CN106750377A - Hydrogel, the composition for preparing hydrogel and hydrogel preparation method - Google Patents
Hydrogel, the composition for preparing hydrogel and hydrogel preparation method Download PDFInfo
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- CN106750377A CN106750377A CN201510812793.1A CN201510812793A CN106750377A CN 106750377 A CN106750377 A CN 106750377A CN 201510812793 A CN201510812793 A CN 201510812793A CN 106750377 A CN106750377 A CN 106750377A
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- glycine betaine
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Abstract
The present invention provides a kind of new composition for manufacturing hydrogel, it includes hydroxyethyl methacrylate and betanin derivative, wherein the betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group's glycine betaine, wherein in the composition, hydroxyethyl methacrylate and the mass ratio of betanin derivative are 0.875/1 to 14/1.
Description
Technical field
The present invention relates to a kind of medical material, more particularly to a kind of hydrogel.The present invention further provides one kind for preparing water
The composition of gel.The present invention is further directed to the preparation of hydrogel.
Background technology
Gel generally comprises plastic component and decentralized medium, and wherein the plastic component forms three-dimensional structure, to allow dispersion to be situated between
Matter, such as water, the three-dimensional structure that dispersed distribution is formed in the plastic component.Hydrogel is because of its good hydrophily, bio-compatible
Property and three-dimensional structure retentivity, are widely used in multiple fields.These characteristics of hydrogel its biomedical material lead
Domain has exclusive advantage and with huge development space.Its excellent biocompatibility makes it be obtained in field of tissue engineering technology
Extensive use, is such as used for artificial skin, artificial blood vessel, artificial cornea, contact lenses, joint prosthesis and various artificial dirty
Device and slow releasing carrier of medication etc..Additionally, the hydrogel being made based on hydroxyethyl methacrylate (HEMA) is due to inside it
The hydrogen bond action of presence, makes it have mechanical performance higher.Therefore, hydroxyethyl methacrylate class hydrogel is preferable because of its
Biocompatibility and mechanical performance, and be widely used in contact glass material, artificial blood vessel and other organizational projects aspect.
However, hydroxyethyl methacrylate hydrogel has, moisture content low (being generally not more than 50%), oxygen permeability be poor, anti-albumen
Adsorption capacity low (20%), transparency be not high, modulus loss height causes poor skin tactile, wearability and lubricity inadequate etc.
Shortcoming, these shortcomings limit extensive use of the hydroxyethyl methacrylate hydrogel in biomedical materials field.
The content of the invention
A kind of composition for preparing hydrogel (material), wherein said composition are provided it is a primary object of the present invention to it
Main constituents be hydroxyethyl methacrylate, the structural formula of the wherein hydroxyethyl methacrylate is：
A kind of composition for preparing high-performance water gel is provided another object of the present invention is to it, wherein said composition is entered
One step includes betanin derivative, such as sulfonic group glycine betaine (SBMA) and/or carboxylic acid group's glycine betaine (CBMA), wherein
The betanin derivative has following structural formula：
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein by
There is high-moisture percentage and good biocompatibility containing the hydrogel that said composition is made.
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein by
There is the anti-protein adsorption effect of good antibacterial containing the hydrogel that said composition is made.
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein by
There is the hydrogel (material) of good oxygen permeability containing the hydrogel that said composition is made.
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein by
The hydrogel being made containing said composition while with moisture content higher, with good pliability and higher smooth
Degree.
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein by
The plastic component of the hydrogel being made containing said composition is hydroxyethyl methacrylate, and helper component is betanin derivative.
A kind of composition for preparing high-performance water gel (material) is provided another object of the present invention is to it, wherein should
Composition includes hydroxyethyl methacrylate-betanin derivative, and the wherein betanin derivative can be sulfonic group glycine betaine
And/or carboxylic acid group's glycine betaine (CBMA) (SBMA).
It is used to prepare the composition of high-performance water gel (material) the present invention further provides one kind, wherein by said composition bag
Hydroxyethyl methacrylate and betanin derivative are included, wherein the betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group
Glycine betaine, wherein in the composition, the mass ratio of hydroxyethyl methacrylate and betanin derivative for 0.875/1 to
14/1。
It is used to prepare the composition of high-performance water gel (material) the present invention further provides one kind, wherein being entered by said composition
One step includes crosslinking agent and initiator, wherein in the composition, the mass fraction of crosslinking agent is 0.01%-1%, initiator
Mass fraction be 0.1%-1%.
It is used to prepare the composition of high-performance water gel (material) the present invention further provides one kind, wherein being combined by containing this
The water-setting hydrogel (material) that thing is made it is cheap, and when using said composition manufacture hydrogel when, its manufacture work
Skill is simple and does not need the structure of accurate instrument and complexity, low cost of manufacture.
The present invention further provides a kind of hydrogel for being suitable for use as biomedical material, the wherein hydrogel includes plastic group
Point, helper component and decentralized medium, the wherein plastic component includes hydroxyethyl methacrylate, and the helper component includes beet
Alkali derivant, the decentralized medium of the hydrogel is water, and wherein the betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group
Glycine betaine, wherein in the hydrogel, the mass fraction of hydroxyethyl methacrylate is 2.33% to 56%, and the glycine betaine spreads out
Biological mass fraction is 2.67% to 32%.
The present invention further provides a kind of hydrogel for being suitable for use as biological engineering material, wherein in the hydrogel, methyl-prop
The mass fraction of olefin(e) acid hydroxyl ethyl ester is 2.33% to 56%, and the mass fraction of the betanin derivative is 2.67% to 32%.It is excellent
Selection of land, in the hydrogel, the content of hydroxyethyl methacrylate is 2.33% to 45% (mass fraction), and glycine betaine spreads out
The content of biological (SBMA) is not more than 25% (mass fraction).
The present invention further provides a kind of hydrogel for being suitable for use as biological engineering material, the wherein hydrogel is further included
Initiator, wherein in the hydrogel, the mass fraction of the initiator is 0.04%-0.4%, and wherein the initiator is 2,4,6-
Trimethyl benzoyl diphenyl base phosphine oxide, (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones or azodiisobutyronitrile or
Benzoyl peroxide.
The present invention further provides a kind of method for manufacturing hydrogel, wherein using manufacture method of the present invention and of the present invention group
In hydrogel obtained in compound, the mass fraction of hydroxyethyl methacrylate is 2.33% to 56%, the betanin derivative
Mass fraction is 2.67% to 32%.Preferably, in the hydrogel, the content of hydroxyethyl methacrylate for 2.33% to
- 45% (mass fraction), the content of betanin derivative (SBMA) is not more than 25% (mass fraction).
Other purposes of the invention and feature are able to fully demonstrate and can be by appended claims by following detailed descriptions
In the combination of means and device specially pointed out be achieved.
According to the present invention, can realize that object defined above and other purposes and the subject hydrogel of advantage include plastic component, auxiliary
Component and decentralized medium, wherein the plastic component include hydroxyethyl methacrylate, and the helper component includes betanin derivative,
The decentralized medium of the hydrogel is water, and the wherein betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group's glycine betaine, its
In in the hydrogel, the mass fraction of hydroxyethyl methacrylate is 2.33% to 56%, the quality of the betanin derivative
Fraction is 2.67% to 32%.
The present invention further provides a kind of hydrogel preparation method, it is comprised the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and thermal initiator, and be sufficiently mixed, with
To reactant mixture, the wherein plastic component is hydroxyethyl methacrylate (HEMA), and the helper component is [2- (methyl-props
Enoyl- epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) and/or carboxylic acid group's glycine betaine (CBMA)；
(B) oxygen in the reactant mixture is removed using inert gas or nitrogen；
(C) reactant mixture is heated, the temperature of the reactant mixture is lifted to the thermal initiator needs and is initiated
Temperature, and be incubated to the thermal initiator and triggered completely, to prepare hydrogel；With
(D) deionized water washing hydrogel.
The present invention furthermore provides a kind of hydrogel preparation method, and it is comprised the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and light trigger, and be sufficiently mixed, with
To reactant mixture, the wherein plastic component is hydroxyethyl methacrylate (HEMA), and the helper component is [2- (methyl-props
Enoyl- epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) and/or carboxylic acid group's glycine betaine (CBMA)；
With
(B) ultraviolet light reacts the mixture until the light trigger is triggered completely.
Therefore, as described above, subject hydrogel (material) is with least one in following beneficial effects：
1st, the present invention has for manufacturing the hydrogel (material) that the composition of hydrogel prepares and (contains compared with high-moisture percentage
95%) water rate reaches as high as；
2nd, the present invention has good biocompatibility for manufacturing the hydrogel (material) that the composition of hydrogel is prepared；
3rd, the present invention has good oxygen permeability for manufacturing the hydrogel (material) that the composition of hydrogel is prepared；
4th, the present invention has the anti-albumen of good antibacterial for manufacturing the hydrogel (material) that the composition of hydrogel is prepared
Absorption (no more than 10%) effect；
5th, the present invention for manufacture the hydrogel (material) that the composition of hydrogel prepares have good pliability and
Smoothness higher；
6th, the present invention has more preferable light transmittance (no for manufacturing the hydrogel (material) that the composition of hydrogel is prepared
Less than 95%).
By the understanding to subsequent description and accompanying drawing, further aim of the present invention and advantage will be fully demonstrated.
These and other objects of the invention, feature and advantage, by following detailed descriptions, drawings and claims are able to
Fully demonstrate.
Brief description of the drawings
Fig. 1 is according to the hydrogel front view of present pre-ferred embodiments.
Fig. 2 be according to the water-cut variation schematic diagram of the hydrogel of present pre-ferred embodiments, wherein according to the figure, with
The increase of betanin derivative content in subject hydrogel, its moisture content is consequently increased.
Fig. 3 is according to the dehydration curve map of the hydrogel of present pre-ferred embodiments, wherein according to the figure, with the present invention
The increase of betanin derivative content in hydrogel, under identical environment, through same losing time, its final moisture content
It is consequently increased.
Fig. 4 is according to the dehydration curve map of the hydrogel of present pre-ferred embodiments, wherein according to the figure, with the present invention
The increase of betanin derivative content in hydrogel, its light transmittance brings up to 90% or so from 20% or so.
Fig. 5 is that " variation diagram, the figure is shown with the change of vibration stress the G according to the hydrogel of present pre-ferred embodiments
Change, the change of the storage modulus and loss modulus of material.
Fig. 6 is according to the anti-protein adsorption capacity variation diagram of the hydrogel of present pre-ferred embodiments, wherein according to the figure institute
Show, with the increase of betanin derivative content in subject hydrogel, its anti-protein adsorption capacity is improved.
Fig. 7 is that, according to the antibacterial adsorption capacity variation diagram of the hydrogel of present pre-ferred embodiments, composite aquogel is respectively provided with well
Antibacterial adsorption capacity.
Fig. 8 is according to the hydrogel manufacture method of present pre-ferred embodiments.Fig. 9 is according to the another kind of present pre-ferred embodiments
Hydrogel manufacture method.
Specific embodiment
It is described below to be disclosed for so that those skilled in the art manufacture and use the present invention.Middle offer described below it is preferable
Only as the example and modification that will be apparent to those skilled in the art, it does not constitute the limit to the scope of the invention to embodiment
System.General Principle defined in described below can be applied to without departing substantially from spirit of the invention and invention scope other embodiments,
Optional replacement, modification, equivalent implementation and application.
The present invention provides a kind of composition for manufacturing hydrogel, and it includes for the plastic component that manufactures hydrogel and changes
The helper component of kind hydrogel properties, wherein said composition include hydroxyethyl methacrylate, and the helper component includes glycine betaine
Derivative, wherein hydroxyethyl methacrylate have following structural formula：
The betanin derivative has following structural formula：
Preferably, betanin derivative be sulfonic group glycine betaine (SBMA) and/or carboxylic acid group's glycine betaine (CBMA), such as
Shown in structure above.
The present invention is for manufacturing active ingredient (including the plastic component that the composition of hydrogel can be prepared separately as hydrogel
And helper component) with crosslinking agent, initiator etc. for hydrogel preparation, or with crosslinking agent, initiator etc. and it is a kind of or
It is various other to be used suitable for manufacturing the compound or combination of compositions of hydrogel, for the preparation of hydrogel.
The present invention furthermore provides a kind of hydrogel, and the wherein plastic component of the hydrogel is hydroxyethyl methacrylate
(HEMA), the helper component is [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide
(SBMA) and/or carboxylic acid group's glycine betaine (CBMA), decentralized medium is water, wherein the plastic component in the hydrogel and
The quality of helper component and the percentage for accounting for hydrogel gross mass are 5%-60%.
Preferably, the crosslinking agent of the hydrogel has following molecular structural formula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
It is highly preferred that the crosslinking agent of the hydrogel is polyethylene glycol dimethacrylate.It is understood that of the invention
The crosslinking agent for being used can also be other crosslinking agents well-known to those skilled in the art.
Preferably, the initiator of the hydrogel is light trigger, and wherein the light trigger is 2,4,6- trimethylbenzoyls two
Phenyl phosphine oxide (TPO), (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones (Irgacure2959) or other abilities
Light trigger known to field technique personnel.
Alternatively, the initiator of the hydrogel be thermal initiator, wherein the thermal initiator be azodiisobutyronitrile (ABIN),
Benzoyl peroxide (BPO) or other thermal initiators well-known to those skilled in the art.
As shown in Fig. 8 of accompanying drawing, the present invention furthermore provides a kind of hydrogel preparation method, and it is comprised the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and thermal initiator, and be sufficiently mixed, with
To reactant mixture, the wherein plastic component is hydroxyethyl methacrylate (HEMA), and the helper component is [2- (methyl-props
Enoyl- epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) and/or carboxylic acid group's glycine betaine (CBMA)；
(B) oxygen in the reactant mixture is removed using inert gas or nitrogen；
(C) reactant mixture is heated, the temperature of the reactant mixture is lifted to the thermal initiator needs and is initiated
Temperature, and be incubated to the thermal initiator and triggered completely, to prepare hydrogel；With
(D) deionized water washing hydrogel.
Wherein, the crosslinking agent of the hydrogel has following molecular structural formula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
Usually, the thermal response time of the reactant mixture be not higher than 1 hour.Preferably, in the reactant mixture, first
The mass fraction of base hydroxy-ethyl acrylate (HEMA) is 20%-45%, [2- (methylacryloyl epoxide) ethyl] dimethyl
The mass fraction of-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) is 0-25%, and the mass fraction of crosslinking agent is 0.01%-1%,
The mass fraction of thermal initiator is 0.1%-1%.
It is highly preferred that in the reactant mixture, crosslinking agent is 1 with the mol ratio of plastic component:1000 to 1:100；Thermal initiation
Agent is 1 with the mass ratio of plastic component and the total amount of crosslinking agent:1000 to 5:1000.
Most preferably, thermal initiator and the mass ratio of plastic component and the total amount of crosslinking agent are 1:1000 to 3:1000.
It will be understood by those skilled in the art that step (D) to hydrogel obtained in step (C) when cleaning, water
Gel will further water absorption and swelling.Therefore, before hydrogel obtained in step (C) is placed into deionized water washing,
Water content in hydrogel is typically relatively low.After step (D), that is, hydrogel obtained in step (C) is put into
Deionized water washing after, hydrogel obtained in step (C) will water swelling so that obtained hydrogel is finally produced
The water content of the hydrogel of product reaches as high as 95%.
As shown in Fig. 9 of accompanying drawing, the present invention furthermore provides a kind of hydrogel preparation method, and it is comprised the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and light trigger, and be sufficiently mixed, with
To reactant mixture, the wherein plastic component is hydroxyethyl methacrylate (HEMA), and the helper component is [2- (methyl-props
Enoyl- epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) and/or carboxylic acid group's glycine betaine (CBMA)；
(B) ultraviolet light reacts the mixture until the light trigger needs the temperature being initiated and maintains the temperature extremely
The light trigger is triggered completely；With
(C) deionized water washing hydrogel.
Wherein, the crosslinking agent of the hydrogel has following molecular structural formula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
Usually, the wavelength of the ultraviolet is 300nm-415nm, and optimal wavelength is 365nm.
Usually, the optical response time of the reactant mixture is 25min to 60min.
Preferably, in the reactant mixture, the mass fraction of hydroxyethyl methacrylate (HEMA) is 20%-45%,
The mass fraction of [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide (SBMA) is 0-25%,
The mass fraction of crosslinking agent is 0.01%-1%, and the mass fraction of light trigger is 0.1%-1%.
It is highly preferred that in the reactant mixture, crosslinking agent is 1 with the mol ratio of plastic component:1000 to 1:100；Thermal initiation
Agent is 1 with the mass ratio of plastic component and the total amount of crosslinking agent:1000 to 5:100.
Most preferably, thermal initiator and the mass ratio of plastic component and the total amount of crosslinking agent are 1:1000 to 3:1000.
It is worth noting that, crosslinking agent herein can be polyethylene glycol dimethacrylate, thermal initiator can be
Azodiisobutyronitrile (ABIN) or benzoyl peroxide (BPO), light trigger can be 2,4,6- trimethylbenzoyls two
Phenyl phosphine oxide (TPO) or (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones (Irgacure2959).
It will be understood by those skilled in the art that step (C) to hydrogel obtained in step (B) when cleaning, water
Gel will further water absorption and swelling.Therefore, before hydrogel obtained in step (B) is placed into deionized water washing,
Water content in hydrogel is typically relatively low.After step (C), that is, hydrogel obtained in step (B) is put into
Deionized water washing after, hydrogel obtained in step (B) will water swelling so that obtained hydrogel is finally produced
The water content of the hydrogel of product reaches as high as 95%.
Example 1:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), 0.75mL hydroxyethyl methacrylates (HEMA) are taken, add 1mL
Deionized water after ultrasonic 20min, is well mixed, and is subsequently adding 0.75uL crosslinking agent (glycol dimethacrylates
Ester, molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, Irgacure2959),
After uniform mixing, reactant mixture is obtained.Then, by solution (the reaction mixing containing HEMA, crosslinking agent and initiator
Thing) closed mold is injected, ultra violet lamp 1h triggers radical polymerization and prepares hydrogel.Then, by mould and water
Gel is together put into deionized water, and a water is changed every 12h, records usually time, is rushed repeatedly with deionized water after degumming
Wash and soak 5 days, obtain HEMA hydrogels as shown in Figure 1.
Example 2:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulphurs of 0.05g is taken
Sour propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding
0.7mL hydroxyethyl methacrylates (HEMA), are well mixed, and are subsequently adding 0.75uL crosslinking agents (polyethylene glycol diformazan
Base acrylate, molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.70：0.05.
Example 3:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.1g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.65mL
Hydroxyethyl methacrylate (HEMA), is well mixed, and is subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethyl allene
Acid esters, molecular weight 550) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.65：0.10.
Example 4:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulphurs of 0.15g is taken
Sour propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding
The hydroxyethyl methacrylate (HEMA) of 0.6mL, is well mixed, and is subsequently adding 0.75uL crosslinking agents (polyethylene glycol two
Methacrylate, molecular weight 1000) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.60：0.15.
Example 5:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.2g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.55mL
Hydroxyethyl methacrylate (HEMA), be well mixed, be subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethyl propylene
Olefin(e) acid ester, molecular weight 20000) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.55：0.20.
Example 6:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulphurs of 0.25g is taken
Sour propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding
The hydroxyethyl methacrylate (HEMA) of 0.5mL, is well mixed, and is subsequently adding 0.75uL crosslinking agents (polyethylene glycol two
Methacrylate, molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.50：0.25.
Example 7:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.3g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water of 1mL, fully dissolving.It is subsequently adding the methyl-prop of 0.45mL
Olefin(e) acid hydroxyl ethyl ester (HEMA), be well mixed, be subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethacrylate,
Molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, Irgacure2959),
After uniform mixing, reactant mixture is obtained.Then, by the solution containing SBMA, HEMA, crosslinking agent and initiator
(reactant mixture) injects closed mold, and ultra violet lamp 1h triggers radical polymerization and prepares hydrogel.Then,
Mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time, spent after degumming from
Sub- water is rinsed and soaked 5 days repeatedly, and the mass ratio for obtaining the HEMA and SBMA in hydrogel is 0.45：0.30.
Example 8:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.4g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.35mL
Hydroxyethyl methacrylate (HEMA), be well mixed, be subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethyl propylene
Olefin(e) acid ester, molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.35：0.40.
Example 9:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.1g is taken
Propyl group) ammonium hydroxide (SBMA), 1mL water is added, fully dissolving is subsequently adding 0.65mL hydroxyethyl methacrylates
(HEMA), it is well mixed, is subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethacrylate, molecular weight 330)
With 7.5mg light triggers TMDPO (TPO), after uniform mixing, reaction is obtained mixed
Compound.Then, the solution (reactant mixture) containing SBMA, HEMA, crosslinking agent and initiator is injected closed
Mould, ultra violet lamp 1h triggers radical polymerization and prepares hydrogel.Then, mould and hydrogel are together put into
In deionized water, a water is changed every 12h, record usually time, rinse with deionized water and soak 5 after degumming repeatedly
My god, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is 0.65：0.10.
Example 10:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.1g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.65mL
Hydroxyethyl methacrylate (HEMA), is well mixed, and is subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethyl allene
Acid esters, molecular weight 550) and 7.5mg thermal initiator AIBN, after uniform mixing, obtain reactant mixture.Then, with
Nitrogen removes the oxygen in reactant mixture in advance.Again then, SBMA, HEMA, crosslinking agent and initiator will be contained
Solution (reactant mixture) injects closed mold, reacts 30-60 minutes at room temperature, triggers radical polymerization and prepares water-setting
Glue.Then, mould and hydrogel are together put into deionized water, a water is changed every 12h, record usually time, taken off
Rinsed repeatedly and soaked 5 days with deionized water after glue, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.65：0.10.
Example 11:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.1g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.65mL
Polyethylene glycol methyl methacrylate (PEGDMA), be well mixed, be subsequently adding 0.75uL crosslinking agents (poly- second two
Alcohol dimethylacrylate, molecular weight 330) and 7.5mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methylbenzenes third
Ketone, Irgacure2959), after uniform mixing, obtain reactant mixture.Then, SBMA, HEMA, crosslinking will be contained
Solution (reactant mixture) the injection closed mold of agent and initiator, ultra violet lamp 1h triggers radical polymerization and system
Standby hydrogel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, during record degumming
Between, rinsed repeatedly and soaked 5 days with deionized water after degumming, the quality of the HEMA in the hydrogel for obtaining and SBMA
Than being 0.65：0.10.
Example 12:It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), the carboxybetaine (CBMA) of 0.1g is taken, add 1mL ultrasounds 20min
Deionized water afterwards, fully dissolving.0.65mL hydroxyethyl methacrylates (HEMA) are subsequently adding, are well mixed,
It is subsequently adding 0.75uL crosslinking agents (polyethylene glycol dimethacrylate, molecular weight 330) and 7.5mg light triggers (2-
Hydroxyl -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, Irgacure2959), after uniform mixing, obtain reactant mixture.Then,
Solution (reactant mixture) containing SBMA, HEMA, crosslinking agent and initiator is injected into closed mold, uviol lamp
Irradiation 1h, triggers radical polymerization and prepares hydrogel.Then, mould and hydrogel are together put into deionized water,
A water is changed every 12h, usually time is recorded, is rinsed repeatedly and is soaked 5 days, the water-setting for obtaining with deionized water after degumming
The mass ratio of the HEMA and SBMA in glue is 0.65：0.10.
Example 13：It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.4g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.35mL
Hydroxyethyl methacrylate (HEMA), be well mixed, be subsequently adding 1.5uL crosslinking agents (polyethylene glycol dimethyl propylene
Olefin(e) acid ester, molecular weight 330) and 15mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.35：0.40.
Example 14：It is prepared by hydrogel
Under the conditions of room temperature (preferably 25 DEG C), [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid of 0.4g is taken
Propyl group) ammonium hydroxide (SBMA), add the deionized water after 1mL ultrasounds 20min, fully dissolving.It is subsequently adding 0.35mL
Hydroxyethyl methacrylate (HEMA), be well mixed, be subsequently adding 7.5uL crosslinking agents (polyethylene glycol dimethyl propylene
Olefin(e) acid ester, molecular weight 330) and 75mg light triggers (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones,
Irgacure2959), after uniform mixing, reactant mixture is obtained.Then, will containing SBMA, HEMA, crosslinking agent and
Solution (reactant mixture) the injection closed mold of initiator, ultra violet lamp 1h triggers radical polymerization and prepares water
Gel.Then, mould and hydrogel are together put into deionized water, a water are changed every 12h, record usually time,
Rinsed repeatedly and soaked 5 days with deionized water after degumming, the mass ratio of the HEMA and SBMA in the hydrogel for obtaining is
0.35：0.40.
Example 15：Moisture determination
Under the conditions of room temperature (preferably 25 DEG C), take dry EP and manage and weigh, quality is designated as m.Afterwards, take respectively
Example 1, example 2, example 3, example 4, example 5, example 6, example 7 and obtained hydrogel is appropriate in example 8,
After wiping surface free water away with filter paper, it is put into EP pipes and weighs, is designated as m1.The sample that will be taken is in freeze drier
Middle freeze-drying 24h, takes out and weighs, and is designated as m2.Hydrogel moisture content can be calculated by below equation：
EWC%=[(m1-m)-(m2-m)]/(m1-m) × 100%
Every group of sample surveys 3 parallel groups, takes arithmetic mean of instantaneous value.
Wherein the testing result is as shown in Fig. 2 of accompanying drawing.
Example 16：Percentage of water loss is determined
Under the conditions of room temperature (preferably 25 DEG C), take dry EP and manage and weigh, quality is designated as m.Afterwards, take respectively
Example 1, example 3 and obtained hydrogel is appropriate in example 8, after wiping surface free water away with filter paper, are put into EP pipes
And weigh, it is designated as m1.The EP pipes of sample will be added to be put into 60 DEG C of baking ovens, so that the rapid dehydration of hydrogel, every 10min
Take out EP to manage and weigh, be designated as m2.Hydrogel percentage of water loss can be obtained by below equation：
Percentage of water loss (%)=[(m1-m)-(m2-m)]/(m1-m) × 100%
Every group of sample surveys 3 parallel groups, takes arithmetic mean of instantaneous value.Wherein the testing result is as shown in Fig. 3 of accompanying drawing.
Example 17：Determination of light transmittance
Under the conditions of room temperature (preferably 25 DEG C), respectively by example 1, example 3 and in example 8 obtained hydrogel from water
Middle taking-up, the free water on surface is dried with lens wiping paper, and its optical transparence is characterized with ELIASA, obtains OD values (X),
Detection wavelength can be 400nm-650nm, and practical measurement is 450nm.And light transmittance is calculated by below equation：
T=10^ (- X) × 100%
Wherein the testing result is as shown in Fig. 4 of accompanying drawing.
Example 18：Loss modulus is determined with the rheological property of storage modulus
Under the conditions of room temperature (preferably 25 DEG C), respectively by example 1, example 3 and in example 8 obtained hydrogel from water
Middle taking-up, after saturation is swelling, is placed in TA-AR-G2, and with 25mm, 2.008 ° of conical plate is sheared to hydrogel.
Shear strain 0.1% to 100% is set, and shearing frequency is 10rad/s, and temperature is 25 DEG C, obtains storage modulus G ' with loss
Modulus G ".
Wherein the testing result is as shown in Fig. 5 of accompanying drawing.
Example 19：Anti- protein adsorption ability is determined
Hydrogel sample is determined to nonspecific proteins with the method for the EUSA (ELISA) after improvement
The adsorption capacity of matter.Model protein is the goat anti-human immunoglobulin (HRP-IgG) of horseradish peroxidase-labeled, right
It is tissue culturing polystyrene (TCPS) according to group.After adding the substrate o-phenylene diamine of HRP, o-phenylenediamine is catalyzed by HRP
As color products, the amount of product is directly related with the amount of HRP-IgG materials, therefore can be quantified according to the depth of colour generation
Analysis.
First, example 1, example 3 are taken respectively and obtained hydrogel is appropriate in example 8, and by hydrogel sample and TCPS
Piece is put into 24 orifice plates, after adding the HRP-IgG solution 1mL of 1 μ g/mL, is incubated 1.5 hours, then uses PBS solution
Rinse 5 times, then take out sample and be put into new hole.1mL is added containing 0.03% hydrogen peroxide and 1mg/mL neighbour's benzene two
(5.0) 0.1mol/L, pH value is to the citrate phosphate buffer of amine (OPD).After 15 minutes, isometric 1mol/L is added
H2SO4Terminate enzymatic activity.OD value (OD values) is determined at 492nm using ELIASA.
Wherein the testing result is as shown in Fig. 6 of accompanying drawing.
Example 20：Antibacterial adsorption capacity is determined
The anti-bacterial attachment performance of hydrogel is detected as model bacterium using the staphylococcus aureus of the poison that goes out.First,
By S. aureus Inoculate on aseptic LB agar plates, 37 DEG C of overnight incubations.Then in 37 DEG C, 200rpm conditions
Under, cultivate single bacterium colony (being obtained from initial incubation thing) 12 hours in flasks of the 60mL containing sterile LB medium.So
Culture is poured into two centrifuge tubes of 50mL afterwards, is centrifuged 20 minutes under the conditions of 4 DEG C, 4750rpm.Supernatant discarded
Liquid, cell pellet is suspended in the aseptic PBS solution of 30mL again, and washing bacterium passes through ultraviolet spectrometry light 2 times afterwards
Bacterial concentration is adjusted to 1 × 10 by degree meter6/ mL, the experiment for measuring bacterial adhesion.Before measure, take respectively example 3,
Obtained hydrogel is appropriate in example 5 and example 8, and is separately immersed in 70% (volume fraction) ethanol and pre-processes 5
Minute, then soaked 10 minutes with PBS.Then adsorbed 1 hour in hydrogel being placed into bacterial suspension, PBS solution
Gram's staining is carried out after washing.Adhesion results are directly observed under 40 times of camera lenses using Nikon Ti-E series microscopes.
Wherein the testing result is as shown in Fig. 7 of accompanying drawing.
It can be seen from above-mentioned example 1 to example 20, to adding less SBMA (or CBMA) in gel reaction mixture
Can greatly improve HEMA hydrogels light transmittance.And as the content of SBMA increases, the light transmittance of material is bright
Aobvious to improve, storage modulus and loss modulus progressively decline, and complete moisture content is also significantly improved, and show its lubricity and thoroughly
Oxygen rate improves significantly.And protein adsorption experiment and germ experiment are all indicated as the content of SBMA increases, material
Anti- protein adsorption and the antibacterial absorption of material are also significantly improved.
Those skilled in the art would appreciate that the embodiment of the present invention shown in accompanying drawing and described above is only to of the invention
Example is rather than limitation.
It can thus be seen that the object of the invention can be efficiently accomplished fully.For explaining being somebody's turn to do for function and structure principle of the present invention
Embodiment is absolutely proved and described, and the present invention is not limited by based on the change on these embodiment basis.Cause
This, the present invention includes covering all modifications within appended claims claimed range and spirit.
Claims (14)
1. a kind of composition for manufacturing hydrogel, it is characterised in that including hydroxyethyl methacrylate and glycine betaine
Derivative, the wherein betanin derivative are sulfonic group glycine betaine and/or carboxylic acid group's glycine betaine, wherein in the composition,
Hydroxyethyl methacrylate is 0.875/1 to 14/1 with the mass ratio of betanin derivative.
2. composition according to claim 1, it is characterised in that further include crosslinking agent and initiator, wherein
In the composition, the mass fraction of crosslinking agent is 0.01%-1%, and the mass fraction of initiator is 0.1%-1%.
3. a kind of hydrogel for being suitable for use as biomedical material, it is characterised in that the hydrogel includes plastic component, auxiliary
Component and decentralized medium are helped, wherein the plastic component includes hydroxyethyl methacrylate, the helper component derives including glycine betaine
Thing, the decentralized medium of the hydrogel is water, and the wherein betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group's glycine betaine,
Wherein in the hydrogel, the mass fraction of hydroxyethyl methacrylate is 2.33% to 56%, the matter of the betanin derivative
Amount fraction is 2.67% to 32%.
4. hydrogel according to claim 3, it is characterised in that crosslinking agent is further included, wherein in the water-setting
In glue, the mass fraction of the crosslinking agent is 0.004%-0.4%.
5. hydrogel according to claim 4, it is characterised in that initiator is further included, wherein in the water-setting
In glue, the mass fraction of the initiator is 0.04%-0.4%, and wherein the initiator is 2,4,6- trimethyl benzoyl diphenyl bases
Phosphine oxide, (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones or azodiisobutyronitrile or benzoyl peroxide.
6. the hydrogel according to claim 4 or 5, it is characterised in that the crosslinking agent has following molecular structural formula：Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
7. a kind of hydrogel for being suitable for use as biomedical material, it is characterised in that the hydrogel includes plastic component, auxiliary
Component and decentralized medium are helped, wherein the plastic component includes hydroxyethyl methacrylate, the helper component derives including glycine betaine
Thing, the decentralized medium of the hydrogel is water, and the wherein betanin derivative is sulfonic group glycine betaine and/or carboxylic acid group's glycine betaine,
Wherein in the hydrogel, hydroxyethyl methacrylate is 0.875/1 to 14/1 with the mass ratio of betanin derivative.
8. hydrogel according to claim 7, it is characterised in that further include crosslinking agent, wherein the crosslinking agent
With following molecular structural formula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
9. the hydrogel according to claim 7 or 8, it is characterised in that initiator is further included, wherein at this
In hydrogel, the mass fraction of the initiator is 0.04%-0.4%, and wherein the initiator is 2,4,6- trimethylbenzoyls two
Phenyl phosphine oxide, (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones or azodiisobutyronitrile or benzoyl peroxide.
10. hydrogel according to claim 9, it is characterised in that the mass fraction of the crosslinking agent is 0.004%-0.4%,
The mass fraction of the initiator is 0.04%-0.4%.
11. a kind of hydrogel preparation methods, it is characterised in that comprise the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and light trigger, and be sufficiently mixed, to obtain
Reactant mixture, wherein the plastic component are hydroxyethyl methacrylate, and the helper component is [2- (methylacryloyl epoxide)
Ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide and/or carboxylic acid group's glycine betaine；With
(B) ultraviolet light reacts the mixture up to the light trigger is triggered completely, and the wavelength of the wherein ultraviolet is
330nm to 385nm.
12. preparation methods according to claim 11, it is characterised in that the light trigger is 2,4,6- trimethylbenzenes
Formoxyl diphenyl phosphine oxide and/or (2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, the crosslinking agent has following point
Subformula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
13. a kind of hydrogel preparation methods, it is characterised in that comprise the following steps：
(A) deionized water dissolving plastic component, helper component, crosslinking agent and thermal initiator, and be sufficiently mixed, with
To reactant mixture, the wherein plastic component is hydroxyethyl methacrylate, and the helper component is [2- (methylacryloyl oxygen
Base) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide and/or carboxylic acid group's glycine betaine；
(B) oxygen in the reactant mixture is removed using inert gas or nitrogen；With
(C) reactant mixture is heated, the temperature of the reactant mixture is lifted to the thermal initiator needs and is initiated
Temperature, and be incubated to the thermal initiator and triggered completely, to prepare hydrogel.
14. preparation methods according to claim 13, it is characterised in that the thermal initiator be azodiisobutyronitrile and/
Or benzoyl peroxide, the wherein crosslinking agent has following molecular structural formula：
Wherein the molecular weight of the crosslinking agent is not less than 300, no more than 20000.
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| CN107789093A (en) * | 2017-10-30 | 2018-03-13 | 广州新诚生物科技有限公司 | The artificial nasolacrimal canal that self-expanding is fixed |
| CN107793579A (en) * | 2017-10-30 | 2018-03-13 | 广州新诚生物科技有限公司 | A kind of hydrogel and its application |
| CN108404225A (en) * | 2018-03-08 | 2018-08-17 | 广州锐澄医疗技术有限公司 | A kind of lacrimal bolt and preparation method thereof |
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| CN110885408A (en) * | 2018-09-10 | 2020-03-17 | 天津大学 | Method for regulating and controlling mechanical properties of acrylonitrile-based binary copolymerization high-strength hydrogel by using molecular weight of cross-linking agent |
| CN112538173A (en) * | 2019-09-23 | 2021-03-23 | 天津大学 | Hydroxyethyl methacrylate based bulk polymerized hydrogel and preparation method thereof |
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| CN112795030B (en) * | 2020-12-29 | 2022-10-28 | 浙江工业大学 | Drug-loaded anti-adhesion contact lens hydrogel material and preparation method thereof |
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