CN105754037A - Biodegradable cross-linking agent, polyacrylamide hydrogel and preparation method - Google Patents

Biodegradable cross-linking agent, polyacrylamide hydrogel and preparation method Download PDF

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CN105754037A
CN105754037A CN201610209236.5A CN201610209236A CN105754037A CN 105754037 A CN105754037 A CN 105754037A CN 201610209236 A CN201610209236 A CN 201610209236A CN 105754037 A CN105754037 A CN 105754037A
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laminarin
glycidyl methacrylate
preparation
biodegradable cross
cross
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谢文泽
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Shenzhen Duebio Technology Co Ltd
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Shenzhen Duebio Technology Co Ltd
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52Amides or imides
    • C08F120/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56Acrylamide; Methacrylamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246Intercrosslinking of at least two polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24Homopolymers or copolymers of amides or imides
    • C08L33/26Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24Homopolymers or copolymers of amides or imides
    • C08J2333/26Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24Homopolymers or copolymers of amides or imides
    • C08J2433/26Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/02Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
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    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Abstract

The invention provides a biodegradable cross-linking agent, polyacrylamide hydrogel and a preparation method. The biodegradable cross-linking agent is glycidyl methacrylate grafted laminarin; and the glycidyl methacrylate grafted laminarin is formed by grafting a polarized hydroxyl on the laminarin by methylene of the glycidyl methacrylate, and removing glycidol from the glycidyl methacrylate. The polyacrylamide hydrogel is formed by cross-linking and polymerizing by taking polyallylamine as a monomer, and taking the glycidyl methacrylate grafted laminarin as a cross-linking agent.

Description

A kind of Biodegradable cross-linked dose, polyacrylamide hydrophilic gel and preparation method
Technical field
The invention belongs to technical field of hydrogel, particularly relate to a kind of Biodegradable cross-linked dose, polyacrylamide hydrophilic gel and preparation method.
Background technology
Hydrogel is a kind of hydrophilic polymer with tridimensional network, water insoluble but can abundant swelling moisture, effect is cross-linked with each other, tangling forms, because it integrates water suction, water conservation, alleviates and be used widely can to pass through chemical bond, ionic bond, intermolecular Van der Waals force, hydrogen bond etc..
According to source, hydrogel can be divided into: natural hydrogel and chemosynthesis hydrogel.At present, natural hydrogel is generally by the natural macromolecular material in nature-obtain such as polysaccharide, the processing of protein-based and derivant.Natural hydrogel has good biocompatibility and biodegradability, and environment is safe from harm, and meets environmental protection theory.But, the hydrogel performance prepared due to natural macromolecular material has limitation, particularly bad mechanical property, and the material source of natural macromolecular material is limited, and therefore, the application development of natural hydrogel is restricted.Based on the problems referred to above that natural hydrogel exists, the hydrogel of chemosynthesis arises at the historic moment, and they can significantly improve the mechanical performance of gel and increase the application characteristic etc. of gel.At present; common chemosynthesis hydrogel is generally polymerized through causing with cross-linking agent by monomer; common cross-linking agent mainly has: N; N-methylene-bisacrylamide, acrylated polyvinyl alcohol etc.; but hydrogel prepared by these common cross-linking agent is usually nondegradable, seriously limit its application at biomedical sector.
Therefore, in order to solve the problems referred to above, scholars investigated a kind of effective method, namely replaces common chemical cross-linking agent to prepare hydrogel with biodegradable cross-linking agent so that it is load crosslinking points potential drop solution under certain condition.In recent years, the research of biodegradable hydrogel increasingly receives the concern of people.But, current existing degradable crosslinker can not meet the requirements such as nontoxic, good biocompatibility, biodegradable simultaneously, therefore, develop a kind of hydrogel cross-linking agent that can simultaneously meet the requirements such as nontoxic, good biocompatibility, biodegradable to be particularly important.
Summary of the invention
It is an object of the invention to provide a kind of Biodegradable cross-linked dose, it is intended to solve existing hydrogel cross-linking agent and can not meet the problem that nontoxic, good biocompatibility, biodegradable etc. require simultaneously.
Another object of the present invention is to the preparation method providing a kind of Biodegradable cross-linked dose.
It is still another object of the present invention to provide a kind of polyacrylamide hydrophilic gel and preparation method thereof.
The present invention is realized in, a kind of Biodegradable cross-linked dose, described Biodegradable cross-linked dose is glycidyl methacrylate graft laminarin, and described glycidyl methacrylate graft laminarin is grafted on the polarization hydroxyl of laminarin by the methylene of glycidyl methacrylate and described glycidyl methacrylate is sloughed (+)-2,3-Epoxy-1-propanol and formed.
Accordingly, the preparation method of a kind of Biodegradable cross-linked dose, comprise the following steps:
Thering is provided laminarin, glycidyl methacrylate agent, base catalyst and aprotic solvent, and described base catalyst is dimethylamino naphthyridine, described aprotic solvent is dimethyl sulfoxide;
Described laminarin and dimethylamino naphthyridine are dissolved in described dimethyl sulfoxide, form the first reactant liquor;
Adding described glycidyl methacrylate agent in described first reactant liquor, reaction generates glycidyl methacrylate graft laminarin.
And, a kind of polyacrylamide hydrophilic gel, described polyacrylamide hydrophilic gel is using polypropylene amine as monomer, be polymerized using above-mentioned glycidyl methacrylate graft laminarin as cross-linking agents.
Accordingly, the preparation method of a kind of polyacrylamide hydrophilic gel, comprise the following steps:
Thering is provided polypropylene amine monomer, glycidyl methacrylate graft laminarin and initiator, wherein, described initiator is the composite initiator of APS and TEMED composition;
Described polypropylene amine monomer, glycidyl methacrylate graft laminarin after mix homogeneously, being added described initiator and carry out mixing process in distilled water, polymerization forms polyacrylamide hydrophilic gel.
Biodegradable cross-linked dose provided by the invention, using the laminarin of natural origin as raw material, and polarizing graft glycidyl methacrylate on hydroxyl at laminarin, the cross-linking agent thus obtained is nontoxic, composite green environmental protection concept, and its biocompatibility and biodegradable are all good.The preparation method of described Biodegradable cross-linked dose, simple to operate easily-controllable, it may be achieved large-scale production.
Polyacrylamide hydrophilic gel provided by the invention, not only has good mechanical performance, has good biocompatibility and degradability simultaneously, meets environmental protection theory, has good application prospect, can be used for biomedical sector.The preparation method of described polyacrylamide hydrophilic gel is simple, and easy controlled operation has good application prospect.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Embodiments provide a kind of Biodegradable cross-linked dose, described Biodegradable cross-linked dose is glycidyl methacrylate graft laminarin (Lam-GMA), and described glycidyl methacrylate graft laminarin is grafted on the polarization hydroxyl of laminarin by the methylene of glycidyl methacrylate and described glycidyl methacrylate is sloughed (+)-2,3-Epoxy-1-propanol and formed.
Concrete, in the embodiment of the present invention, described laminarin (Lam) is the green pure natural polysaccharide of a kind of wide material sources, there is good biocompatibility, antibiotic property and low cytotoxicity, tumor growth can be suppressed, reduce urine protein, purified blood medicine uric acid, improve serum lipid concentrations, gout, hyperlipidemia, early metaphase renal failure are had good preventive and therapeutic effect.Additionally, described laminarin good water solubility, containing great amount of hydroxy group in molecule, it is easy to modified, the ideal chose of biodegradable cross-linker can be prepared as the embodiment of the present invention.In order to obtain quality Biodegradable cross-linked dose preferably, described laminarin is preferably the laminarin of purity >=96%.
In the embodiment of the present invention, described glycidyl methacrylate (GMA), as modifying agent, can be grafted in described laminarin molecular structure and it is modified so that formation-O-CH in molecular structure2-and double bond structure, thus giving the described glycidyl methacrylate graft laminarin reactivity as cross-linking agent.The embodiment of the present invention has good mechanical performance through the modified described glycidyl methacrylate graft laminarin obtained.Concrete, the embodiment of the present invention is difference on described laminarin, according to grafting degree by described glycidyl methacrylate graft, it is possible to obtain the glycidyl methacrylate graft laminarin of different degree of substitution (DS).In the embodiment of the present invention, the number that described substitution value is defined as in every 100 glucose residues containing unsaturated double-bond, i.e. DS=100* (GMA/Lam).When the too low i.e. described glycidyl methacrylate graft degree of described substitution value is low ,-O-CH in the Lam-GMA obtained2-and the content of double bond structure relatively fewer, then its and addition relatively low as reactivity when preparing the cross-linking agent of hydrogel increases accordingly;When the too high i.e. described glycidyl methacrylate graft degree height of described substitution value ,-O-CH in the Lam-GMA obtained2-and the content of double bond structure relatively many, then it is as when preparing the cross-linking agent of hydrogel, and due to being significantly increased of cross-linking agent mechanical strength, the gel resulted in is too crisp and can not meet demand.Accordingly, as preferred embodiment, the substitution value of described Biodegradable cross-linked dose is 5-20, and namely the mol ratio of laminarin described in the embodiment of the present invention and described glycidyl methacrylate is 1:(0.05-0.2).As specific embodiment, the substitution value of described Biodegradable cross-linked dose is 10, and namely the mol ratio of laminarin described in the embodiment of the present invention and described glycidyl methacrylate is 1:0.1.
The embodiment of the present invention is carried described Biodegradable cross-linked dose and can be prepared by following method.
Accordingly, the preparation method embodiments providing a kind of Biodegradable cross-linked dose, comprise the following steps:
S01. providing laminarin, glycidyl methacrylate agent, base catalyst and aprotic solvent, and described base catalyst is dimethylamino naphthyridine, described aprotic solvent is dimethyl sulfoxide;
S02. described laminarin and dimethylamino naphthyridine are dissolved in described dimethyl sulfoxide, form the first reactant liquor;
S03. adding described glycidyl methacrylate agent in described first reactant liquor, reaction generates glycidyl methacrylate graft laminarin.
Concrete, in above-mentioned steps S01, described base catalyst is dimethylamino naphthyridine (DMAP), and described dimethylamino naphthyridine can efficiently cause the nucleophilic substitution between described laminarin and described glycidyl methacrylate agent as base catalyst.Simultaneously, the embodiment of the present invention selects described dimethyl sulfoxide as reaction dissolvent, owing to described dimethyl sulfoxide is polar non-solute, therefore can so that the hydroxyl on described laminarin is polarized by described dimethylamino naphthyridine, thus for grafting new construction ready.
In above-mentioned steps S02, the formation of described first reactant liquor, it is possible to realized by stirring and dissolving.As the presently preferred embodiments, the mass ratio of described laminarin and dimethylamino naphthyridine is 1:(0.15-0.25).
In above-mentioned steps S03, owing to the hydroxyl on described laminarin is polarized by described dimethylamino naphthyridine, polarized hydroxyl can sterically hindered less methylene in glycidyl methacrylate agent epoxy group group described in attack, cause glycidyl methacrylate open loop, slough little molecule (+)-2,3-Epoxy-1-propanol, generate glycidyl methacrylate graft laminarin Lam-GAM, thus introducing double bond on described laminarin.The addition of described glycidyl methacrylate agent directly affects the substitution value in graft product, i.e. the content of double bond in described Lam-GMA.Therefore, as the presently preferred embodiments, the product suitable in order to obtain described substitution value, and then can be well used as preparing the cross-linking agent of degradable hydrogel, the mol ratio of described laminarin and described glycidyl methacrylate is 1:(0.05-0.2).
As it is preferred that embodiment, after reacting, also include
S04. the pH of the reaction mixture being obtained by reacting is regulated so that it is in neutrality;
S05. being stirred in neutral reaction mixture instillation anhydrous organic solvent, precipitate out, sucking filtration obtains glycidyl methacrylate graft laminarin filter cake after processing;
S06. undertaken described glycidyl methacrylate graft laminarin filter cake dialysing, obtain glycidyl methacrylate graft laminarin after frozen dried.
In above-mentioned steps S04, regulating pH can realize with organic acid.Owing to the oxidisability of nitric acid is too strong, it is easy to other side reactions in initiation reaction system, and in sulphuric acid, acid ion also easily participates in reaction as reactive ion, thus affecting product quality, therefore, organic acid described in the embodiment of the present invention selects excellent hydrochloric acid.
In above-mentioned steps S05, described anhydrous organic solvent is used for evolution reaction product glycidyl methacrylate graft laminarin.Concrete, described anhydrous organic solvent can be selected for not reacting with product and nontoxic anhydrous organic solvent, and owing to the consumption of described anhydrous organic solvent is more, it is preferred to use the anhydrous organic solvent that cost is told somebody what one's real intentions are.As specific embodiment, described anhydrous organic solvent is dehydrated alcohol.After the complete sucking-off of question response product, water pump collected by suction filter cake can be adopted.
In above-mentioned steps S06, being placed in distilled water by described glycidyl methacrylate graft laminarin filter cake, dialyse below 4 DEG C in distilled water, dialysis is completely as after dialysis one week, carry out lyophilization process, obtain white feather shape glycidyl methacrylate graft laminarin.
Biodegradable cross-linked dose of embodiment of the present invention offer, using the laminarin of natural origin as raw material, and polarizing graft glycidyl methacrylate on hydroxyl at laminarin, the cross-linking agent thus obtained is nontoxic, composite green environmental protection concept, and its biocompatibility and biodegradable are all good.The preparation method of described Biodegradable cross-linked dose, simple to operate easily-controllable, it may be achieved large-scale production.
And, the embodiment of the present invention additionally provides a kind of polyacrylamide hydrophilic gel, and described polyacrylamide hydrophilic gel is using polypropylene amine as monomer, be polymerized using above-mentioned glycidyl methacrylate graft laminarin as cross-linking agents.
Polyacrylamide hydrophilic gel described in the embodiment of the present invention can adopt following method to prepare.
Accordingly, the preparation method embodiments providing a kind of polyacrylamide hydrophilic gel, comprise the following steps:
Q01., polypropylene amine monomer, glycidyl methacrylate graft laminarin and initiator are provided, wherein, described initiator is Ammonium persulfate. (APS) and N, N, N ', N ' composite initiator that forms of-tetramethylethylenediamine (TEMED);
Q02. described polypropylene amine monomer (AM), glycidyl methacrylate graft laminarin (Lam-GMA) after mix homogeneously, being added described initiator and carry out mixing process in distilled water, polymerization forms polyacrylamide hydrophilic gel.
Concrete, in above-mentioned steps Q01, in order to prevent the polymerization rate in polypropylene amine monomer and cross-linking agent too fast uncontrollable, thus causing at the bottom of hydrogel purity or deformation (being creamy white as opaque), the embodiment of the present invention preferably employs composite initiator to regulate and control polyreaction.Further, owing to the regulation and control of polyreaction are had a certain impact by the concentration of described APS and the content of described APS and TEMED, then can cause that such as described APS too high levels reaction is too fast, affect product property, therefore, preferably, described APS is weight percentage is the APS solution of 3-5%, and the volume ratio of described APS and TEMED is 10:(0.8-1.2).As particular preferred embodiment, described APS is weight percentage be 4% APS solution, and the volume ratio of described APS and TEMED is 10:1.
In above-mentioned steps Q02, owing to the properties of product impact on obtaining of the content of described polypropylene amine monomer is relatively big, concrete, if the content of described polypropylene amine monomer is too low, then gel not easily even can not molding;If the too high levels of described polypropylene amine monomer, then polymerization rate is too fast, can cause that the hydrogel performance that obtains is not enough, as opaque, degradability is poor, poor solubility etc..Accordingly, as preferred embodiment, in described mixed reaction solution, the weight/mass percentage composition of described polypropylene amine monomer is 8-12%.
The content of described glycidyl methacrylate graft laminarin (Lam-GMA) needs to determine according to its substitution value, common, and in order to obtain metastable hydrogel, if the substitution value of Lam-GMA is high, then its addition is relatively low;If the substitution value of described Lam-GMA is high, then its addition is relatively high.
Further, taking out, be soaked in a large amount of deionized water after the embodiment of the present invention at room temperature polyreaction 24h, every 4h changes water, to remove the monomer having neither part nor lot in reaction, namely obtains biodegradable hydrogel.
The polyacrylamide hydrophilic gel that the embodiment of the present invention provides, not only has good mechanical performance, has good biocompatibility and degradability simultaneously, meet environmental protection theory, have good application prospect, can be used for biomedical sector.The preparation method of described polyacrylamide hydrophilic gel is simple, and easy controlled operation has good application prospect.
Illustrate below in conjunction with specific embodiment, in specific embodiment, described dimethyl sulfoxide adopts analytical pure, described dimethylamino naphthyridine is the dimethylamino naphthyridine of purity >=99%, described glycidyl methacrylate purity > 95%, and described hydrochloric acid selects top grade pure, described dehydrated alcohol adopts analytical pure, purity >=99% of described acrylamide, purity >=99% of described TEMED, described APS is analytical pure.
Embodiment 1
Lam, DMAP is weighed in 20mlDMSO by each material content shown in embodiment 1 in table 1, stirring and dissolving, form the first reactant liquor;
After fully dissolving, adding the GMA of respective amount, products therefrom is designated as Lam-5;
After reacting completely, adding and the considerable amount of hydrochloric acid of DMAP, stir, it is neutral for making reactant mixture;
Being slowly dropped into by reactant mixture in 200ml dehydrated alcohol, magnetic agitation precipitates out solid, solution turned cloudy.After laminarin derivant precipitates out completely, water pump sucking filtration, collect filter cake;
Again filter cake is dissolved in distilled water, dialyses with distilled water at 4 DEG C, dialyse one week, after dialysis completely, then liquid freezing in bag is dried, obtain white feather shape product.
Embodiment 2
Method, with embodiment 1, is different in that in each material content such as table 1 shown in embodiment 2, and products therefrom is designated as Lam-10.
Embodiment 3
Method, with embodiment 1, is different in that in each material content such as table 1 shown in embodiment 3, and products therefrom is designated as Lam-15.
Embodiment 4
Laminarin derivative L am-10 is weighed respectively in vessel by each material content shown in embodiment 4 in table 2, it is separately added into acrylamide monomer, distilled water again, stir, it is subsequently adding initiator A PS and TEMED, quickly stirs, take out after polyreaction 24h under room temperature, it is soaked in a large amount of deionized water, every 4h changes water, to remove unreacted monomer, namely obtains hydrogel.
Embodiment 5
Method, with embodiment 4, is different in that in each material content such as table 2 shown in embodiment 5.
Embodiment 6
Method, with embodiment 4, is different in that in each material content such as table 2 shown in embodiment 6.
Embodiment 7
Method, with embodiment 4, is different in that in each material content such as table 2 shown in embodiment 7.
Table 1
Table 2
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.

Claims (10)

1. one kind Biodegradable cross-linked dose, it is characterized in that, described Biodegradable cross-linked dose is glycidyl methacrylate graft laminarin, and described glycidyl methacrylate graft laminarin is grafted on the polarization hydroxyl of laminarin by the methylene of glycidyl methacrylate and described glycidyl methacrylate is sloughed (+)-2,3-Epoxy-1-propanol and formed.
2. as claimed in claim 1 Biodegradable cross-linked dose, it is characterised in that the substitution value of described Biodegradable cross-linked dose is 5-20.
3. the preparation method of Biodegradable cross-linked dose, comprises the following steps:
Thering is provided laminarin, glycidyl methacrylate agent, base catalyst and aprotic solvent, and described base catalyst is dimethylamino naphthyridine, described aprotic solvent is dimethyl sulfoxide;
Described laminarin and dimethylamino naphthyridine are dissolved in described dimethyl sulfoxide, form the first reactant liquor;
Adding described glycidyl methacrylate agent in described first reactant liquor, reaction generates glycidyl methacrylate graft laminarin.
4. the preparation method of Biodegradable cross-linked dose as claimed in claim 3, it is characterised in that the mol ratio of described laminarin and described glycidyl methacrylate is 1:(0.05-0.2).
5. the preparation method of Biodegradable cross-linked dose as claimed in claim 3, it is characterised in that the mass ratio of described laminarin and dimethylamino naphthyridine is 1:(0.15-0.25).
6. the preparation method of Biodegradable cross-linked dose as described in as arbitrary in claim 3-5, it is characterised in that also include the pH regulating the reaction mixture being obtained by reacting so that it is in neutrality;
To be stirred in neutral reaction mixture instillation anhydrous organic solvent, precipitate out, sucking filtration obtains glycidyl methacrylate graft laminarin filter cake after processing;
Undertaken described glycidyl methacrylate graft laminarin filter cake dialysing, obtain glycidyl methacrylate graft laminarin after frozen dried.
7. a polyacrylamide hydrophilic gel, it is characterised in that described polyacrylamide hydrophilic gel is using polypropylene amine as monomer, be polymerized using the arbitrary described glycidyl methacrylate graft laminarin of claim 1-2 as cross-linking agents.
8. a preparation method for polyacrylamide hydrophilic gel, comprises the following steps:
Thering is provided polypropylene amine monomer, glycidyl methacrylate graft laminarin and initiator, wherein, described initiator is the composite initiator of APS and TEMED composition;
Described polypropylene amine monomer, glycidyl methacrylate graft laminarin mix homogeneously in distilled water being formed mixed reaction solution, adds described initiator and carry out mixing process, polymerization forms polyacrylamide hydrophilic gel.
9. the preparation method of polyacrylamide hydrophilic gel as claimed in claim 8, it is characterised in that in described mixed reaction solution, the weight/mass percentage composition of described polypropylene amine monomer is 8-12%.
10. the preparation method of as claimed in claim 8 or 9 polyacrylamide hydrophilic gel, it is characterised in that described APS is weight percentage is the APS solution of 3-5%, and the volume ratio of described APS and TEMED is 10:(0.8-1.2).
CN201610209236.5A 2016-04-06 2016-04-06 Biodegradable cross-linking agent, polyacrylamide hydrogel and preparation method Pending CN105754037A (en)

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