CN101785874A - 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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- CN101785874A CN101785874A CN201010101464A CN201010101464A CN101785874A CN 101785874 A CN101785874 A CN 101785874A CN 201010101464 A CN201010101464 A CN 201010101464A CN 201010101464 A CN201010101464 A CN 201010101464A CN 101785874 A CN101785874 A CN 101785874A
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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 by 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 most widely used because it has better biocompatibility and optical transparence.
The thermal shape memory 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 the material that uses mostly is collapsible material at present, promptly by implanting ophthalmic after the material doubling, be subjected to the restriction of the material and the mode of implantation, under the prerequisite that reduces operative incision as far as possible, this class material often can not the whole implant cavity of complete filling (as lens capsule bag, vitreous chamber), and this just stays hidden danger for Post-operative complications (as after cataract, detachment of retina).
Eye with shape memory function promptly is prepared from by the macromolecular material with thermal shape memory function with material.By 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 by 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 different polymerization single polymerization monomers 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 preparation method 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 preparation method 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 by 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 have the acrylate monomer of different structure as the thermal polymerization monomer.Material is being injected mould behind the mix homogeneously under the situation of nitrogen protection by a certain percentage, carry out heat polymerization in 70 ℃ of-90 ℃ of environment, the response time is 24-48 hour.Wherein azodiisobutyronitrile is as thermal initiator.The method that the polymerizate that copolymerization forms extracts by the isopropyl alcohol Soxhlet is removed unreacted monomer and oligomer.
The cross-linking agent that the present invention has a different molecular weight by employing is regulated the heat-mechanical property and the shape-memory properties of macromolecular material.
But but key of the present invention is to determine the type of the thermal polymerization monomer selected for use and cross-linking agent and the proportioning of control thermal polymerization monomer and cross-linking agent.
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, by 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 by 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
Example 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%, the content of the thermal initiator (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) that adds 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 Soxhlet is extracted and removed unreacted monomer and oligomer, makes shape memory acrylate material.The refraction index of this material is 1.51, the visible region transmitance as shown in Figure 2, glass transition temperature is 29.5 ℃, elastic modelling quantity is 4.07MPa, deformation recovery time is 35.0s in the time of 37 ℃, the deformation recovery rate is 98%, the deformation photo is as shown in Figure 3.
Example 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%, the content of the thermal initiator (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) that adds 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 Soxhlet is extracted and removed unreacted monomer and oligomer, makes shape memory acrylate material.The refraction index of this material is 1.52, the visible region transmitance as shown in Figure 4, glass transition temperature is 19.4 ℃, elastic modelling quantity is 1.37MPa, deformation recovery time is 11.3s in the time of 37 ℃, the deformation recovery rate is 99%.
Example 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%, the content of the thermal initiator (azodiisobutyronitrile, Shanghai the 4th chemical reagents corporation) that adds 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 Soxhlet is extracted and removed unreacted monomer and oligomer, makes shape memory acrylate material.The refraction index of this material is 1.51, the visible region transmitance as shown in Figure 5, glass transition temperature is 21.2 ℃, elastic modelling quantity is 1.94MPa under the room temperature, deformation recovery time is 18.2s in the time of 37 ℃, the deformation recovery rate is 99%.
Claims (5)
1. an ophthalmic implanted material and preparation method 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 by 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.
2. a kind of ophthalmic implanted material and preparation method 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.
3. a kind of ophthalmic implanted material and preparation method as claimed in claim 1 with shape memory function, it is characterized in that: the molar percentage of 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.
4. a kind of ophthalmic implanted material and preparation method as claimed in claim 1 with shape memory function, the bulk thermal polymerization method is adopted in the polymerization that it is characterized in that having the ophthalmic implanted material of shape memory function, reaction temperature is 70 ℃-90 ℃, and the response time is 24-48 hour.
5. a kind of ophthalmic implanted material and preparation method with shape memory function as claimed in claim 1 is characterized in that the polymerizate purification, the mode that adopts Soxhlet to extract, and solvent for use is an isopropyl alcohol, extraction time is 24 hours.
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| CN2010101014643A CN101785874B (en) | 2010-01-26 | 2010-01-26 | Ophthalmic implanted material with shape memory function and preparation method thereof |
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| CN2010101014643A CN101785874B (en) | 2010-01-26 | 2010-01-26 | Ophthalmic implanted material with shape memory function and preparation method thereof |
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| CN101785874A true CN101785874A (en) | 2010-07-28 |
| CN101785874B CN101785874B (en) | 2012-08-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105164204A (en) * | 2012-11-21 | 2015-12-16 | 路易斯维尔大学研究基金会 | Compositions and methods for reducing oxidative damage |
| WO2020231073A1 (en) * | 2019-05-10 | 2020-11-19 | 서울대학교 산학협력단 | Method for coating implant using heat |
| CN114523685A (en) * | 2022-01-28 | 2022-05-24 | 华南理工大学 | Flame-retardant rapid software driver based on shape memory effect and preparation method and application thereof |
| CN115466426A (en) * | 2022-08-08 | 2022-12-13 | 清华大学 | Preparation method of post-elastic layer implanted film for treating corneal edema |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090189303A1 (en) * | 2006-05-09 | 2009-07-30 | Carl Zeiss Vision Australia Holdings Limited | Methods for forming coated high index optical elements |
| CA2655360C (en) * | 2006-07-12 | 2014-09-16 | Novartis Ag | Actinically crosslinkable copolymers for manufacturing contact lenses |
| CN101564551B (en) * | 2009-06-05 | 2012-07-25 | 北京科技大学 | Acrylic acid ester shape-memory intraocular lens material and preparation method thereof |
-
2010
- 2010-01-26 CN CN2010101014643A patent/CN101785874B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105164204A (en) * | 2012-11-21 | 2015-12-16 | 路易斯维尔大学研究基金会 | Compositions and methods for reducing oxidative damage |
| WO2020231073A1 (en) * | 2019-05-10 | 2020-11-19 | 서울대학교 산학협력단 | Method for coating implant using heat |
| KR20200130780A (en) * | 2019-05-10 | 2020-11-20 | 서울대학교산학협력단 | Method for coating prosthesis via thermal procedure |
| KR102259292B1 (en) | 2019-05-10 | 2021-06-03 | 서울대학교 산학협력단 | Method for coating prosthesis via thermal procedure |
| CN114523685A (en) * | 2022-01-28 | 2022-05-24 | 华南理工大学 | Flame-retardant rapid software driver based on shape memory effect and preparation method and application thereof |
| CN115466426A (en) * | 2022-08-08 | 2022-12-13 | 清华大学 | Preparation method of post-elastic layer implanted film for treating corneal edema |
| CN115466426B (en) * | 2022-08-08 | 2023-09-22 | 清华大学 | Preparation method of posterior elastic layer implanted film for treating corneal edema |
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| CN101785874B (en) | 2012-08-22 |
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