CN101785874B - Ophthalmic implanted material with shape memory function and preparation method thereof - Google Patents
Ophthalmic implanted material with shape memory function and preparation method thereof Download PDFInfo
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- CN101785874B CN101785874B CN2010101014643A CN201010101464A CN101785874B CN 101785874 B CN101785874 B CN 101785874B CN 2010101014643 A CN2010101014643 A CN 2010101014643A CN 201010101464 A CN201010101464 A CN 201010101464A CN 101785874 B CN101785874 B CN 101785874B
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- memory function
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Abstract
The invention relates to an ophthalmic implanted material with the shape memory function and a preparation method thereof, belonging to the field of biomedical materials. Thermally polymerizable acrylate monomers are used as the basic material, and the mol ratio thereof is 10.0-98.0%; polyethylene glycol diacrylates or polyethylene glycol dimethyl acrylates, which have different molecular weights, are used as the cross-linking agent, and the mol ratio thereof is 2.0-90.0%; and thermal initiator accounts for 0.2-1.0% of the total mass. The thermally polymerizable monomers, the thermal initiator and the cross-linking agent are uniformly mixed under the protection of nitrogen gas, then the mixture is injected into a mold to be subject to the thermal polymerization reaction at the temperature of 70-90 DEG C for 24-48 hours, and the Soxhlet extraction is adopted to remove the unreacted monomers and oligomers to obtain the ophthalmic implanted material with the shape memory function. The invention has the advantages that the prepared material has the shape memory property, the memory property transition temperature of the material can be adjusted to the body temperature, and the material has large deformation extent and higher light transmittance in visible light areas.
Description
Technical field
The invention belongs to biomedical materials field, relate to a kind of ophthalmic implanted material and preparation method thereof, particularly select the cross-linking agent of different molecular weight to carry out thermal polymerization, preparation has the ophthalmic implanted material of shape memory function.
Background technology
The organizational structure of eyeball is very fine, and the major function of ophthalmic implant is promptly replaced the eye refraction medium, recovered visual performance.Therefore, the major requirement to ophthalmic implant promptly has the good transparency and can reduce the damage to eyeball through as far as possible little otch implantation ophthalmic.Common ophthalmic implant mainly contains artificial cornea, intraocular lens, artificial vitreous etc. at present.Implant material mainly contains esters of acrylic acid, silicone-hydrogel class etc.Wherein therefore esters of acrylic acid is used the most extensive because it has better biocompatibility and optical transparence.
Thermal shape memory property material is meant under higher temperature, and deformation can take place, and deformation is fixed and can long-term storage when temperature is reduced to lower temperature, and when being warming up to a certain specific response temperature once more, material can be replied the polymer of original shape fast.Because temperature control is adopted in deformation, and is easy to use, therefore also active to its research and development, what be used for technical field of biological material research mainly also is this type of thermal shape memory macromolecular material.But mostly the material that uses at present is collapsible material; Promptly through with implanting ophthalmic after the material doubling; Receive the restriction of the material and the mode of implantation; Under the prerequisite that reduces operative incision as far as possible, this type material often can not the whole implant cavity of complete filling (like lens capsule bag, vitreous chamber), and this just stays hidden danger for Post-operative complications (like after cataract, detachment of retina).
Eye with shape memory function promptly is prepared from the macromolecular material with thermal shape memory function with material.Through selecting the big and transition temperature of deformation quantity is the shape memory macromolecule of body temperature, and the shape after making it moulding is thin and thin, can inject ophthalmic through little otch, and its shape is recovered to launch under the heating of body temperature, obtains to have the implant of optical surface greatly.In field of ophthalmology, this embedded material can be used as artificial cornea, intraocular lens, artificial vitreous etc.Utilize the characteristics of its thermoregulation deformation, can after implantation, obtain bigger optical surface and be full of whole implant cavity, thereby realize maximized simulation normal eye structure, effectively reduce the generation of various post-operative complication.In addition, this design can be carried out moulding and fixing in the course of processing to material, has simplified in the operation material folding waited operation, only needs the typical ophthalmic apparatus just implantable, has reduced the requirement to operating theater instruments and operation skill effectively.
Key link with ophthalmic implanted material preparation of shape memory function is the deformation transition temperature of material is regulated and control to body temperature, guarantees that simultaneously material has the higher transparency, increases deformation quantity thereby will make material have stronger pliability in addition.Therefore the selection and the mixed ratio of various polymerization monomer and cross-linking agent seem particularly important.
Summary of the invention
The object of the present invention is to provide a kind of ophthalmic implanted material and method for preparing with shape memory function; This material can be used as artificial cornea, intraocular lens, artificial vitreous, and can overcome shortcomings such as the implantation otch that existing ophthalmology embedded material exists is big, material can not be filled whole implant cavity, post-operative complication is many.
A kind of ophthalmic implanted material and method for preparing with shape memory function; It is characterized in that: different cross-linking agent and two or more the acrylate monomer material copolymerization of molecular weight form copolymer through having following structure, and unreacted monomer is removed in the polymerizate purification and oligomer promptly makes the ophthalmic implanted material with shape memory function; Wherein the general structure of cross-linking agent is:
Wherein, X is H or CH
3N is 2-20;
The general structure of acrylate monomer is:
Wherein, X is H or CH
3M is 2-17; Y is not for having or O; Z is phenyl ring or methyl.
The inventive method adopts has different molecular weight polyethylene glycol diacrylate or polyethylene glycol dimethacrylate as cross-linking agent, but various acrylate monomer with different structure is as the thermal polymerization monomer.Material is being injected mould behind the mix homogeneously under the situation of nitrogen protection by a certain percentage, in 70 ℃ of-90 ℃ of environment, carrying out heat polymerization, the response time is 24-48 hour.Wherein azodiisobutyronitrile is as thermal initiator.The polymerizate that copolymerization forms is removed unreacted monomer and oligomer through the method that isopropyl alcohol Suo Shi extracts.
The cross-linking agent that the present invention has a different molecular weight through employing is regulated the heat-mechanical property and the shape-memory properties of macromolecular material.
But but key of the present invention is thermal polymerization monomer and the type of cross-linking agent and the proportioning of control thermal polymerization monomer and cross-linking agent that will confirm to select for use.
The present invention adopts the method preparation of thermal polymerization to have the ophthalmic implanted material of shape memory function.But stock is the acrylic ester monomer of thermal polymerization and cross-linking agent with various different molecular weights, and the content of cross-linking agent accounts for the 2.0%-90.0% of total molal weight.It is 0.2%-1.0% that but the content of the thermal initiator that adds accounts for the mass percent of thermal polymerization monomer and cross-linking agent gross mass.
But the monomer of the present invention monomeric mixture that is thermal polymerization.The acrylic ester monomer that wherein has benzene ring structure can be acrylic acid-2-phenoxy ethyl, methacrylic acid-2-phenoxy ethyl, phenylethyl, methacrylic acid phenethyl ester, and alkyl acrylate can comprise n-butyl acrylate, n-BMA, dodecyl acrylate, metering system dodecyl gallate, octadecyl acrylate, octadecyl methacrylate etc.But the thermal polymerization acrylic ester monomer of other kinds can use with these monomer blends.
Cross-linking agent of the present invention is to have different molecular weight polyethylene glycol diacrylate or polyethylene glycol dimethacrylate.
The present invention has utilized the acrylic ester monomer chemical crosslinking to form the characteristics of shape memory macromolecular material; Through selecting the cross-linking agent of different molecular weight; Regulate the proportioning of cross-linking agent; The memory performance transition temperature that makes the shape memory material is a body temperature, and the material deformation amount is big, the visible region spectral transmittance, thereby reaches the novel purpose with ophthalmic implanted material of shape memory function of preparation.
Advantage or good effect
But through adopting the acrylic ester monomer of thermal polymerization; Under the cross-linking agent effect of various different molecular weights; Can prepare the ophthalmic implanted material with shape-memory properties, and the memory performance transition temperature of material is adjustable to body temperature, the material deformation amount is big, higher at the visible region light transmittance.
Description of drawings
But Fig. 1 is the chemical structural formula of the thermal polymerization acrylate monomer, cross-linking agent and the initiator that use among the embodiment.
Fig. 2 is the spectrum transmitting rate curve of the ophthalmic implanted material with shape memory function of embodiment 1 preparation.
Fig. 3 recovers photo for the deformation of the ophthalmic implanted material with shape memory function of embodiment 1 preparation.
Fig. 4 is the spectrum transmitting rate curve of the ophthalmic implanted material with shape memory function of embodiment 2 preparations.
Fig. 5 is the spectrum transmitting rate curve of the ophthalmic implanted material with shape memory function of embodiment 3 preparations.
The specific embodiment
Instance 1
Selecting monomer for use is (a): acrylic acid-2-phenoxy ethyl (Sigma-Aldrich company), (b): methacrylic acid-2-phenoxy ethyl (Sigma-Aldrich company).The monomer molar ratio of selecting for use is a/b=4/1; The shared molar content of the two is 90.0%; Cross-linking agent is polyethyleneglycol diacrylate 400 (a Sigma-Aldrich company); Molar content is 10.0%, and the content of the thermal initiator of adding (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) is 0.5% of gross mass.Monomer, cross-linking agent and initiator are injected mould behind mix homogeneously under the nitrogen protection, 80 ℃ of heated polymerizables are 24 hours in baking oven, and Suo Shi extracts and removes unreacted monomer and oligomer, processes shape memory acrylic ester material.The refraction index of this material is 1.51, and the visible region transmitance is as shown in Figure 2, and glass transition temperature is 29.5 ℃, and elastic modelling quantity is 4.07MPa, and deformation recovery time is 35.0s in the time of 37 ℃, and the deformation recovery rate is 98%, and the deformation photo is as shown in Figure 3.
Instance 2
Selecting monomer for use is (a): acrylic acid-2-phenoxy ethyl (Sigma-Aldrich company), (b): methacrylic acid-2-phenoxy ethyl (Sigma-Aldrich company).The monomer molar ratio of selecting for use is a/b=4/1; The shared molar content of the two is 95.0%; Cross-linking agent is polyethyleneglycol diacrylate 1000 (a Sigma-Aldrich company); Molar content is 5.0%, and the content of the thermal initiator of adding (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) is 0.5% of gross mass.Monomer, cross-linking agent and initiator are injected mould behind mix homogeneously under the nitrogen protection, 75 ℃ of heated polymerizables are 36 hours in baking oven, and Suo Shi extracts and removes unreacted monomer and oligomer, processes shape memory acrylic ester material.The refraction index of this material is 1.52, and the visible region transmitance is as shown in Figure 4, and glass transition temperature is 19.4 ℃, and elastic modelling quantity is 1.37MPa, and deformation recovery time is 11.3s in the time of 37 ℃, and the deformation recovery rate is 99%.
Instance 3
Selecting monomer for use is (a): acrylic acid-2-phenoxy ethyl (Sigma-Aldrich company), (b): dodecyl acrylate (Tianjin proud son of heaven chemical industry company limited).The monomer molar ratio of selecting for use is a/b=5/1; The shared molar content of the two is 90.0%; Cross-linking agent is polyethylene glycol dimethacrylate 600 (a Sigma-Aldrich company); Molar content is 10.0%, and the content of the thermal initiator of adding (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) is 0.5% of monomer gross mass.Monomer, cross-linking agent and initiator are injected mould behind mix homogeneously under the nitrogen protection, 75 ℃ of heated polymerizables are 24 hours in baking oven, and Suo Shi extracts and removes unreacted monomer and oligomer, processes shape memory acrylic ester material.The refraction index of this material is 1.51, and the visible region transmitance is as shown in Figure 5, and glass transition temperature is 21.2 ℃, and elastic modelling quantity is 1.94MPa under the room temperature, and deformation recovery time is 18.2s in the time of 37 ℃, and the deformation recovery rate is 99%.
Claims (2)
1. an ophthalmic implanted material and method for preparing with shape memory function; It is characterized in that: different cross-linking agent and two or more the acrylate monomer materials of molecular weight adopts the bulk thermal polymerization method through having following structure; Reaction temperature is 70 ℃-90 ℃; Response time is 24-48 hour, forms copolymer, and unreacted monomer is removed in the polymerizate purification and oligomer promptly makes the ophthalmic implanted material with shape memory function;
Wherein, the general structure of cross-linking agent is:
Wherein, X is H or CH
3N is 2-20;
The general structure of acrylate monomer is:
Wherein, X is H or CH
3M is 2-17; Y is not for having or O; Z is phenyl ring or methyl;
The molar percentage of said cross-linking agent is the 2.0%-90.0% of acrylate monomer and the total molal weight of cross-linking agent; The molar percentage of acrylate monomer is the 10.0%-98.0% of acrylate monomer and the total molal weight of cross-linking agent; Azodiisobutyronitrile is a thermal initiator, accounts for the 0.2%-1.0% of acrylate monomer and cross-linking agent gross mass;
Said polymerizate is purified, the mode that adopts Suo Shi to extract, and solvent for use is an isopropyl alcohol, extraction time is 24 hours.
2. a kind of ophthalmic implanted material and method for preparing with shape memory function as claimed in claim 1 is characterized in that the structure of acrylate monomer is selected from: two or more in acrylic acid-2-phenoxy ethyl, methacrylic acid-2-phenoxy ethyl, phenylethyl, methacrylic acid phenethyl ester, n-butyl acrylate, n-BMA, dodecyl acrylate, metering system dodecyl gallate, octadecyl acrylate and the octadecyl methacrylate.
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| EP2922919B1 (en) * | 2012-11-21 | 2020-03-25 | University Of Louisville Research Foundation, Inc. | Compositions and methods for reducing oxidative damage |
| KR102259292B1 (en) * | 2019-05-10 | 2021-06-03 | 서울대학교 산학협력단 | Method for coating prosthesis via thermal procedure |
| CN114523685B (en) * | 2022-01-28 | 2023-04-21 | 华南理工大学 | Flame-retardant rapid software driver based on shape memory effect and preparation method and application thereof |
| CN115466426B (en) * | 2022-08-08 | 2023-09-22 | 清华大学 | Preparation method of posterior elastic layer implanted film for treating corneal edema |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101466529A (en) * | 2006-05-09 | 2009-06-24 | 卡尔蔡司视觉澳大利亚控股有限公司 | Methods for forming coated high index optical elements |
| CN101490099A (en) * | 2006-07-12 | 2009-07-22 | 诺瓦提斯公司 | Actinically crosslinkable copolymers for manufacturing contact lenses |
| CN101564551A (en) * | 2009-06-05 | 2009-10-28 | 北京科技大学 | Acrylic acid ester shape-memory intraocular lens material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101466529A (en) * | 2006-05-09 | 2009-06-24 | 卡尔蔡司视觉澳大利亚控股有限公司 | Methods for forming coated high index optical elements |
| CN101490099A (en) * | 2006-07-12 | 2009-07-22 | 诺瓦提斯公司 | Actinically crosslinkable copolymers for manufacturing contact lenses |
| CN101564551A (en) * | 2009-06-05 | 2009-10-28 | 北京科技大学 | Acrylic acid ester shape-memory intraocular lens material and preparation method thereof |
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