CN101555306A - Method for synthesizing hydrogel - Google Patents
Method for synthesizing hydrogel Download PDFInfo
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- CN101555306A CN101555306A CNA2009100274265A CN200910027426A CN101555306A CN 101555306 A CN101555306 A CN 101555306A CN A2009100274265 A CNA2009100274265 A CN A2009100274265A CN 200910027426 A CN200910027426 A CN 200910027426A CN 101555306 A CN101555306 A CN 101555306A
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Abstract
The invention discloses a method for synthesizing hydrogel, one out of N, N-(dimethylamino) ethyl methacrylate or methylacrylic acid polyethylene glycol single methyl ether ester is taken as a monomer, the monomer, an initiator, a cross-linking agent, a catalyst, a complexing agent and a reductant are added according to the molar ratio that monomer: initiator: cross-linking agent: catalyst: complexing agent and reductant is equal to 100-1000: 1: 1-50: 0.05-3: 0.15-9: 1-10, so as to carry out the AGET ATRP reaction and synthesize the hydrogel; wherein the initiator is selected from one out of polyethylene glycol bis (alpha-bromoisobutyrate) ester or 2,6-dibromo dimethyl heptanedioate; the cross-linking agent is one out of ethylene glycol dimethacrylate or poly(ethylene glycol) dimethacrylate; and the catalyst is selected from one out of hexahydrated high ferric chloride or ferric bromide. The method can control the crosslinking degree by regulating the using amount of the cross-linking agent, so that the method can control the mesh size of the hydrogel, control the liquid absorption performance of the hydrogel and obtain the hydrogel with good biocompatibility.
Description
Technical field
The present invention relates to a kind of preparation method of gel, be specifically related to a kind of method of synthetic water gel.
Background technology
Colloidal particle or polymer in colloidal sol or the solution interconnect under certain condition, form spacial framework, have been full of the liquid as dispersion medium in the structure, and a kind of so special dispersion system is called gel.Because the affinity of liquid and macromolecule network, liquid is enclosed in the inside by macromolecule network, lost flowability, so gel can demonstrate certain shape as solid.Gel is in swelling process, and on the one hand solvent is tried hard to infiltrate and made its volumetric expansion in the superpolymer, because the cross-linked polymer volume expands, makes molecular network be subjected to stress and shrinks on the other hand, when these two kinds of opposite tendencies are contended with mutually, has reached swelling equilibrium.The character of the swelling behavior of high-molecular gel and its network structure and the liquid that network comprised has close ties, and is also relevant with temperature and pressure, and the quantitative relationship between them can derive with Flory-Huggins osmotic pressure formula.Swelling or contraction can take place in volume when this intelligent gel was subjected to the stimulation (as pH, ionic strength, temperature, electric field, light) of outside atmosphere, this volume change is discontinuous, utilize this stimuli responsive characteristic to be with a wide range of applications in fields such as Aeronautics and Astronautics, agricultural, medical and health and biomimetic engineerings with it as material of transmitter power element, switch and shape memory etc.
Gel can be divided into 2 big class, i.e. oil absorbency gel (not absorbing water) and hydrogels.Existing gel adopts traditional free radical polymerisation process synthetic mostly, as solution polymerization, suspension polymerization, inverse suspension polymerization etc.The main drawback of these methods is: because high rate of polymerization and the heat effect in the reaction process, chain transfer, chain termination reaction and the autoacceleration phenomenon etc. of conventional radical polymerization, make the gel synthesize can not control segment molecular mass between the cross-linking density of network and cross-linking set, the cross-linking set skewness and be difficult to control, the structure of synthetic high-molecular gel all is metamict, there is not regularity, irritant reaction to outside atmosphere is blunt, there is not synergetic property, therefore the gellifying property that synthesizes is undesirable, has limited its application in material is synthetic.Therefore, how to synthesize the regular polymer of specified structure with free radical polymerisation process, and make its industrialization be polymer circle for many years one greatly the dream.
Atom transfer radical polymerization (being called for short ATRP) is a kind of activity/controllable free radical polymerization process that proposes nineteen ninety-five.ATRP integrates common radical polymerization and living polymerization, and compare with other living polymerizations, its monomer that is suitable for is wider, the molecular designing ability is stronger, and especially its polymerizing condition gentleness, technology are simple, and these are that other living polymerizations are incomparable.Therefore ATRP is very promising activity/controllable polymerization technology, in the polymer molecule design broad application prospect is arranged, and also has a large amount of bibliographical informations to be used for synthesized gel rubber.But having had 14 days so far, this method development still can't see industrialized sign, analyzing its reason mainly is because due to some shortcomings of existing ATRP polymerization system, for example: (1) needs to use the transition metal salt catalyst of big consumption in the ATRP of routine system, this catalyzer can remain in the polymkeric substance and bring pollution to polymkeric substance, although have more bibliographical information to remove the method for metal residue in the polymkeric substance, will inevitably cause the rising of industrial cost; (2) since to use low-oxidation-state transition metal salt (as CuCl, FeCl
2), moisture-sensitive and oxidation make troubles for preservation and use; (3) whole polymerization system will carry out deoxygenation, troublesome poeration in advance.In order to overcome the deficiency of conventional ATRP, developed another kind of ATRP system again, i.e. reverse ATRP, this method with the transition metal salt of high oxidation state stable under the usual conditions (as CuCl
2, FeCl
3Thereby) replace the transition metal salt of low-oxidation-state to avoid the deficiency of conventional ATRP, but this method must be used the transition metal salt of bigger consumption and owing to used conventional radical initiator (as AIBN etc.), make polymerization process bring " pair " product that the conventional free radical initiated polymerization brings inevitably and the end-functionalization degree of final polymerisate is reduced, thereby influence its " activity ".
Therefore, develop a kind of method of synthetic water gel simple to operate, not only can carry out the hydrogel network structure design, synthetic grid adjustable size control, the transformable hydrogel of grid structure, and avoid the negative impact of catalyzer, for synthetic intelligent gel rubber material lays the first stone, has significant and positive significance.
On the other hand, (the Jakubowski W. of Matyjaszewski seminar, Matyjaszewski K.Macromolecules, 2005,38,4139-4146.) a kind of new ATRP method (ATRPusing Activators Generated by Electron Transfer is called for short AGET ATRP) proposed in 2005.Still adopt Organohalogen compounds used among the conventional ATRP as initiator in this reaction system, but the transition metal salt that adopts employed high oxidation state in the reverse ATRP is (as CuCl
2) be catalyzer, the transition metal salt (as CuCl) that is used for producing the low-oxidation-state of free radical among the conventional ATRP is then reacted by the transition metal salt of the high oxidation state of adding system and reductive agent and original position produces; Described reductive agent is generally polyose organic compound (as glucose), and xitix and stannous octoate etc. is easy to get and nontoxic or low toxicity compounds.Owing to produce in position in the reaction of transition metal salt (as CuCl) of low-oxidation-state, reductive agent only and the transition metal salt of high oxidation state (as CuCl
2) reaction and not with system in Organohalogen compounds and monomer react, produce so in position in the process of transition metal salt of low-oxidation-state with regard to the reaction between the transition metal salt that can not have influence on Organohalogen compounds and low-oxidation-state.The particularly important is: (1) is because the oxygen that the existence of reductive agent exists in can also the consumption reaction system, so before carrying out AGET ATRP polymerization, as long as add an amount of reductive agent (removing the amount that consumes oxygen), whole polymerization system then needn't will carry out deoxygenation in advance as conventional and reverse ATRP; (2) transition metal salt catalyst owing to low-oxidation-state produces in position, then the amount of needed catalyzer can descend greatly in the system, can be reduced to 5ppm even lower, be significantly less than the level of the required hundreds of of conventional ATRP～several thousand ppm, the residual quantity of the transition metal salt in the polymerisate that obtains like this is very low, and product does not even need to carry out aftertreatment.These 2 then mean a great concerning commercial run.
Yet aforesaid method is to be used for the synthesizing linear polymkeric substance, does not relate to the synthetic field of hydrogel; In addition, the catalyzer that aforesaid method relates to substantially only is confined to the mantoquita catalyst system, and the mantoquita catalyst system is because its inherent bio-toxicity makes synthetic the going up of its intelligent aqueous gel capable material that is applied to good biocompatibility bring material with bigger toxic problem with regard to existing.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthetic water gel with synthetic grid adjustable size control, grid structure can change and the hydrogel of good biocompatibility, and is avoided the negative impact of catalyzer.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of method of synthetic water gel, with methacrylic acid-N, a kind of in N dimethylamine base ethyl ester or the Methylacrylic acid polyethylene glycol single armor ether ester as monomer, in molar ratio, monomer: initiator: linking agent: catalyzer: coordination agent: reductive agent=100～1000: 1: 1～50: 0.05～3: 0.15～9: 1～10, add monomer, initiator, linking agent, catalyzer, coordination agent and reductive agent, carry out AGET ATRP reaction, the synthetic water gel;
Wherein, described initiator is selected from polyoxyethylene glycol two (α-isobutyl bromide) ester or 2, a kind of in the 6-dibromo NSC 52563; Described linking agent is a kind of in ethylene glycol dimethacrylate or the polyethylene glycol dimethacrylate; Described catalyzer is selected from a kind of in high iron(ic) chloride of six hydrations or the iron bromide.
Above, described methacrylic acid-N, N dimethylamine base ethyl ester or Methylacrylic acid polyethylene glycol single armor ether ester are water miscible.
What in the technique scheme, described coordination agent was selected from three (3,6-dioxy heptyl) amine or N, N, N ', N ", N " in the PMDETA is a kind of.
In the technique scheme, described reductive agent is a kind of in xitix or the glucose.
Principle of work of the present invention is: utilize AGET ATRP method to have activity, controlled polymerization characteristics, the molecular weight and the cross-linking density of the hydrogel that can designing institute gets, and can come the character of telomerized polymer by changing monomeric kind, thereby change the performance of final hydrogel.In addition, because the method applied in the present invention can directly carry out under air atmosphere, and employed catalyzer is that the trivalent iron salt of high oxidation state is stable under air atmosphere, thereby this building-up process is simple to operation, helps suitability for industrialized production.
Because the employing of technique scheme, compared with prior art, the present invention has following advantage:
1. the present invention adopts AGET ATRP method, thereby the molecular weight of polymkeric substance can design easily, can regulate the consumption of linking agent simultaneously and control degree of crosslinking, thereby can control the sizing grid of hydrogel, the absorbent of control hydrogel, the regular hydrogel of synthetic specified structure.
2. to adopt good biocompatibility and the little molysite of toxicity be catalyzer in the present invention, and its synthetic hydrogel that obtains is nontoxic or toxicity is very little, can obtain the intelligent aqueous gel capable material of good biocompatibility.
3. the catalyzer and the chemical reagent of the present invention's employing are stable in the air, make this reaction directly to carry out under air atmosphere, are convenient to suitability for industrialized production.
4. preparation method of the present invention is simple and cost is lower, has a good application prospect.
5. the present invention can come the character of telomerized polymer by changing monomeric kind, thereby change the performance of final hydrogel in polymerization process.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Use reagent among the embodiment for convenience of description, unify explanation at this, as follows:
Methacrylic acid-N, N dimethylamine base ethyl ester (DMAEMA), 99%, Aldrich company;
Methylacrylic acid polyethylene glycol single armor ether ester (PEGMA), 99%, molecular weight is 475g/mol, Aldrich company;
Ethylene glycol dimethacrylate (EGDMA), 98%, Aldrich company;
2,6-dibromo NSC 52563 (DMDBH), 97%, Aldrich company;
High iron(ic) chloride (the FeCl of six hydrations
3.6H
2O) and xitix (VC), analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co.;
Polyoxyethylene glycol two (α-isobutyl bromide) ester (Br-PEG-Br), molecular weight are 6300g/mol, self-control;
N, N, N ', N ", N " PMDETA (PMDETA), 98%, Jiang Dian chemical plant, Liyang;
Three-(3,6-dioxy heptyl) amine (TDA-1), 97%, Linhai Xinhua chemical plant;
N, dinethylformamide (DMF) and methyl alcohol, analytical pure, Changshu City Yang Yuan chemical reagent company limited.
Embodiment one
With Br-PEG-Br PPEGMA hydrogel synthetic of initiator
Press proportioning n (PEGMA): n (Br-PEG-Br): n (EGDMA): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=500: 1: 5～40: 3: 9: 5, add FeCl
3.6H
2O, TDA-1, PEGMA (2mL), EGDMA, B r-PEG-Br and VC in the ampoule of 10mL, direct tube sealing (mass polymerization) under air atmosphere.If adopt solution polymerization then after adding above-mentioned all chemical reagent, to add the 2mL deionized water again and direct tube sealing under air atmosphere.Place the oil bath under the steady temperature (90 ℃) to react (3～46h) ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, filter postlyophilization with the appropriate amount of deionized water immersion and promptly obtain xerogel.
Adopt macromole bifunctional initiator (Br-PEG-Br), by changing the consumption of linking agent (EGDMA), the data of the pick up of the polyalcohol hydrogel that obtains (being solvent to be inhaled with deionized water and methyl alcohol respectively) are as shown in table 1.In present embodiment one, two kinds of polymerization processs are that mass polymerization (sequence number 1,3,5) and solution polymerization (sequence number 2,4,6) are used.By data in the table as can be seen, adopt the imbibition ability of the hydrogel that solution polymerization obtains to be greater than mass polymerization, but required polymerization time is longer than mass polymerization.The network size of polymkeric substance can be controlled by the consumption that changes linking agent easily well, thus the absorbent of control hydrogel, this advantage of the present invention just and characteristic place.
Relation between table 1.PPEGMA hydrogel pick up and the dosage of crosslinking agent
aMass polymerization: PEGMA=2.0mL; [PEGMA]/[Br-PEG-Br]/[FeCl
3.6H
2O]/[TDA-1]/[VC]=500/1/3/9/5; T=90 ℃;
bSolution polymerization: PEGMA=2.0mL; Deionized water=2mL; [PEGMA]/[Br-PEG-Br]/[FeCl
3.6H
2O]/[TDA-1]/[VC]=500/1/3/9/5; T=90 ℃.
Embodiment two
With DMDBH PPEGMA hydrogel synthetic of initiator preparation
Press proportioning n (PEGMA): n (DMDBH): n (EGDMA): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=500: 1: 10～30: 3: 9: 3, add FeCl successively
3.6H
2O, TDA-1, PEGMA (2mL), EGDMA, DMDBH, VC and deionized water (2mL) in the ampoule of 10mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (90 ℃) to react (18～21h) ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, filter postlyophilization with the appropriate amount of deionized water immersion and promptly obtain xerogel.
Adopt small molecules initiator (DMDBH), by changing the consumption of linking agent (EGDMA), the data of the pick up of the polyalcohol hydrogel that obtains (being solvent to be inhaled with deionized water and methyl alcohol respectively) are as shown in table 2.By data in the table as can be seen, the network size of polymkeric substance can be controlled by the consumption that changes linking agent equally easily well, thus the absorbent of control hydrogel.
Relation between table 2.PPEGMA hydrogel pick up and the dosage of crosslinking agent
Polymerizing condition: PEGMA=2.0mL; [PEGMA]/[DMDBH]/[FeCl
3.6H
2O]/[TDA-1]/[VC]=500/1/3/9/3; T=90 ℃.
Embodiment three
Synthesizing of PDMAEMA hydrogel
Press proportioning n (DMAEMA): n (DMDBH or Br-PEG-Br): n (EGDMA): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=500: 1: 1～5: 3: 9: 1～5, add FeCl successively
3.6H
2O, TDA-1, PEGMA (2mL), EGDMA, DMDBH or Br-PEG-Br and VC in the ampoule of 10mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (90 ℃) to react (1～4h) ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, promptly obtain xerogel with filtering postlyophilization with the deionized water immersion in right amount.
Adopt small molecules bifunctional initiator (DMDBH), by changing the consumption of linking agent (EGDMA), the data (sequence number 1,2,3) as shown in table 3 of the pick up of the polyalcohol hydrogel that obtains (being solvent to be inhaled with deionized water and methyl alcohol respectively).By data in the table as can be seen, the network size of polymkeric substance is controlled well by the consumption that changes linking agent equally easily, thus the absorbent of control hydrogel.Adopt macromole bifunctional initiator (Br-PEG-Br) can synthesize PDMAEMA hydrogel (sequence number 4 in the table 3) equally in addition.
Relation between table 3.PDMAEMA hydrogel pick up and the dosage of crosslinking agent
aWith micromolecular DMDBH is bifunctional initiator; Polymerizing condition: DMAEMA=2.0mL; [DMAEMA]/[DMDBH]/[FeCl
3.6H
2O]/[TDA-1]/[VC]=500/1/3/9/1; T=90 ℃;
bWith macromolecular Br-PEG-Br is bifunctional initiator; Polymerizing condition: DMAEMA=2.0mL[DMAEMA]/[Br-PEG-Br]/[FeCl
3.6H
2O]/[TDA-1]/[VC]=500/1/3/9/5; T=90 ℃.
Claims (3)
1. the method for a synthetic water gel, it is characterized in that: with methacrylic acid-N, a kind of in N dimethylamine base ethyl ester or the Methylacrylic acid polyethylene glycol single armor ether ester as monomer, in molar ratio, monomer: initiator: linking agent: catalyzer: coordination agent: reductive agent=100～1000: 1: 1～50: 0.05～3: 0.15～9: 1～10, add monomer, initiator, linking agent, catalyzer, coordination agent and reductive agent, carry out AGET ATRP reaction, the synthetic water gel;
Wherein, described initiator is selected from polyoxyethylene glycol two (α-isobutyl bromide) ester or 2, a kind of in the 6-dibromo NSC 52563; Described linking agent is a kind of in ethylene glycol dimethacrylate or the polyethylene glycol dimethacrylate; Described catalyzer is selected from a kind of in high iron(ic) chloride of six hydrations or the iron bromide.
2. what the method for synthetic water gel according to claim 1 is characterized in that: described coordination agent was selected from three (3,6-dioxy heptyl) amine or N, N, N ', N ", N " in the PMDETA is a kind of.
3. the method for synthetic water gel according to claim 1 is characterized in that: described reductive agent is a kind of in xitix or the glucose.
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| CN101824127A (en) * | 2010-04-01 | 2010-09-08 | 江西科技师范学院 | Method for preparing crosslinkable segmented copolymer by utilizing active free radical soap-free emulsion polymerization and prepared compound thereof |
| CN101792510B (en) * | 2010-01-18 | 2012-04-04 | 苏州大学 | Method for carrying out controllable hydrophilic modification on polyvinylidene fluoride (PVDF) |
| CN102492104A (en) * | 2011-11-29 | 2012-06-13 | 苏州大学 | Method for preparing water-soluble polymer in water phase by a controllable mode |
| CN102532407A (en) * | 2011-11-04 | 2012-07-04 | 上海大学 | Method for preparing thermal sensitive macromolecules and thermal sensitive nanometer particles with core shell structures through RAFT copolymerization |
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| CN101792510B (en) * | 2010-01-18 | 2012-04-04 | 苏州大学 | Method for carrying out controllable hydrophilic modification on polyvinylidene fluoride (PVDF) |
| CN101824127A (en) * | 2010-04-01 | 2010-09-08 | 江西科技师范学院 | Method for preparing crosslinkable segmented copolymer by utilizing active free radical soap-free emulsion polymerization and prepared compound thereof |
| CN102532407A (en) * | 2011-11-04 | 2012-07-04 | 上海大学 | Method for preparing thermal sensitive macromolecules and thermal sensitive nanometer particles with core shell structures through RAFT copolymerization |
| CN102492104A (en) * | 2011-11-29 | 2012-06-13 | 苏州大学 | Method for preparing water-soluble polymer in water phase by a controllable mode |
| CN103304733B (en) * | 2013-06-19 | 2016-09-28 | 复旦大学 | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel |
| CN103304733A (en) * | 2013-06-19 | 2013-09-18 | 复旦大学 | Preparation method of degradable environmental sensitive polymer nano hydrogel and application |
| CN104530311A (en) * | 2014-12-17 | 2015-04-22 | 长春工业大学 | Notch-insensitive strengthening-toughening hydrogel and preparation method thereof |
| US10723842B2 (en) | 2015-03-11 | 2020-07-28 | University Of Florida Research Foundation, Inc. | Mesh size control of lubrication in gemini hydrogels |
| CN105220533A (en) * | 2015-10-20 | 2016-01-06 | 湖州博仁纺织品有限公司 | New type gel migration inhibitor that a kind of digit printing coating ink is special and preparation method thereof |
| CN108276514A (en) * | 2018-01-03 | 2018-07-13 | 中国化学赛鼎宁波工程有限公司 | A kind of preparation method of super absorbent resin |
| CN108276514B (en) * | 2018-01-03 | 2020-03-24 | 中国化学赛鼎宁波工程有限公司 | Preparation method of super absorbent resin |
| IT201800005186A1 (en) * | 2018-05-09 | 2019-11-09 | POLYMERIZATION PROCESS FOR THE PRODUCTION OF AROMATIC VINYL POLYMERS WITH A CONTROLLED STRUCTURE | |
| WO2019215626A1 (en) * | 2018-05-09 | 2019-11-14 | Versalis Spa | Polymerization process for the synthesis of vinyl aromatic polymers with a controlled structure |
| CN112154161A (en) * | 2018-05-09 | 2020-12-29 | 维尔萨利斯股份公司 | Polymerization process for the synthesis of vinylaromatic polymers with controlled structure |
| RU2795681C2 (en) * | 2018-05-09 | 2023-05-05 | ВЕРСАЛИС С.п.А. | Polymerization method for synthesis of vinyl aromatic polymers with controlled structure |
| CN112154161B (en) * | 2018-05-09 | 2023-08-01 | 维尔萨利斯股份公司 | Polymerization process for synthesizing vinyl aromatic polymers having controlled structure |
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| CN114230739A (en) * | 2021-12-14 | 2022-03-25 | 西安交通大学 | Linear-nonlinear block polymer and preparation method thereof |
| CN114230739B (en) * | 2021-12-14 | 2023-08-11 | 西安交通大学 | Linear-nonlinear block polymer and preparation method thereof |
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