus produce response ask
Topic, the present invention proposes one temperature and environment ion are had responding ability simultaneously, has advantage and the range of application of uniqueness
The preparation method of Dual Sensitive macromolecule hydrogel based on crown ether more widely.
Technical scheme: in order to solve above-mentioned technical problem, the technical solution adopted in the present invention is: a kind of based on crown ether
The preparation method of Dual Sensitive macromolecule hydrogel, comprises the steps:
(1) synthesis of 4-ADP also-18-crown-6:
Adding 0.483g nitro crown ether in 100mL there-necked flask, stirring is dissolved in glycol monoethyl ether, adds 0.06g
Pd/C and the 7.5mL hydrazine hydrate of 10% reduces, and after backflow 1-3h, TLC follows the tracks of；Filtered while hot, concentrated mother liquor, separate out a large amount of
Solid, uses DMF recrystallization；Obtaining light gray solid 0.332g, yield 74%, fusing point is 165 DEG C-168 DEG C；
(2) synthesis of 4-acrylamide dibenzo-18 crown-6
Adding 1.8g 4-ADP also-18-crown-6 in 250mL there-necked flask, the stirring of 2mL triethylamine is dissolved in 80mL
Ethylene glycol monomethyl ether, under nitrogen protection, is slowly added dropwise 1.2mL acryloyl chloride under condition of ice bath, after reacting 2h under condition of ice bath, and room temperature
Reaction 2h, then it is warming up to 60 DEG C of reaction 2h, TCL tracking；Reaction terminates, in the frozen water that rear solution pours excess into, to filter out precipitation
Solid, washes with water repeatedly, DMF recrystallization；Obtaining pale solid 1.3g, yield 60%, fusing point is 158 DEG C-162 DEG C；
(3) synthesis of the hydrogel of Modified with Crown Ether
In the there-necked flask of 50mL, add raw material NIPA100mg, 4-acrylamide dibenzo-18 crown-6 1-4mg, hand over
Connection agent BIS 2-3.5mg, with H2O/THF mixed system is solvent, under nitrogen protection add initiator A PS0.0025mg and
TEMD20g；Reaction temperature controls at 25 DEG C, obtains gel solids after reaction 6h；
(4), after reaction terminates, gel cutting is decomposed into volume is 1cm3Square；It is then immersed in 48h in distilled water to obtain
To hydrogel finished product, to remove unreacted monomer and raw material.
Beneficial effect: the preparation method of a kind of based on crown ether the Dual Sensitive macromolecule hydrogel that the present invention provides is logical
Crossing easy synthetic route, introduce crown ether, utilize the ion identification function of crown ether on the main chain of hydrogel, it is a kind of right to construct
Temperature and environment ion produce the macromolecular material of response simultaneously, are typically only capable to outside to one compared to current intelligent aqueous gel capable
Stimulate and produce response, there is the advantage of uniqueness and the most wide application prospect, can be widely applied to flexibly direct writing element, microcomputer
The fields such as tool, drug release slow-releasing system, separation film parasite material；Additionally, preparation method of the present invention is simple, the response time
Short, industrialization degree is high, and practical value is notable.
Accompanying drawing explanation
Fig. 1 (a) is embodiment 1-4 and comparative example contains the hydrogel of different crown ether amount of monomer in pure water less than 5 DEG C
Swelling curve schematic diagram；
Fig. 1 (b) is embodiment 1-4 and comparative example contains the temperature sensitive curve signal of hydrogel of different crown ether amount of monomer
Figure；
Fig. 2 is that embodiment 4 adds the swelling curve schematic diagram of crown ether hydrogel before and after potassium ion；
Fig. 3 is that in pure water and potassium ion solution, the hydrogel of different content crown ether affects schematic diagram to SR.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1:
The preparation method of a kind of Dual Sensitive macromolecule hydrogel based on crown ether, comprises the steps:
(1) synthesis of 4-ADP also-18-crown-6:
Adding 0.483g nitro crown ether in 100mL there-necked flask, stirring is dissolved in glycol monoethyl ether, adds 0.06g
Pd/C and the 7.5mL hydrazine hydrate of 10% reduces, and after backflow 1-3h, TLC follows the tracks of；Filtered while hot, concentrated mother liquor, separate out a large amount of
Solid, uses DMF recrystallization；Obtaining light gray solid 0.332g, yield 74%, fusing point is 165 DEG C-168 DEG C；
(2) synthesis of 4-acrylamide dibenzo-18 crown-6
Adding 1.8g 4-ADP also-18-crown-6 in 250mL there-necked flask, the stirring of 2mL triethylamine is dissolved in 80mL
Ethylene glycol monomethyl ether, under nitrogen protection, is slowly added dropwise 1.2mL acryloyl chloride under condition of ice bath, after reacting 2h under condition of ice bath, and room temperature
Reaction 2h, then it is warming up to 60 DEG C of reaction 2h, TCL tracking；Reaction terminates, in the frozen water that rear solution pours excess into, to filter out precipitation
Solid, washes with water repeatedly, DMF recrystallization；Obtaining pale solid 1.3g, yield 60%, fusing point is 158 DEG C-162 DEG C；
(3) synthesis of the hydrogel of Modified with Crown Ether
Raw material NIPA100mg, 4-acrylamide dibenzo-18 crown-6 1mg, crosslinking is added in the there-necked flask of 50mL
Agent BIS 3mg, with H2O/THF mixed system is solvent, adds initiator A PS0.0025mg and TEMD20g under nitrogen protection；
Reaction temperature controls at 25 DEG C, obtains gel solids after reaction 4-6h；
(4), after reaction terminates, gel cutting is decomposed into volume is 1cm3Square；It is then immersed in 48h in distilled water to obtain
To hydrogel finished product, to remove unreacted monomer and raw material.
Route is synthesized as follows:
Embodiment 2-4:
Remaining step is identical, and in step (3), the usage amount of 4-acrylamide dibenzo-18 crown-6 (hereinafter referred to as CE) is not
With, wherein embodiment 2CE amount of application is 2mg, and in embodiment 3, CE usage amount is 3mg, and in embodiment 4, middle CE usage amount is 4mg.
Comparative example:
Arranging comparative example, remaining step is identical, and in step (3), CE addition is 0mg, carries out contrast test.
The temperature-sensitive of the Dual Sensitive macromolecule hydrogel based on crown ether that embodiment 1-4 and comparative example are prepared from
And ion-sensitive character research:
A) hydrogel temperature-sensitive research:
Fig. 1 (a) is comparative example and embodiment 1-4 contain different crown ether amount of monomer (figure is labeled as successively CE0%,
CE1%, CE2%, CE3%, CE4%) hydrogel swelling curve of less than 5 DEG C in pure water；It can be seen that with pure
PNIPA hydrogel compare, along with the introducing of crown ether group, the swelling ratio of hydrogel can be caused to reduce, equilibration time increase, molten
Swollen rate is reduced to about 12% from 33%, and equilibration time increased to about 400 minutes from 200 minutes；Reason is probably hat
The hydrophobic group of ether causes the hydrophilic reduced capability of hydrogel；It will be appreciated, however, that the swelling curve of hydrogel be not along with
The increase of the content dullness of crown ether or reduction；When the content of hydrogel increases to 3% from 1%, swelling ratio increases, and from
3% when increasing to 4%, and swelling ratio reduces.The number of the hydrophilic and hydrophobic group that reason is probably in the crown ether structures of different content
Mesh competition results is caused.
Fig. 1 (b) curve is the temperature sensitive curve of hydrogel, marks same Fig. 1 (a), along with temperature rises to 40 DEG C from 5 DEG C, and water
Gel swelling rate is gradually reduced.It should be apparent that contain the LCST of the temperature-sensitive hydrogel of dibenzo-18 crown-6 from figure
About at about 35 DEG C, it can be deduced that introducing crown ether group affects the least on the LCST of hydrogel.
B) the ion-sensitive character research of hydrogel:
Example 4 (BIS addition be 3mg, CE introduction volume be 4mg) carries out potassium ion sensitive natur test: Fig. 2 is to add
Before and after entering potassium ion, the swelling curve of crown ether hydrogel；Experimental result shows, compared with pure water, after adding potassium ion, and crown ether
The SR of hydrogel rises to 28% from 15%.After reason is crown ether complexation potassium ion, due to the impact of solvation effect, crown ether cycle
The hydrophilic ability of upper oxygen atom strengthens, and causes crown ether cycle surrounding water molecules to increase so that gel network structure water content increases,
Swelling behavior rate is caused to increase eventually.
In order to verify above-mentioned analysis further, we measure the hydrogel of embodiment difference crown ether content of monomer the most respectively
(introduction volume of CE3% and CE5%) swelling ratio in pure water and the solution containing potassium ion.As shown in Figure 3.It can be seen that
Adding after potassium ion, crown ether content of monomer is the hydrogel of 5%, and swelling ratio rises to 21.62% from 14.35%, and crown ether
Content of monomer is the hydrogel of 3%, and swelling ratio rises to 19.67% from 14.75%, and the increase along with Crown Ether Content is described, right
The complexation strength of potassium ion increases, and is conducive to promoting the swelling ratio of hydrogel.
From above-mentioned result of the test it can be seen that introduce crown ether on the main chain of hydrogel, utilize the ion identification merit of crown ether
Can, a kind of macromolecular material that temperature and environment ion are produced simultaneously response can be built, lead to compared to current intelligent aqueous gel capable
Often a kind of outside stimulus can only be produced response, there is the advantage of uniqueness and the most wide application prospect, can be widely applied to
The fields such as flexibly direct writing element, micromechanics, drug release slow-releasing system, separation film parasite material.
It should be pointed out that, that above detailed description of the invention is merely to illustrate the present invention rather than limits the scope of the present invention,
After having read the present invention, the amendment of the various equivalent form of values of the present invention is all fallen within and weighs appended by the application by those skilled in the art
Profit requires limited range.
Claims (1)
1. the preparation method of a Dual Sensitive macromolecule hydrogel based on crown ether, it is characterised in that comprise the steps:
(1) synthesis of 4-ADP also-18-crown-6:
Adding 0.483g nitro crown ether in 100mL there-necked flask, stirring is dissolved in glycol monoethyl ether, adds 0.06g 10%
Pd/C and 7.5mL hydrazine hydrate reduce, backflow 1-3h after, TLC follow the tracks of；Filtered while hot, concentrated mother liquor, separate out a large amount of solid
Body, uses DMF recrystallization；Obtaining light gray solid 0.332g, yield 74%, fusing point is 165 DEG C-168 DEG C；
(2) synthesis of 4-acrylamide dibenzo-18 crown-6
Adding 1.8g 4-ADP also-18-crown-6 in 250mL there-necked flask, the stirring of 2mL triethylamine is dissolved in 80mL second two
Alcohol methyl ether, under nitrogen protection, is slowly added dropwise 1.2mL acryloyl chloride under condition of ice bath, after reacting 2h under condition of ice bath, and room temperature reaction
2h, then it is warming up to 60 DEG C of reaction 2h, TCL tracking；Reaction terminates, in the frozen water that rear solution pours excess into, to filter out consolidating of precipitation
Body, washes with water repeatedly, DMF recrystallization；Obtaining pale solid 1.3g, yield 60%, fusing point is 158 DEG C-162 DEG C；
(3) synthesis of the hydrogel of Modified with Crown Ether
Raw material NIPA100mg, 4-acrylamide dibenzo-18 crown-6, crosslinking agent B IS 2-is added in the there-necked flask of 50mL
3.5mg, with H2O/THF mixed system is solvent, adds initiator A PS0.0025mg and TEMD20g under nitrogen protection；Reaction
Temperature controls at 25 DEG C, obtains gel solids after reaction 4-6h；
(4), after reaction terminates, gel cutting is decomposed into volume is 1cm3Square；It is then immersed in 48h in distilled water and obtains water-setting
Glue finished product, to remove unreacted monomer and raw material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867799A (en) * | 2019-03-16 | 2019-06-11 | 济南敏杰电子有限责任公司 | A kind of heat sensitive compounds and preparation method thereof |
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| US20030166736A1 (en) * | 2001-12-28 | 2003-09-04 | Jeol Ltd. And Jeol Engineering Co., Ltd. | Method of producing ion sensitive film for ion sensor |
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| CN102786616A (en) * | 2012-08-03 | 2012-11-21 | 天津工业大学 | Benzocrown ether graft polymer with lithium isotopic separation effect and preparation method thereof |
| CN104245801A (en) * | 2012-02-20 | 2014-12-24 | 剑桥实业有限公司 | Cucurbituril-based hydrogels |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030166736A1 (en) * | 2001-12-28 | 2003-09-04 | Jeol Ltd. And Jeol Engineering Co., Ltd. | Method of producing ion sensitive film for ion sensor |
| US20030213691A1 (en) * | 2002-03-11 | 2003-11-20 | Auburn University | Ion-detecting sensors comprising plasticizer-free copolymers |
| CN104245801A (en) * | 2012-02-20 | 2014-12-24 | 剑桥实业有限公司 | Cucurbituril-based hydrogels |
| CN102786616A (en) * | 2012-08-03 | 2012-11-21 | 天津工业大学 | Benzocrown ether graft polymer with lithium isotopic separation effect and preparation method thereof |
Non-Patent Citations (3)
| Title |
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| XUE-WEN LIU ET AL: ""Response behavior of ion-sensitive hydrogel based on crown ether"", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867799A (en) * | 2019-03-16 | 2019-06-11 | 济南敏杰电子有限责任公司 | A kind of heat sensitive compounds and preparation method thereof |
| CN109867799B (en) * | 2019-03-16 | 2021-08-27 | 济南敏杰电子有限责任公司 | Thermal-sensitive compound and preparation method thereof |
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