CN101787105A - Preparation method of network interpenetrating functional aquagel - Google Patents

Abstract

The invention discloses a method for preparing network interpenetrating functional hydrogel by synchronous reaction of click chemistry and atom transfer radical polymerization (ATRP). The polymer network is formed by the click reaction of a monomer A containing three or more terminal alkynyl groups and a monomer B containing at least two terminal azido groups; the interpenetrating polymer is composed of functional groups The double bond-containing monomer C was obtained by atom transfer radical polymerization (ATRP). Click chemistry and atom transfer radical polymerization are carried out simultaneously in the same catalytic system to obtain an interpenetrating functional hydrogel with a regular structure. The method of the present invention has the advantages of click chemistry and ATRP, and is simple to operate and reacts quickly; the functional hydrogel based on polyethylene glycol prepared by the method of the present invention has good biocompatibility, high tensile strength, and water absorption. High rate and swelling rate, regular structure and so on.

Description

A kind of preparation method of network interpenetrating functional hydrogel

technical field

The invention relates to a preparation method of a functional hydrogel, in particular to a preparation method of a network interpenetrating functional hydrogel.

Background technique

The application of polymer functional gels has attracted more and more attention, and its special properties have also attracted more and more people's interest. The so-called functional gel refers to a class of polymers that can perceive small stimuli or changes in the external environment (such as temperature, pH value, light, magnetism, electricity or pressure, etc.), and at the same time produce corresponding chemical properties and physical structure changes. gel. It is precisely because of the intelligence of this kind of polymer gel that it may be applied in many fields, especially in biomedical fields such as drug sustained release, protein separation and purification, and active enzyme embedding. . However, due to the low mechanical strength of the gel in the swollen state, its application in some aspects is greatly limited. In order to improve the mechanical strength of the gel, methods such as copolymerization and blending are adopted to increase its strength. However, copolymerization usually weakens or reduces some properties of the original polymer, such as preparing gel by copolymerizing N-isopropylacrylamide with monomers with hydrophilic or hydrophobic groups, which tends to make poly-N-isopropylacrylamide The phase transition temperature of endoacrylamide increases or decreases, and even lowers its temperature sensitivity.

Due to the urgent need for polymer modification, interpenetrating network (IPN) has been widely developed as an important means of polymer modification. Interpenetrating network (IPN) technology is one of many polymer blending modification technologies. As an important and effective means of polymer material modification, it opens up a new way for the preparation of polymer materials with special properties. It is considered to be a new technology to achieve physical blending by chemical methods, including full-IPN and semi-IPN. The difference is that the polymers in the full interpenetrating network (full-IPN) system are all cross-linked, and one polymer in the semi-IPN system is linear. The characteristic of IPN is that it contains an interpenetrating network that can play the role of "forced compatibility", and different polymer molecules are entangled with each other to form a whole, which cannot be released. In IPN, different polymers exist in their own phases, and there is no chemical combination between the polymers.

Synthetic methods of IPN include step-by-step and simultaneous methods. The step-by-step method is to place the already crosslinked polymer (first network) into another monomer or prepolymer containing catalyst, crosslinker, etc., let it swell, and then make the second monomer or prepolymer In situ polymerization and cross-linking to form a second network, the resulting product is called step-by-step interpenetrating polymer network. The synchronous method is to react two or more monomers in the same reactor according to their respective polymerization and crosslinking processes to form a synchronous interpenetrating network.

The use of interpenetrating network (IPN) technology in the preparation of functional gels, especially in combination with click chemistry, will bring new prospects and space for the preparation of functional gels and the improvement of their properties.

Polyethylene glycol (PEG) is a polyether polymer compound with a wide range of uses, and it can be used in many fields such as medicine, hygiene, food, and chemical industry. PEG can be dissolved in water and many solvents, has excellent biocompatibility, can dissolve in tissue fluid in vivo, and can be quickly excreted by the body without any toxic side effects. What's more, when PEG is combined with other molecules, many of its excellent properties will be transferred to new compounds. Therefore, it has been widely valued and applied in medicine. The polymer hydrogel prepared by it has good biocompatibility.

Hydrogels based on polyethylene glycol and its derivatives interpenetrating network (IPN) have good biocompatibility and swelling properties, and have the characteristics of functional monomers, so they have broad application prospects in the field of biomedicine .

Contents of the invention

The present invention provides a method for preparing a functional hydrogel with a regular structure of interpenetrating network (IPN) or semi-IPN, which is composed of click chemistry (click chemistry) and atom transfer radical polymerization (ATRP) to achieve synchronous network interpenetration in the same catalytic system to prepare functional hydrogels.

In the method of the present invention, click chemistry and ATRP synchronously react to prepare network interpenetrating functional hydrogel, and the click chemistry reaction to form a regular polymer network and the ATRP reaction to form an interpenetrating network polymer are completed in a single reactor and the same catalytic system.

The method of the present invention prepares polyethylene glycol-based network interpenetrating functional hydrogels, the network of which is mainly formed based on polyethylene glycol or its derivatives via click chemistry, and interpenetrating or semi-interpenetrating in this network The wear polymer is a functional polymer obtained by atom transfer radical polymerization (ATRP). The click chemistry and atom transfer radical polymerization are completed simultaneously under the same catalytic system.

The inventive method is realized through the following technical solutions:

A method for preparing a network interpenetrating functional hydrogel, comprising the following synchronous reaction process:

(a) Click reaction: a monomer (A) containing three or more terminal alkynyl groups undergoes a click chemical reaction with a monomer (B) containing at least two terminal azido groups to form a polymer network;

(b) ATRP reaction: the monomer (C) with a double bond undergoes an ATRP reaction to form an interpenetrating network polymer;

In the method, monomers A, B and C, initiators and ligands are added into a solvent, and a transition metal catalyst is added, and the above reactions are carried out in the same reactor.

The monomer (A) includes a compound containing three or more terminal alkynyl groups, such as pentaerythynyl ether, or an alkynylated polyethylene glycol containing three or more terminal alkynyl groups Esters, such as polyethylene glycol esters containing four terminal alkyne groups. Pentaerythrynyl ethers can be prepared by reacting pentaerythritol with alkyne bromide. A preparation method of alkynylated polyethylene glycol ester is that diethyl malonate and acetylenic alcohol react to generate diethyl malonate alkyne derivatives containing two alkynyl groups, which are hydrolyzed, decarboxylated, and acid chlorinated The reaction results in propionic acid chloride derivatives containing two alkynyl groups, which are then esterified with PEG to generate polyethylene glycol esters containing four terminal alkynyl groups.

The monomer (B) is a polymer containing at least two terminal azido groups, which can be obtained by azidation of polymers obtained by polymerization with an initiator containing two or more halogen groups or modified by polymer terminal groups. Sex gets. Polyethylene glycol or its derivatives including more than two terminal azido groups, in the embodiment, the required azido functional group is obtained after PEG or its derivatives are acyl chlorinated and azidated to obtain the desired azido group; or have three Polyisobutene and its derivatives (Marko Rother, HaithamBarqawi, Macromol.Chem.Phys.2010, 211, 204-214) with two terminal azido groups, or polystyrene with two terminal azido groups (Haifeng Gao, Guillaume Louche, Mcaromol. 2005, 38, 8979-8982) et al.

The monomer (C) is a compound containing a double bond, including but not limited to, styrene and its derivatives, such as styrene, halogenated styrene, methoxystyrene, acetoxystyrene, hydroxybenzene Ethylene, nitrostyrene and aminostyrene, etc.; (meth)acrylic acid and its derivatives, such as acrylic acid, methacrylic acid, etc.; (meth)acrylate and its derivatives, such as hydroxyethyl acrylate, glycidyl acrylate ester, tert-butyl acrylate, fluoroacrylate, cyanoacrylate, etc., as well as methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate, 2-(dimethylamine) ethyl methyl hydroxyethyl methacrylate (DMAEMA), hydroxyethyl methacrylate (HEMA) and silyl-protected hydroxyethyl methacrylate, methacrylic acid (by alkyl protection or in salt form), oligoethylene oxide esterified Methacrylate and fluorinated methacrylate, etc.; nitriles such as acrylonitrile (AN), etc.; acrylamide and its derivatives such as methacrylamide, isopropylacrylamide, etc. Monomer (C) also includes functional polymers containing double bonds, such as polyethylene glycol diacrylate and the like.

The monomer (C) is preferably a monomer with a functional group, such as (a) a temperature-sensitive monomer, such as N-isopropylacrylamide, hydroxyethyl acrylate, 2-(dimethylamine) Ethyl methacrylate, etc.; (b) monomers with pH sensitivity, such as acrylic acid, N, N'-diethylaminoethyl acrylate, etc.; (c) monomers with electrical sensitivity, such as acrylamide and Its derivatives; (d) optically sensitive monomers, such as azo group-containing monomers, triphenylmethane derivatives; (f) chemically sensitive monomers, such as hydroxyethyl methacrylate, N,N'-dimethylaminoethyl methacrylate, etc. and functional polymer polyethylene glycol diacrylate.

The monomer (C) also includes blends of the above monomers. When one monomer (C) is used, a semi-network interpenetrating hydrogel is formed; when two or more monomers (C) are used, a full-network interpenetrating hydrogel is formed.

The target hydrogel can be formed by mixing the above-mentioned monomers (A, B and C), initiators, catalysts, ligands, etc., in a single-step reaction in an appropriate solvent. The reaction temperature is 40-120°C, and the reaction takes 2 minutes to 24 hours.

Monomers A and B undergo a click chemical reaction under the action of the catalyst system to form a regular polymer network. Wherein the molar ratio of A and B is preferably alkynyl: azido 1:1. The catalyst system used, including catalyst and ligand, was the same as for ATRP as detailed below.

Monomer C forms an interpenetrating or semi-interpenetrating functional polymer in the polymer network formed by the above-mentioned click reaction through polymerization reaction. The polymerization reaction of monomer C is atom transfer radical polymerization, and the initiation system adopted includes initiator, catalyst and ligand, etc., and the dosage is 0.01%-5% of the total weight of the monomer respectively. The initiator of the atom transfer radical polymerization is an organic halide, including ethyl bromoacetate, ethyl α-bromobutyrate, ethyl α-bromoisobutyrate, α-bromophenylethane, α-chlorophenylethane, α-ethyl chloropropionate, ethyl α-bromopropionate, α-chloroacetonitrile, α-chloropropionitrile, carbon tetrachloride, chloroform, benzyl bromide and benzyl chloride, etc. . Ethyl α-bromoisobutyrate is preferred.

The catalyst is a transition metal catalyst, iron-based catalysts, rhodium-based catalysts such as RhCl (PPh ₃ ), etc., lithium-molybdenum (V) complex systems, rhenium-based (V) catalysts or copper-based catalysts, such as rosinous bromide Copper or Cuprous Chloride. Cuprous bromide is preferred.

The ligand is a nitrogen-containing multidentate ligand system, such as 2,2'-bipyridine (bpy) and its derivatives, or N, N, N', N", N"-pentamethyldimethoxy Ethylenetriamine (PMDETA), tetramethylethylenediamine (TMEDA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) and tris(N,N-dimethyl (aminoethyl)amine (Me ₆ -TREN), N-n-hexyl-2-pyridylformamide. N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) is preferred

The solvent may be selected from toluene, ethyl acetate, xylene, N,N'-dimethylformamide, dichlorobenzene, diphenyl ether, anisole, tetrahydrofuran, n-hexane, dimethylsulfoxide, Deionized water, methanol, cyclohexanone, 2-butanol or 2-methyl-2-butanol, or mixtures thereof. Preference is given to tetrahydrofuran, dimethylsulfoxide or N,N'-dimethylformamide, or a mixture thereof.

The transition metal catalyst in the synchronous network interpenetrating hydrogel obtained by the above method can be removed with EDTA solution to obtain a colorless transparent hydrogel.

The method for preparing a structurally regular network interpenetrating functional hydrogel by synchronous reaction of click chemistry and atom transfer radical polymerization (ATRP) of the present invention overcomes the shortcomings of the functional gel preparation method in the prior art. This method does not need to add different catalysts and ligands twice when preparing functional hydrogels, the network interpenetration is carried out in the same catalytic system, the reaction time is short, and it has the advantages of click chemistry and ATRP at the same time. The polyethylene glycol-based functional hydrogel prepared by the method of the present invention is colorless and tasteless, has good biocompatibility, high tensile strength, high water absorption rate and swelling rate, and regular structure, and can be used in drug sustained release, enzyme catalysis, and human body. Organs and many other aspects have great potential application value.

Specifically, compared with the prior art, the present invention has the following advantages:

(1) The method for synchronously preparing structurally regular interpenetrating functional hydrogels by combining click chemistry and atom transfer radical polymerization (ATRP) provided by the present invention has the advantages of simple operation and rapid reaction.

(2) The present invention is a method for preparing a gel by synchronous network interpenetration of click chemistry and atom transfer radical polymerization (ATRP), so it has the advantages of click chemistry and ATRP.

(3) Polyethylene glycol and its derivatives can be selected as the macromolecule used to form the polymer network in the present invention, which has excellent swelling property and biocompatibility.

(4) Compared with the traditional method of preparing gel by network interpenetration, network interpenetration is carried out simultaneously in the same system, so there is no need to add catalyst and ligand twice, and the reaction time is short.

(5) The polyethylene glycol-based functional gel prepared by the method of the present invention has the characteristics of colorless and odorless, good biocompatibility, high tensile strength, high water absorption rate and swelling rate, and regular structure.

The present invention will be described in detail below in conjunction with specific embodiments. The scope of the present invention is not limited by the specific embodiments but by the scope of the claims.

Detailed ways

Example One-terminal azido-based PEG preparation

Accurately weigh 10 g of polyethylene glycol (Mn=2000) and dissolve it in 50 ml of anhydrous pyridine. Ice bath, the temperature of the system was lowered to 0°C. Weigh 1.43g (12.5mmol) of methanesulfonyl chloride and dissolve it in 10ml of anhydrous dichloromethane.

The methanesulfonyl chloride dichloromethane solution was slowly added dropwise into the polyethylene glycol pyridine solution using a constant pressure dropping funnel at 0° C. (about 20 minutes). The reaction system was raised to room temperature, and reacted for 12 hours under magnetic stirring.

Excess solvent was distilled off and extracted several times with saturated NaHCO ₃ and dichloromethane. The organic layer was dried over anhydrous magnesium sulfate. After fully drying and filtering, the clear liquid was placed in a pear-shaped flask, and the excess solvent was removed by rotary evaporation, and precipitated in ether. 8.5 g of white polyethylene glycol dimethanesulfonic acid solid was obtained.

Accurately weigh 8 g of polyethylene glycol dimethanesulfonic acid and 0.65 g of sodium azide, and dissolve them in 50 ml of anhydrous DMF. After 4 hours of magnetic stirring at 105°C, the system was cooled to room temperature and continued to react for 18 hours. After the reaction was completed, excess sodium azide was removed by cooling through a column (Al ₂ O ₃ ). Precipitate in ether. 7.65 g of white polyethylene glycol azide product was obtained. Yield 90%.

The azidation products of PEG (Mn=4000) and PEG (Mn=6000) were prepared in the same manner as above.

Example two contains the preparation of polyethylene glycol esters of four terminal alkynyl groups

The preparation of the polyethylene glycol ester comprises the following steps:

1. Synthesis of Diethyl Diacetylmalonate

4.27ml of diethyl malonate, 25ml of ethanol, and 1.3g of solid sodium were placed in a 100ml round bottom flask. After the mixture was reacted for 5 minutes, 5.072ml of propyne bromide was added dropwise to the round bottom flask. After the reaction was refluxed for half an hour, the solvent was evaporated to dryness, the residue was dissolved in water and extracted three times with ether, the organic layers were combined, dried and evaporated to remove the ether to obtain a yellow oily liquid, the fractions were collected by distillation and placed in a refrigerator to obtain white crystals. Yield 80%.

2. Synthesis of bis-alkynyl malonic acid

Add concentrated NaOH solution to the white crystals and react overnight, adjust the pH value to 1-2 with HCl, extract with ether, and dry to obtain a white powdery solid.

3. Synthesis of bis-alkynyl propionic acid chloride

Dissolve white powdery bis-alkynylpropionic acid in 20ml of sulfuric acid solution, decarboxylate at high temperature for 24 hours to obtain white powdery bis-alkynylpropionic acid. Weigh 0.3 g of bis-alkynyl propionic acid solid, react with 4.4 ml of thionyl chloride for 5 h in the presence of nitrogen, and evaporate excess thionyl chloride to obtain bis-alkynyl propionic acid chloride.

4. Polyethylene glycol esterification

In the bis-alkynylpropionic acid chloride obtained in the previous step, add anhydrous THF solution containing polyethylene glycol with a molecular weight of 2000, 4000 and 6000 respectively, react overnight to remove THF, wash the product with ethyl acetate and ether, Esterified polyethylene glycol containing four terminal alkyne groups is obtained.

The preparation of example tripentaerythroxypropargyl ether

Accurately weigh 2 g (0.014 mmol) of pentaerythritol and 12.5 g (0.22 mmol) of potassium hydroxide and dissolve in 25 ml of anhydrous DMF. In an ice bath, the system was kept at 5°C under magnetic stirring for 30 minutes. Under the condition of ice bath, propargyl bromide was slowly added dropwise using a constant pressure dropping funnel (dropping was completed in about 30 minutes). Then the reaction system was heated to 40°C overnight.

Stop stirring and cool to room temperature, add 100ml deionized water. Diethyl ether was extracted several times. The organic layer was washed several times with deionized water and saturated saline respectively. Dry over anhydrous magnesium sulfate overnight. After fully drying and filtering, the supernatant was placed in a pear-shaped bottle, and the excess solvent was evaporated by rotary evaporation. Separation and purification by column chromatography (ethyl acetate:n-hexane 2:8).

Example Preparation of Tetrapoly-Hydroxyethyl Methacrylate Full Network Interpenetrating Hydrogel

Accurately weigh 0.25g (1.9mmol) of hydroxyethyl methacrylate, 0.27g (0.475mmol) of polyethylene glycol diacrylate, 0.037g (0.214mmol) of pentamethyldiethylenetriamine (PMDETA ), 0.011g (0.057mmol) ethyl α-bromoisobutyrate, 0.1g (0.025mmol) end group azide polyethylene glycol (Mn=4000)/0.186g (0.025mmol) terminal azide polystyrene (Mn=7500), and 0.026g/0.051g/0.076g (0.0125 mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125 millimoles) of pentaerythroxypropargyl ether, put them together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A colorless gel was obtained.

Preparation of example pentameric hydroxyethyl methacrylate semi-network interpenetrating gel

Accurately weigh 0.74g (2.85mmol) of hydroxyethyl methacrylate, 0.037g (0.214mmol) of pentamethyldiethylenetriamine (PMDETA), 0.011g (0.057mmol) of α-bromoisobutyl Ethyl acetate, 0.1g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186g (0.025 mmol) terminal azidated polystyrene (Mn=7500) and 0.026g /0.051g/0.076g (0.0125mmol) tetraacetylenyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125mmol) pentaerythroxypropargyl ether, put into dry ampoule together in the bottle. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A milky white gel was obtained.

Preparation of example hexameric 2-(dimethylamine) ethyl methacrylate full network interpenetrating gel

Accurately weigh 0.3g (1.9 mmol) 2-(dimethylamine) ethyl methacrylate, 0.27g (0.475 mmol) polyethylene glycol diacrylate, 0.037g (0.214 mmol) pentamethyl dimethacrylate Ethylenetriamine (PMDETA), 0.011g (0.057mmol) ethyl α-bromoisobutyrate, 0.1g (0.025mmol) azide-treated polyethylene glycol (Mn=4000)/0.186g (0.025 mmol) terminal azide polystyrene (Mn=7500) and 0.026g/0.051g/0.076g (0.0125 mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108) And/0.036g (0.0125mmol) of pentaerythroxypropargyl ether, put them together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A colorless gel was obtained.

The preparation of example heptameric 2-(dimethylamine) ethyl methacrylate semi-network interpenetrating gel

Accurately weigh 0.448g (2.85 mmol) 2-(dimethylamine) ethyl methacrylate, 0.037g (0.214 mmol) pentamethyldiethylenetriamine (PMDETA), 0.011g (0.057 mmol) ) ethyl α-bromoisobutyrate, 0.1g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186 g (0.025 mmol) terminal azidated polystyrene ( Mn=7500) and 0.026g/0.051g/0.076g (0.0125 mmol) tetraynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmol) pentaerythroxypropargyl ether , together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A milky white gel was obtained.

Preparation of example octamer methacrylic acid full network interpenetrating gel

Accurately weigh 0.16g (1.9 mmol) methacrylic acid, 0.27g (0.475 mmol) polyethylene glycol diacrylate, 0.037g (0.214 mmol) pentamethyldiethylenetriamine (PMDETA), 0.011 g (0.057 mmol) ethyl α-bromoisobutyrate, 0.1 g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186 g (0.025 mmol) terminal azidation Polystyrene (Mn=7500) and 0.026g/0.051g/0.076g (0.0125 mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmol) pentaerythr tetrapropargyl ether, together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A colorless gel was obtained.

Preparation of example nine polymethacrylic acid semi-network interpenetrating gel

Accurately weigh 0.245g (2.85mmol) of methacrylic acid, 0.037g (0.214mmol) of pentamethyldiethylenetriamine (PMDETA), 0.011g (0.057mmol) of ethyl α-bromoisobutyrate , 0.1g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186g (0.025 mmol) terminal azidated polystyrene (Mn=7500) and 0.026g/0.051g /0.076g (0.0125 mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125 mmol) pentaerythroxypropargyl ether, put them together into a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A milky white gel was obtained.

Example 10 Preparation of polymethyl methacrylate full network interpenetrating gel

Accurately weigh 0.19g (1.9 mmol) methyl methacrylate, 0.27g (0.475 mmol) polyethylene glycol diacrylate, 0.037g (0.214 mmol) pentamethyldiethylenetriamine (PMDETA) , 0.011g (0.057 mmol) ethyl α-bromoisobutyrate, 0.1 g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186 g (0.025 mmol) terminal Nitrided polystyrene (Mn=7500) and 0.026g/0.051g/0.076g (0.0125mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125mmol) Pentaerythroxypropargyl ether, together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A colorless gel was obtained.

Example 11 Preparation of polymethyl methacrylate semi-network interpenetrating gel

Accurately weigh 0.289g (2.85mmol) of methyl methacrylate, 0.037g (0.214mmol) of pentamethyldiethylenetriamine (PMDETA), 0.011g (0.057mmol) of α-bromoisobutyric acid Ethyl ester, 0.1g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186g (0.025 mmol) terminal azidated polystyrene (Mn=7500) and 0.026g/ 0.051g/0.076g (0.0125mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125mmol) pentaerythroxypropargyl ether, put together into a dry ampoule middle. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A milky white gel was obtained.

Example twelve poly N-isopropylacrylamide preparation of the whole network interpenetrating gel

Accurately weigh 0.215g (1.9 mmol) N-isopropylacrylamide, 0.27g (0.475 mmol) polyethylene glycol diacrylate, 0.037g (0.214 mmol) pentamethyldiethylenetriamine ( PMDETA), 0.011g (0.057 mmol) ethyl α-bromoisobutyrate, 0.1 g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186 g (0.025 mmol) terminal Azidated polystyrene (Mn=7500) and 0.026g/0.051g/0.076g (0.0125mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125mmol) mol) of pentaerythroxypropargyl ether, put them together in a dry ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A colorless gel was obtained.

Example 13 poly N-isopropylacrylamide semi-network interpenetrating gel preparation

Accurately weigh 0.323g (2.85mmol) of N-isopropylacrylamide, 0.037g (0.214mmol) of pentamethyldiethylenetriamine (PMDETA), 0.011g (0.057mmol) of α-bromoiso Ethyl butyrate, 0.1 g (0.025 mmol) azide-treated polyethylene glycol (Mn=4000)/0.186 g (0.025 mmol) terminal azidated polystyrene (Mn=7500) and 0.026 g/0.051g/0.076g (0.0125mmol) tetrakynyl polyethylene glycol ester (Mn=2108/4108/6108)/0.036g (0.0125mmol) pentaerythroxypropargyl ether, put into dry in an ampoule. Add 1.5ml of DMF, blow nitrogen for 20 minutes, and quickly add 0.0154g (0.107mmol) of CuBr. It can be observed that the gel forms immediately after the addition of CuBr. Seal and react in an oil bath (T: 60°C 24h). After 24 hours the reaction was terminated by exposure to air. 5% EDTA solution to remove copper. A milky white gel was obtained.

Embodiment Fourteen

According to the same method as in Examples 4-13, functional gels were prepared using azide polyethylene glycol (Mn=2000) and azide polyethylene glycol (Mn=6000), respectively.

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.