CN101787105A - Preparation method of network interpenetrating functional aquagel - Google Patents
Preparation method of network interpenetrating functional aquagel Download PDFInfo
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Abstract
The invention discloses a method for preparing network interpenetrating functional aquagel through the click chemistry and the atom transfer radical polymerization (ATRP) synchronous reaction. The polymer network is generated through the click reaction of monomers A containing three or more than three end alkynyl radicals and monomers B at least containing two end laminated nitrogen radicals, and network interpenetrating polymers are obtained through the atom transfer radical polymerization (ATRP) by double-bond-containing monomers C with functional groups. The click chemistry and the atom transfer radical polymerization are synchronously carried out in the same catalytic system, and the network interpenetrating functional aquagel with the regular structure is obtained. The method of the invention has the advantages of the click chemistry and the ATRP, and also has the advantages of simple operation and fast reaction. The functional aquagel prepared by the method of the invention based on polyethyleneglycol has the characteristics of good biocompatibility, high tensile strength, high water absorption capacity, high swelling ratio, regular structure and the like.
Description
Technical field
The present invention relates to a kind of preparation method of functional aquagel, particularly relate to a kind of preparation method of network interpenetrating functional aquagel.
Background technology
The application of high molecular functional gel has caused people's concern more and more widely, and its property that has has also caused more and more people's interest.The called function gel is meant small stimulation or the variation of energy perception external environment (as temperature, pH value, light, magnetic, electricity or pressure etc.), self can produce the family macromolecule gel that corresponding chemical property and physical structure change simultaneously.Intelligent just because of this family macromolecule gel makes it and might be used in various fields, and especially the biomedical sectors such as embedding at medicament slow release, proteinic separation purification, organized enzyme have obtained broad research and application.But, make its application in some aspects be subjected to bigger restriction because the gel physical strength under the solvent swelling state is lower.In order to improve the physical strength of gel, people take methods such as copolymerization and blend to increase its intensity.But copolymerization can weaken or reduce some performance of original copolymer usually; as N-N-isopropylacrylamide and the monomer copolymerization that has wetting ability or hydrophobic group are prepared gel; tend to make poly-N-different in the phase transition temperature of basic acrylamide increase or reduce, more serious even can reduce its temperature sensitive property.
Because to pressing for of polymer modification, network interpenetrating (IPN) has obtained development widely as a kind of important means of polymer modification.Network interpenetrating (IPN) technology is a kind of in the numerous polymer blending modification technology, as the important and effective means of polymer modification, for the polymer materials of preparation property has been opened up new approach.It is considered to chemically realize the new technology of physical blending, comprises full interpenetrating(polymer)networks (full-IPN) and partly wears two kinds on network (semi-IPN).Difference is that the polymkeric substance in full interpenetrating(polymer)networks (full-IPN) system all is crosslinked, wears partly that in network (semi-IPN) system a kind of polymkeric substance to be arranged be linear.The characteristics of IPN are to contain the interpenetrating(polymer)networks that can play " forcing compatible " effect, and tangling mutually between the different polymer molecules forms an integral body, can not free.There is phase separately in different polymkeric substance in IPN, and Chemical bond does not take place between the polymkeric substance.
The synthetic method of IPN comprises the method for fractional steps and same footwork.The method of fractional steps is that crosslinked polymkeric substance (first network) is inserted in another monomer or prepolymer that contains catalyzer, linking agent etc., make its swelling, make second monomer or performed polymer polymerization in situ then and be cross-linked to form second network, products obtained therefrom claims the substep interpenetrating polymer networks.And rule is that two or more monomers are reacted by each auto-polymerization and crosslinked course in same reactor synchronously, forms synchronous interpenetrating(polymer)networks.
Network interpenetrating (IPN) technology is used for functional preparing gel, particularly combines and bring new prospect and space will for the preparation of functional gel and the improvement of performance thereof with click chemistry.
Polyoxyethylene glycol (PEG) is a kind of purposes polyether high molecular compound very widely, and it can be applicable to various fields such as medicine, health, food, chemical industry.PEG can be dissolved in water and the many solvents, has excellent biocompatibility, can be dissolved in vivo in the tissue juice, can be got rid of rapidly external by body and does not produce any toxic side effects.Rareer is, when PEG and other molecule in conjunction with the time, its a lot of advantageous properties also can be transferred in the new compound thereupon.Therefore, it is paid attention to widely and uses pharmaceutically being subjected to.Macromolecule hydrogel with its preparation has excellent biological compatibility.
Hydrogel based on polyoxyethylene glycol and derivative interpenetrating(polymer)networks (IPN) formation thereof has excellent biological compatibility and swelling property, possesses the characteristic of functional monomer simultaneously, therefore has a wide range of applications at biomedical sector.
Summary of the invention
The invention provides the preparation method of the functional aquagel of a kind of network interpenetrating (IPN) with ordered structure or half network interpenetrating (semi-IPN), this method is combined by click chemistry (click chemistry) and atom transfer radical polymerization (ATRP), realizes that in same catalyst system the synchronizing network IPN prepares functional aquagel.
Click chemistry and ATRP synchronous reaction prepare network interpenetrating functional aquagel in the inventive method, and the click chemistry reaction that forms the regular polymer network is reflected in single reaction vessel, the same catalyst system with the ATRP that forms interpenetrating net polymer to be finished.
The inventive method preparation is based on the network interpenetrating functional aquagel of polyoxyethylene glycol, its network mainly is based on the polyoxyethylene glycol or derivatives thereof and forms via the method for click chemistry, and carrying out IPN or Semi-IPN polymkeric substance in this network is the functional superpolymer that obtains by atom transfer radical polymerization (ATRP).Wherein click chemistry and atom transfer radical polymerization are finished under same catalyst system simultaneously.
The inventive method is achieved through the following technical solutions:
A kind of preparation method of network interpenetrating functional aquagel comprises following synchronous reaction process:
(a) click-reaction: contain the monomer (A) of three or three above Terminal Acetylenes bases and chemical reaction takes place to click, form polymer network with the monomer (B) that contains two end azido-s at least;
(b) ATRP reaction: the ATRP reaction takes place in the monomer (C) that has two keys, forms the polymkeric substance of interpenetrating(polymer)networks;
Described method adds monomer A, B and C in solvent, and initiator and part, adds transition-metal catalyst, and above-mentioned being reflected in the same reactor carried out.
Described monomer (A) comprises the compound that contains three or three above Terminal Acetylenes bases, as Ji Wusi alkynes alkyl oxide, or contains the alkynyl polyethylene glycol ester of three or three above Terminal Acetylenes bases, as contains the macrogol ester of four Terminal Acetylenes bases.Ji Wusi alkynes alkyl oxide can be by tetramethylolmethane and the preparation of alkynes bromine reaction.A kind of preparation method of alkynyl polyethylene glycol ester is, diethyl malonate and alkynol reaction generate the diethyl malonate ethynylation derivative that contains two alkynyls, obtain containing the propionic acid chloride derivative of two alkynyls through hydrolysis, decarboxylation, acyl chloride reaction, with PEG esterification takes place again and generate the macrogol ester that contains four Terminal Acetylenes bases.
Described monomer (B) is for containing the polymkeric substance of two end azido-s at least, and the polymkeric substance azide that can obtain by polymerization by the initiator that contains two above halogen groups obtains or obtains by the polymer terminal group modification.The polyoxyethylene glycol or derivatives thereof that comprises more than two the end azido-obtains needed azido-functional group after with its hydroxy-acid chlorideization, azide by the PEG or derivatives thereof in an embodiment; The polyisobutene and derivative (the Marko Rother thereof that perhaps have three end azido-s, HaithamBarqawi, Macromol.Chem.Phys.2010,211,204-214), perhaps have polystyrene (the Haifeng Gao of two end azido-s, Guillaume Louche, Mcaromol.2005,38,8979-8982) etc.
Described monomer (C) includes but not limited to that for containing the compound of two keys vinylbenzene and derivative thereof are as vinylbenzene, halogenated styrenes, methoxy styrene, acetoxy-styrene, hydroxy styrenes, nitrostyrolene and amino-benzene ethene etc.; (methyl) vinylformic acid and derivative thereof are as vinylformic acid, methacrylic acid etc.; (methyl) acrylate and derivative thereof, as Hydroxyethyl acrylate, glycidyl acrylate, tert-butyl acrylate, fluoro acrylic ester, cyanoacrylate etc., and the methacrylic ester of the hydroxyethyl methylacrylate of methyl methacrylate (MMA), Jia Jibingxisuanyizhi, butyl methacrylate, 2-(dimethylamine) ethyl-methyl acrylate (DMAEMA), hydroxyethyl methylacrylate (HEMA) and silylation protection, methacrylic acid (by the alkyl protection or with the form of salt), the esterification of oligomerisation oxyethane and fluorinated methyl acrylate etc.; Nitrile such as vinyl cyanide (AN) etc.; Acrylamide and derivative thereof such as Methacrylamide, N-isopropylacrylamide etc.Monomer (C) also comprises the functional polymer that contains two keys, as polyethyleneglycol diacrylate etc.
Described monomer (C) preferably has the monomer of functional group, the monomer that has temperature sensitivity as (a), and as the N-N-isopropylacrylamide, hydroxy ethyl methacrylate, 2-(dimethylamine) ethyl-methyl acrylate etc.; (b) have the monomer of pH susceptibility, as vinylformic acid, vinylformic acid N, N '-lignocaine ethyl ester etc.; (c) has the monomer of electric susceptibility, as acrylamide and derivative thereof; (d) have the monomer of optical sensibility, as contain monomer, the triphenyl methane derivative of azo group; (f) have the chemosensitivity monomer, as hydroxyethyl methylacrylate, methacrylic acid N, N '-dimethyl aminoethyl ester etc.And functional polymer polyethyleneglycol diacrylate.
Described monomer (C) also comprises above-mentioned monomeric blend.When using a kind of monomer (C), form half network interpenetrating hydrogel; When using two or more monomer (C), then form whole network IPN hydrogel.
Above-mentioned monomer (A, B and C), initiator, catalyzer, part etc. are mixed back one-step reaction under appropriate solvent, can generate the target compound hydrogel.40～120 ℃ of temperature of reaction were reacted 2 minutes～24 hours.
The click chemistry reaction takes place in monomer A and B under the catalyst system effect, form regular polymer network.The preferred alkynyl of the mol ratio of A and B wherein: azido-1: 1.Used catalyst system comprises catalyzer and part, and is identical with the ATRP that hereinafter describes in detail.
Monomer C forms IPN or Semi-IPN functional superpolymer by polyreaction in the polymer network that above-mentioned click-reaction forms.The polyreaction of monomer C is an atom transfer radical polymerization, and the initiator system that is adopted comprises initiator, catalyzer and part etc., and consumption is respectively 0.01%～5% of total monomer weight.The initiator of described atom transfer radical polymerization is Organohalogen compounds, comprise bromoethyl acetate, alpha-brominated ethyl butyrate, alpha-brominated ethyl isobutyrate, alpha-brominated phenylethane, the alpha-chloro phenylethane, α-Lv Bingsuan ethyl ester, ethyl, α-chloromethyl cyanide, α-chloroethyl nitrile, tetracol phenixin, chloroform, bromotoluene and benzyl chloride etc.Preferred alpha-brominated ethyl isobutyrate.
Described catalyzer is a transition-metal catalyst, can adopt Fe-series catalyst, rhodium series catalysts such as RhCl (PPh
3) wait, lithium molybdenum (V) complex systems, rhenium system's (V) catalyzer or Cu-series catalyst, as cuprous bromide or cuprous chloride.Preferred cuprous bromide.
Described part is nitrogenous polydentate ligand system, as 2, and 2 '-dipyridyl (bpy) and derivative thereof, or N, N, N '; N "; N "-five methyl diethylentriamine (PMDETA), Tetramethyl Ethylene Diamine (TMEDA), 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA) and three (N, N-dimethyl aminoethyl) amine (Me
6-TREN), N-n-hexyl-2 pyridyl methane amide.Preferred N, N, N ', N ", N "-five methyl diethylentriamine (PMDETA)
Described solvent can be selected from toluene, ethyl acetate, dimethylbenzene, N, N '-dimethyl formamide, dichlorobenzene, phenyl ether, methyl-phenoxide, tetrahydrofuran (THF), normal hexane, dimethyl sulfoxide (DMSO), deionized water, methyl alcohol, pimelinketone, 2-butanols or 2-methyl-2-butanols, or their mixture.Preferred tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or N, N '-dimethyl formamide, or their mixture.
Transition-metal catalyst in the synchronizing network IPN hydrogel that obtains by aforesaid method can be removed with EDTA solution, obtains the water white transparency hydrogel.
Of the present inventionly prepare the method for the network interpenetrating functional aquagel of compound with regular structure, overcome the shortcoming of functional gel process for preparing in the prior art by click chemistry and atom transfer radical polymerization (ATRP) synchronous reaction.This method does not need during functional aquagel secondary to add different catalyzer and part in preparation, and network interpenetrating carries out in same catalyst system, and the reaction times is short, and the advantage that has click chemistry and ATRP simultaneously and had.The functional aquagel colorless and odorless based on polyoxyethylene glycol of the inventive method preparation, good biocompatibility, tensile strength are big, water-intake rate and swelling ratio height, compound with regular structure has bigger potential using value in all many-sides such as medicament slow release, enzyme catalysis, human organs.
Specifically, the present invention has the advantage of the following aspects compared with prior art:
(1) provided by the invention have simple to operately by click chemistry and atom transfer radical polymerization (ATRP) method of the network interpenetrating functional aquagel of preparation compound with regular structure that combines synchronously, and advantage such as be swift in response.
(2) the present invention is the method that is prepared gel by click chemistry and atom transfer radical polymerization (ATRP) synchronizing network IPN, the advantage that therefore has click chemistry and ATRP and had.
(3) the present invention's polymer of being used for forming polymer network can be selected polyoxyethylene glycol and derivative thereof, has and good swelling property and biocompatibility.
(4) compare with the method that the legacy network IPN prepares gel, network interpenetrating carries out in same system simultaneously, does not therefore need secondary to add catalyzer and part, and the reaction times is short.
(5) the functional gel based on polyoxyethylene glycol of the inventive method preparation have that colorless and odorless, good biocompatibility, tensile strength are big, water-intake rate and swelling ratio height, characteristics such as compound with regular structure.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Embodiment
The preparation of example one end azido-PEG
Accurately taking by weighing 10g polyoxyethylene glycol (Mn=2000) is dissolved in the 50ml anhydrous pyridine.Ice bath is reduced to 0 ℃ with system temperature.Taking by weighing 1.43g (12.5 mmole) Methanesulfonyl chloride is dissolved in the 10ml anhydrous methylene chloride.
Under 0 ℃ of condition, utilize constant pressure funnel that the Methanesulfonyl chloride dichloromethane solution slowly is added dropwise to (about 20 minutes) in the polyoxyethylene glycol pyridine solution.Reaction system rises to room temperature, and reaction is 12 hours under the magnetic agitation.
Unnecessary solvent is removed in distillation, uses saturated NaHCO
3Repeatedly extract with methylene dichloride.The anhydrous magnesium sulfate drying organic layer.The thorough drying after-filtration places the pyriform bottle with clear liquid, and rotary evaporation is removed unnecessary solvent, precipitates in ether.Get white polyoxyethylene glycol diformazan sulfonic acid solid 8.5g.
Accurately take by weighing 8g polyoxyethylene glycol two methylsulfonic acids and 0.65g sodiumazide, be dissolved in the 50ml dry DMF.105 ℃ of lower magnetic force stirring reactions after 4 hours system reduce to room temperature and continue reaction 18 hours.Reaction was cooled off post (Al after finishing
2O
3) remove excessive sodiumazide.Precipitate in the ether.Get white polyoxyethylene glycol nitrine product 7.65g.Productive rate 90%.
Produce the azide product of PEG (Mn=4000) and PEG (Mn=6000) respectively according to method same as described above.
Example two contains the preparation of the macrogol ester of four Terminal Acetylenes bases
The preparation of described macrogol ester may further comprise the steps:
1, two alkynyl diethyl malonates is synthetic
Diethyl malonate 4.27ml is housed, 25ml ethanol, 1.3g solid sodium, Dropwise 5 .072ml propargyl bromide in the row round-bottomed flask after the mixed solution reaction 5min in the 100ml round-bottomed flask.The reaction solvent evaporated after half an hour that refluxes is dissolved in the water residue with extracted with diethyl ether three times, merges organic layer, dryly steams ether and gets yellow oily liquid, and distillation is collected cut and put into refrigerator and obtain white crystals.Productive rate 80%.
2, two alkynyl propanedioic acid is synthetic
White crystals enriching NaOH solution reaction after one night, is regulated the pH value to 1-2 with HCl, get the white powder solid after extracted with diethyl ether, the drying.
3, two alkynyl propionic acid acyl chlorides is synthetic
The two alkynyl propanedioic acid of white powder are dissolved in the 20ml sulphuric acid soln, and high temperature decarboxylation 24 hours gets the two alkynyl propionic acid of white powder.Take by weighing two alkynyl propionic acid solid 0.3g, under the nitrogen existence condition,, steam and remove unnecessary sulfur oxychloride, make two alkynyl propionic acid acyl chlorides with 4.4ml sulfur oxychloride reaction 5h.
4, polyoxyethylene glycol esterification
In two alkynyl propionic acid acyl chlorides that previous step makes, add respectively and contain the anhydrous THF solution that molecular weight is 2000,4000 and 6000 polyoxyethylene glycol, steam except that THF after reacting a night, with ethyl acetate, ether cleaning product, obtain the polyoxyethylene glycol that contains four Terminal Acetylenes bases of esterification.
Three seasons penta 4 of example propargyl ether preparation
Accurately take by weighing 2g (0.014 mmole) tetramethylolmethane and 12.5g (0.22 mmole) potassium hydroxide is dissolved in the 25ml dry DMF.Ice bath, system kept 5 ℃ of condition lower magnetic force stirring reactions 30 minutes.Under condition of ice bath, utilize constant pressure funnel slowly to drip propine bromine (dripping off in about 30 minutes).Reaction system is warming up to 40 ℃ and spends the night subsequently.
Stop to stir and be cooled to room temperature, adding 100ml deionized water.Ether repeatedly extracts.Organic layer repeatedly swings with deionized water and saturated aqueous common salt respectively to be washed.Anhydrous magnesium sulfate drying spends the night.The thorough drying after-filtration places the pyriform bottle with clear liquid, and rotary evaporation falls unnecessary solvent.Column chromatography for separation purification (ethyl acetate: normal hexane 2: 8).
The preparation of example four poly hydroxy ethyl acrylate whole network IPN hydrogels
Accurately take by weighing 0.25g (1.9 mmole) hydroxyethyl methylacrylate, (0.27g 0.475 mmole) polyethyleneglycol diacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide of (0.1g 0.025 mmole) end group azide, and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers, put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get colourless gel.
The preparation of example five poly hydroxy ethyl acrylates half network interpenetrating gel
Accurately take by weighing 0.74g (2.85 mmole) hydroxyethyl methylacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get the oyster white gel.
The preparation of example six poly-2-(dimethylamine) ethyl-methyl acrylate whole network IPN gels
Accurately take by weighing 0.3g (1.9 mmole) 2-(dimethylamine) ethyl-methyl acrylate, (0.27g 0.475 mmole) polyethyleneglycol diacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.1g 0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol esters (Mn=2108/4108/6108) and/0.036g (0.0125 mmole) Ji Wusi propargyl ether, put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get colourless gel.
The preparation of example seven poly-2-(dimethylamine) ethyl-methyl acrylate half network interpenetrating gels
Accurately take by weighing 0.448g (2.85 mmole) 2-(dimethylamine) ethyl-methyl acrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get the oyster white gel.
The preparation of example eight polymethyl acrylic acid whole network IPN gels
Accurately take by weighing 0.16g (1.9 mmole) methacrylic acid, (0.27g 0.475 mmole) polyethyleneglycol diacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get colourless gel.
The preparation of example nine polymethyl acrylic acid half network interpenetrating gel
Accurately take by weighing 0.245g (2.85 mmole) methacrylic acid, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get the oyster white gel.
The preparation of example ten polymethylmethacrylate whole network IPN gels
Accurately take by weighing 0.19g (1.9 mmole) methyl methacrylate, (0.27g 0.475 mmole) polyethyleneglycol diacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get colourless gel.
The preparation of example 11 polymethylmethacrylates half network interpenetrating gel
Accurately take by weighing 0.289g (2.85 mmole) methyl methacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get the oyster white gel.
The preparation of example ten dimerization N-N-isopropylacrylamide whole network IPN gels
Accurately take by weighing 0.215g (1.9 mmole) N-N-isopropylacrylamide, (0.27g 0.475 mmole) polyethyleneglycol diacrylate, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get colourless gel.
The preparation of example ten trimerization N-N-isopropylacrylamide half network interpenetrating gel
Accurately take by weighing 0.323g (2.85 mmole) N-N-isopropylacrylamide, (0.037g 0.214 mmole) five methyl diethylentriamine (PMDETA), (0.011g 0.057 mmole) alpha-brominated ethyl isobutyrate, 0.1g the polystyrene (Mn=7500) of polyoxyethylene glycol (Mn=4000)/0.186g (0.025 mmole) end group azide that (0.025 mmole) nitrine was handled and 0.026g/0.051g/0.076g (0.0125 mmole) four alkynyl macrogol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmole) Ji Wusi propargyl ethers are put into exsiccant ampere bottle jointly.Add 1.5mlDMF, logical nitrogen 20 minutes adds 0.0154g (0.107 mmole) CuBr fast.Can observe that gel forms immediately after adding CuBr.Sealing, oil bath reaction (T:60 ℃ of 24h).Be exposed to after 24 hours and finish reaction in the air.5%EDTA solution copper removal.Get the oyster white gel.
Embodiment 14
According to the method identical, utilize azide polyoxyethylene glycol (Mn=2000) and azide polyoxyethylene glycol (Mn=6000) to prepare functional gel respectively with embodiment four～13.
Claims (12)
1. the preparation method of a network interpenetrating functional aquagel comprises following synchronous reaction process:
(a) click-reaction: contain the monomer (A) of three or three above Terminal Acetylenes bases and chemical reaction takes place to click, form polymer network with the monomer (B) that contains two end azido-s at least;
(b) ATRP reaction: the ATRP reaction takes place in the monomer (C) that has two keys, forms the polymkeric substance of interpenetrating(polymer)networks;
Described method adds monomer A, B and C in solvent, and initiator and part, adds transition-metal catalyst, and above-mentioned being reflected in the same reactor carried out.
2. the preparation method of hydrogel according to claim 1 is characterized in that described click-reaction and ATRP reaction same catalyzer of employing and part.
3. the preparation method of hydrogel according to claim 2 is characterized in that described catalyzer is a cuprous bromide, and described part is five methyl diethylentriamine (PMDETA).
4. the preparation method of hydrogel according to claim 1 and 2 is characterized in that described monomer (A) is Ji Wusi alkynes alkyl oxide or the macrogol ester that contains four Terminal Acetylenes bases.
5. the preparation method of hydrogel according to claim 4, it is characterized in that the described preparation method who contains the macrogol ester of four Terminal Acetylenes bases is, diethyl malonate and alkynol reaction generate the diethyl malonate ethynylation derivative that contains two alkynyls, obtain containing the propionic acid chloride derivative of two alkynyls through hydrolysis, decarboxylation, acyl chloride reaction, with PEG esterification takes place again and generate the macrogol ester that contains four Terminal Acetylenes bases.
6. the preparation method of hydrogel according to claim 1 and 2, it is characterized in that described monomer (B) is for having the polyoxyethylene glycol or derivatives thereof of end azido-more than two, the polyisobutene and the derivative thereof that perhaps have three end azido-s perhaps have two polystyrene of holding azido-s.
7. the preparation method of hydrogel according to claim 1 and 2 is characterized in that described monomer (C) has functional group, comprises (a) temperature sensitivity monomer; (b) pH sensitive monomer; (c) electric sensitive monomer; (d) optical sensibility monomer; (f) chemosensitivity monomer; Or (g) functional polymer.
8. the preparation method of hydrogel according to claim 7, it is characterized in that described monomer (C) is hydroxyethyl methylacrylate, 2-(dimethylamine) ethyl-methyl acrylate, methacrylic acid, methyl methacrylate, N-N-isopropylacrylamide or polyethyleneglycol diacrylate, or its mixture.
9. the preparation method of hydrogel according to claim 1 and 2 is characterized in that 40～120 ℃ of temperature of reaction, reacts 2 minutes～24 hours.
10. the preparation method of hydrogel according to claim 1 and 2 is characterized in that described initiator is Organohalogen compounds.
11. the preparation method of hydrogel according to claim 1 and 2 is characterized in that described part is nitrogenous polydentate ligand.
12. the preparation method of hydrogel according to claim 1 and 2 is characterized in that described solvent is tetrahydrofuran (THF), N, dinethylformamide or dimethyl sulfoxide (DMSO), or their mixing solutions.
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