CN1172723C - Swelled polymer particles filter process for preparing artificial eye holder - Google Patents
Swelled polymer particles filter process for preparing artificial eye holder Download PDFInfo
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- CN1172723C CN1172723C CNB021241341A CN02124134A CN1172723C CN 1172723 C CN1172723 C CN 1172723C CN B021241341 A CNB021241341 A CN B021241341A CN 02124134 A CN02124134 A CN 02124134A CN 1172723 C CN1172723 C CN 1172723C
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- artificial eye
- eye holder
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Abstract
The present invention relates to a method of preparing an artificial eye holder by filtering out swelled polymer particles, which belongs to the field of biomedicine. The artificial eye holder of the present invention has the preparation method that 1) a biocompatible polymer is dissolved by solvent to obtain saturated solution; the saturated solution and a sieved pore-forming agent (with the particle diameter of 300 to 600 micrometers) are stirred and mixed, pressed into a sphere in a mould; after the solvent is volatilized, a spherical semi-finished product is obtained; 2) an initiating agent, a cross-linking agent and a polymer monomer are mixed and prepared into swelling solution; 3) the spherical semi-finished product is placed into a bunsen beaker; the solution in step 2 is poured until the spherical semi-finished product is submerged; the spherical semi-finished product is introduced with nitrogen gas, sealed and swelled for 3 to 100 hours; 4) the swelled spherical semi-finished product is taken out, placed into a reaction vessel, introduced with nitrogen gas, sealed and polymerized; 5) the sphere is taken out, immersed into deionized water which is replaced in definite time for 72 hours and taken out to obtain the required artificial eye holder. The artificial eye holder adopts press forming and has the advantages of precise shape and good cavity communication structure. The porosity of the artificial eye holder can be up to more than 80%. The performance of a material is improved greatly by a network structure generated by swelling and polymerization.
Description
Technical field
The invention belongs to biomedical sector, relate to a kind of preparation that is used to fill the artificial eye holder of eye socket and ram method.
Background technology
Artificial eye holder is to carry out after eyeball excise or ophthalmic hold enucleation, and the eye socket volume reduces, and for preventing the eye socket implant that postoperative eye socket deformity, entropion adopt, has the effect of treatment and beauty treatment simultaneously.Once used some materials in early days as glass, ormolu, plastics, cartilage, fat deposit, silicone etc., but all because complication and undesirable in various degree, as: plastics easily skid off, fat deposit easily is absorbed, silicone has rejection etc., the shortcoming of these material maximums is fixing eye muscle, gives ocular prosthesis vigor and vitality.Use at present synthetic material mainly concentrate on porous material such as polyethylene (MEDPORE, porouspolyethylene), aluminium sesquioxide (Al
2O
3), pottery and hydroxyapatite (HA) etc., but these materials are because its surface is hard, so be easy to generate inflammatory reaction.
Summary of the invention
The purpose of this invention is to provide a kind of better biocompatibility that has, be difficult for the preparation method of the artificial eye holder of initiation inflammatory reaction.
The manufacturing process of artificial eye holder of the present invention at first is to make spherical semi-finished product.With the biocompatible polymer dissolution with solvents, make saturated solution earlier, mix with the pore former of the particle diameter that sieves with standard screen in 300 microns～600 micrometer ranges then, wherein saturated solution: pore former=1: 2～3.5 (weight ratio).Said biocompatible polymer is various types of polyurethane and poly--beta-hydroxy alkanoic acid ester (PHA) class material as PAUR, EU, poly butyric ester (PHB), butyric ester-valerate copolymer (PHBV), butyric ester-alkyl caproate copolymer (PHBH) etc.Said solvent is the good solvent such as the oxolane of above-mentioned material, chloroform etc.Said pore former is NaCl, KCl, Na
2CO
3, NH
4HCO
3, NaHCO
3, water soluble particle such as white sugar.
The saturated solution that will add pore former then is poured into and is pressed into ball (mould is that two parts are formed up and down, the groove of one group of dome-type is respectively arranged, and several passages are arranged, and the diameter of groove is between 10 millimeters～30 millimeters) in the stainless steel mould.Then mould is left standstill under 20 ℃ and treated the solvent evaporates rear demoulding in 24 hours, obtain spherical semi-finished product, spherical semi-finished product are carried out the outward appearance finishing, make its neat appearance, put into the vacuum drying oven evacuation again and removed residual solvent in dry 2 hours, promptly obtain spherical semi-finished product.
After making spherical semi-finished product, initiator, cross-linking agent, polymer monomer are mixed mutually, be mixed with swelling solution.Said initiator is a radical initiator, as azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), dibenzoyl peroxide (BPO), dilauroyl peroxide, potassium peroxydisulfate, Ammonium persulfate. etc.Said cross-linking agent is N,N methylene bis acrylamide, DIETHYLENE GLYCOL (DVG), vinyl ethylene glycol dimethacrylate (EDMA) etc.Said polymer monomer is methyl acrylic ester and acrylic compounds such as 2-hydroxyethyl methacry-late (HEMA), methyl methacrylate (MMA), methacrylic acid-2-ethoxy ethyl ester (EEMA), methacrylic acid (MA) etc.The formula proportion of above-mentioned three kinds of components is: (weight ratio)
Initiator 0.9%～1.0% cross-linking agent 0.4%～0.5% polymer monomer 98.5%～98.7%
Then spherical semi-finished product are put into a dry beaker, poured into the swelling solution of preparation, flooded spherical semi-finished product, logical nitrogen, sealing, swelling 3～100 hours.Take out the spherical semi-finished product after the swelling again, put into reactor, logical nitrogen, sealing, under 20 ℃～90 ℃, polyreaction 3～36 hours.Or after feeding nitrogen protection, sealing was with ultraviolet or Co60 irradiation 0.5～8 hour.Take out reacted spheroid again, it is soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, the pore former dissolving is removed, promptly get artificial eye holder of the present invention.
Therefore the manufacturing process of artificial eye holder of the present invention can be stated as:
1. get the pore former of particle diameter in 300 microns～500 micrometer ranges with the standard screen sieve.
2. with the biocompatible polymer dissolution with solvents, make saturated solution, mix with sieve pore former well then, the ratio of saturated solution and pore former is: saturated solution: pore former=1: 2～3.5 (weight ratio) is poured into and is pressed into ball in the stainless steel mould.
3. mould is left standstill at 20 ℃ and treated the solvent evaporates rear demoulding in 24 hours, obtain spherical semi-finished product, spherical semi-finished product are carried out the outward appearance finishing, make its neat appearance, put into the vacuum drying oven evacuation again and removed residual solvent in dry 2 hours.
4. initiator, cross-linking agent, polymer monomer are mixed mutually, be mixed with swelling solution.
5. the spherical semi-finished product that will make are put into a dry beaker, pour the solution of preparation into, flood spherical semi-finished product, logical nitrogen, sealing, swelling 3～100 hours.
6. the spherical semi-finished product after the taking-up swelling are put into reactor, logical nitrogen, and sealing, under 20 ℃～90 ℃, polyreaction 3～36 hours.Or after feeding nitrogen protection, sealing was with ultraviolet or Co60 irradiation 0.5～8 hour.
7. take out reacted spheroid, it is soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, promptly get required artificial eye holder.
Use method of the present invention, the preparation artificial eye holder has following characteristics and advantage:
1. adopt macromolecule interpenetrating networks thinking to carry out modification, make the compressive strength of porous part that very big raising arranged, but do not influence the biocompatibility of artificial eye holder.
2. the porosity of artificial eye holder can reach more than 80%, and the aperture is adjustable.
3. density of material is little, and soft durometer can be regulated by proportioning, can not produce excessive pressure to the optical fundus.
Description of drawings
Fig. 1 is the profile of spherical semi-finished product mould
Fig. 2 is the profile photo of artificial eye holder.
The specific embodiment
Embodiment 1
1. get the NaCl of particle diameter in 450 microns～520 micrometer ranges by the standard screen sieve.
2. EU saturated solution (solvent is an oxolane) is mixed solution with NaCl: the mass ratio of NaCl is 1: 2, is poured in the mould, and is tightly compacted, obtains spherical semi-finished product through nature volatilization and vacuum drying.
3. get 10 milliliters of methacrylic acids-2-ethoxy ethyl ester (EEMA), 0.1 gram DIETHYLENE GLYCOL, 40 milligrams of AIBN obtain solution in beaker.
4. the spherical semi-finished product after the finishing are placed beaker, add the solution for preparing in 3, to flooding spherical semi-finished product, feed nitrogen protection, sealing, swelling 3 hours.
5. take out spherical semi-finished product, put into beaker, feed nitrogen protection, sealing, under 70 ℃, polymerisation in bulk 24 hours.
6. take out reacted spheroid, be put in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 2
1. get the white sugar of particle diameter in 450 microns～520 micrometer ranges by the standard screen sieve
2. PAUR saturated solution (solvent is an oxolane) and white sugar are mixed solution: the White Sugar Quality ratio is 1: 2.5, is poured in the mould, and is tightly compacted, obtains spherical semi-finished product through nature volatilization and vacuum drying.
3. get 10 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 0.1 gram N,N methylene bis acrylamide, 40 milligrams of ABVN obtain solution in beaker.
4. the spherical semi-finished product after the finishing are placed beaker, add the solution for preparing in 3, to flooding spherical semi-finished product, feed nitrogen protection, sealing, swelling 10 hours.
5. take out spherical semi-finished product, put into beaker, feed nitrogen protection, ultraviolet irradiation 5 hours are used in sealing.
6. take out reacted spheroid, be put in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 3
1. get the NH of particle diameter in 300 microns～400 micrometer ranges by the standard screen sieve
4HCO
3
2. with PHB saturated solution (solvent is a chloroform) and NH
4HCO
3Mix solution: NH
4HCO
3Mass ratio is 1: 3, is poured in the mould, and is tightly compacted, obtains spherical semi-finished product through nature volatilization and vacuum drying.
3. get 7 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 3 milliliters of methacrylic acids (MA), 0.1 gram N,N methylene bis acrylamide, 50 milligrams of Ammonium persulfate .s obtain solution in beaker.
4. the spherical semi-finished product after the finishing are placed beaker, add the solution for preparing in 3, to flooding spherical semi-finished product, feed nitrogen protection, sealing, swelling 36 hours.
5. take out spherical semi-finished product, put into beaker, feed nitrogen protection, sealing, under 60 ℃, polymerisation in bulk 36 hours.
6. take out reacted spheroid, be put in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 4
1. get the KCl of particle diameter in 300 microns～400 micrometer ranges by the standard screen sieve.
2. PHBV saturated solution (solvent is a chloroform) is mixed solution with KCl: the KCl mass ratio is 1: 2, is poured in the mould, and is tightly compacted, obtains spherical semi-finished product through nature volatilization and vacuum drying.
3. get 7 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 3 milliliters of methyl methacrylates (MMA), 0.1 gram DIETHYLENE GLYCOL, 40 milligrams of dibenzoyl peroxides (BPO) obtain solution in beaker.
4. the spherical semi-finished product after the finishing are placed beaker, add the solution for preparing in 3, to flooding spherical semi-finished product, feed nitrogen protection, sealing, swelling 24 hours.
5. take out spherical semi-finished product, put into beaker, feed nitrogen protection, Co60 irradiation (45GY/min) 5 hours are used in sealing.
6. take out reacted spheroid, be put in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Claims (1)
1. a swollen-state polymerization particle leaches the method that legal system is equipped with artificial eye holder, it is characterized in that being made up of the following step:
1) gets the pore former of particle diameter in 300 microns～600 micrometer ranges with the standard screen sieve; Wherein pore former is NaCl, KCl, Na
2CO
3, NH
4HCO
3, NaHCO
3Any;
2) with the biocompatible polymer dissolution with solvents, make saturated solution, mix with sieve pore former well then, be poured into and be pressed into ball in the stainless steel mould; Wherein biocompatible polymer is a PAUR, EU, poly butyric ester, butyric ester-valerate copolymer, any in butyric ester-alkyl caproate copolymer; Solvent is any in oxolane, the chloroform; Saturated solution wherein: pore former=1: 2～3.5;
3) mould is left standstill at 20 ℃ treated the solvent evaporates rear demoulding in 24 hours, obtain spherical semi-finished product, spherical semi-finished product are carried out the outward appearance finishing, make its neat appearance, put into the vacuum drying oven evacuation again and removed residual solvent in dry 2 hours;
4) initiator, cross-linking agent, polymer monomer are mixed mutually, be mixed with swelling solution; Wherein cross-linking agent is a N,N methylene bis acrylamide, DIETHYLENE GLYCOL, any in the vinyl ethylene glycol dimethacrylate; Wherein initiator is an azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, any in potassium peroxydisulfate, the Ammonium persulfate.; Polymer monomer is 2-hydroxyethyl methacry-late, methyl methacrylate, methacrylic acid-2-ethoxy ethyl ester, any in the methacrylic acid; The ratio of initiator, cross-linking agent, polymer monomer is: polymer monomer 98.5%～98.7%, initiator 0.9%～1.0%, cross-linking agent 0.4%～0.5%;
5) the spherical semi-finished product that will make are put into a dry beaker, pour the solution of preparation into, flood spherical semi-finished product, logical nitrogen, sealing, swelling 3～100 hours;
6) take out spherical semi-finished product after the swelling, put into reactor, logical nitrogen, sealing, under 20 ℃～90 ℃, polyreaction 3～36 hours, or after feeding nitrogen protection, sealing was with ultraviolet or Co60 irradiation 0.5～8 hour;
7) take out reacted spheroid, it is soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, promptly get required artificial eye holder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021241341A CN1172723C (en) | 2002-07-12 | 2002-07-12 | Swelled polymer particles filter process for preparing artificial eye holder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021241341A CN1172723C (en) | 2002-07-12 | 2002-07-12 | Swelled polymer particles filter process for preparing artificial eye holder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1390608A CN1390608A (en) | 2003-01-15 |
| CN1172723C true CN1172723C (en) | 2004-10-27 |
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ID=4745344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021241341A Expired - Fee Related CN1172723C (en) | 2002-07-12 | 2002-07-12 | Swelled polymer particles filter process for preparing artificial eye holder |
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049063A (en) * | 2010-12-14 | 2011-05-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Material for preparing expandable artificial eye table and application thereof |
| CN112107734B (en) * | 2020-09-17 | 2021-09-24 | 浙江大学 | Soft porous silica gel artificial eye holder and preparation method thereof |
-
2002
- 2002-07-12 CN CNB021241341A patent/CN1172723C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1390608A (en) | 2003-01-15 |
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Granted publication date: 20041027 |