• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1. Process for the preparation of a three-dimensional structure, characterized in that it consists in forming an acid aqueous solution of a natural, non-crystalline protein polymer of animal or plant origin, or of a mixture of such polymers, these polymers having low molecular weights of not more than 100 000, in heating the solution to a temperature between 55 and 65 degrees C, in adjusting the pH of the solution to between 3.5 and 5.5, in adding a crosslinking agent to the solution and incorporating it therein, in a ratio of 0.5 % to 15 % by weight, the temperature of the solution being kept at between 55 and 65 degrees C, in drying the solution until its moisture content does not exceed 10 % at a maximum temperature of 35 degrees C or an equivalent temperature in vacuo, so as to form a crosslinked polymeric structure, in subjecting this structure to thorough washing with water, in subjecting the structure washed in this way to dehydration by immersion in a water-miscible organic solvent, in subjecting the structure to thorough washing with water, and in drying the structure again at a maximum temperature of 35 degrees C, until its moisture content does not exceed 10 %.
    公开号:SU1011052A3
    申请号:SU792830601
    申请日:1979-10-17
    公开日:1983-04-07
    发明作者:А.Батиста Орландо
    申请人:Эссилор Энтернасьональ Компани Женераль Д@ Оптик (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to high molecular weight compounds of natural origin, namely, the preparation of a hydrogel from animal protein polymers intended for the manufacture of various products used in contact with aqueous liquids.
    A known method for producing a hydrogel involves dissolving a protein of animal origin (gelatin in water when heated and is treated with formaldehyde fl.
    In this method, designed to obtain optically sensitive materials, gelatin is dissolved in water at B5-8 (HS, the resulting gel is used to form articles that are treated with a solution of formaldehyde at.
    The purpose of the invention is to obtain a medical purpose hydrogel with improved physicochemical properties.
    This goal is achieved in that the method of producing a hydrogel, which includes dissolving animal protein in water when heated and treated with formaldehyde, uses gelatin or a mixture of gelatin and gi; molecular weight 50,000-100,000, with an aqueous solution of protein with a concentration of 5-10 w / d acidified to pH t-6.5 with hydrochloric or phosphoric acid at 55-6 ° C, formaldehyde is added in an amount of 1, 3 by weight of protein and mixed at 20-35 ° C to residual moisture, not exceeding 10%, followed by prom Washing with water, treating with ethyl alcohol, re-washing with water and drying under the same conditions.
    In this case, in some cases, before acidification and / or after the first drying, the gel is treated with a dilute solution of hydrogen peroxide.
    From the resulting hydrogel, various medical products can be obtained, for example, optical contact lenses, shells used for burns and wounds, bone prostheses, fibers, and other products that are currently based on synthetic polymers.
    The known gelatin and agar-agar hydrogels are not suitable for obtaining contact lenses, since they have poor physical properties in the wet state.
    Depending on the desired form of the final product, the pH value, temperature, concentration of solids and the dehydration sequence of ethanol will vary. An important parameter is also drying at a temperature not exceeding 35 ° C to a moisture content in the dried form of no more than 10 and preferably 1% or less. If these conditions are not fulfilled, but the product is heated to 40 ° C or more before final drying in air to a moisture content not exceeding 10 and without dehydration with ethyl alcohol, then the final product will be unstable in water. Instead of being extremely flexible and resilient and have good physical stability, in particular, high tensile strength in the wet state, products that are dried X1 in some way to the content
    5 humidity not exceeding 10 and preferably below 1%, not subjected to processing by dehydration with ethyl alcohol, have a friable structure and have an extremely fragile and fragile
    0 physical form when they are saturated with water. The lack of physical stability in the wet state does. these products are completely unsuitable for, for example, flexible contact lenses, ophthalmic shells, artificial cornea, vitreous body, new protein fibers used in the textile industry and in surgery, for making prostheses such as cartilage or artificial bones, membranes, materials for seams, shells used for burns and wounds, etc .. One of the significant advantages of the invention is that it allows you to prepare a wide range of cheap products that have a set of useful voystv pervichyyh of materials originating from natural proteins with a relatively low molecular weight.
    Products are prepared from a solution of natural protein containing 5–10 wt.% Protein or protein mixture. The solution is heated to 55 ° C in order to allow the protein to dissolve the cnoco6ctBOBaTb and obtain a clear solution. After dissolution of the protein, the pH of the solution is adjusted to a value of 5 in order to form an acidic aqueous solution of the protein. The acidic solution is maintained in this temperature range and a structuring agent is added to the solution, which is introduced with vigorous stirring. Commercial formalin, which contains 37% formaldehyde, is used as a structuring agent. The solution is poured or molded into a three-dimensional volumetric form, then dried in air at a temperature not exceeding 35 to reach a moisture content not exceeding 10, preferably less than 7%. When they want to obtain a water-clear product, the dried structure is whitened with an oxidizing agent, hydrogen peroxide. The clarified or unenlightened structure is thoroughly washed with water, then it is subjected to dehydration by immersion in an organic solvent, miscible with water, denatured or not denatured ethyl alcohol. After treatment with ethyl alcohol, the structure is thoroughly washed with water and dried in air at a temperature not exceeding to reduce the moisture content to a value not exceeding 10% and preferably less than 7%. Since the starting material is proteinaceous, the products prepared according to the invention is a year for monochrome or multicolor painting with a pattern according to the usual technique used for polymeric materials containing the groups NH, NH and COOH. Therefore, it is possible, by adding an appropriate dye or pigment, to give these products any color dictated by aesthetic or other considerations. PRI me R. 1. Heat 400 ml of a transparent gel containing 400 ml of 10% gelatin (having a molecular weight of about 50,000 and an opalescence of 225) heated to 60 ° C. To this transparent mixture, which is slowly and continuously / unmixed, k drops of 10W hydrochloric acid are added to obtain a pH of 4.3. Immediately thereafter, add 8 ml of formalin, or about 7.5% formaldehyde, to the gelatin, vigorously mixing the mixture and maintaining it at 60i5 ° C. To obtain a product that is stable with water, immediately after adding the structuring agent. casting or shaping and then drying in a calm state in air during polymer casting or drying in a mold by centrifugal molding. The ejected flexible contact pins are inserted with a burette or a calibrated pipette. Drops of the above mixture are introduced into a standard polymethacrylate form with a diameter of 11 mm at normal temperature. The thickness of the contact lens 5, as well as its refractive properties, is determined by the concavity of these forms and the number of drops that are inserted there at a given concentration. The hydrogel is slowly dried at ordinary temperature (about 25 ° C for at least 2 hours, during which the structuring reaction is carried out almost to its completion. At the end of this drying cycle, the lens, while still in shape, is further dried in a drying oven. air-circulating ovens for a minimum of 4 hours at a maximum temperature of 30-35 ° C or at an equivalent temperature in vacuum in order to be sure that the moisture content in the product will not exceed 10% and preferably below 7%. These are easily removed from the molds and immediately immersed in a dilute aqueous solution of hydrogen peroxide, typically used for household purposes at 3 vol% per hour, at least at ordinary temperatures (25 ° D). This step is especially effective for removing yellow-brown - brown color characteristic of natural proteins with low molecular weight, whether structured or not ... I Then the lenses are subjected to vigorous and thorough washing with water, preferably distilled water, in order to ensure complete removal of Olsha residual amounts of crosslinking agent and hydrogen peroxide. After this washing, the lenses saturated with water are introduced into denatured or non-denatured commercial ethyl alcohol (95% by volume) where they are left for at least 2 hours.
    510
    At the end of dehydration by soaking in ethyl alcohol, the lenses are again thoroughly washed with distilled water in order to wash out any residual ethyl alcohol and denaturation components when denatured ethyl alcohol is used. Re-rinsing, preferably in distilled water, is important at this stage.
    Transparent lenses are then slowly dried in air, which have been thoroughly washed according to the procedure described above, which consists in drying in air for 2k hours at normal temperature (25 ° C), then for at least 2k hours in an air circulation oven at maximum a temperature of 30-35 ° C so that the residual moisture content does not exceed 10 and preferably is below 7%. It is possible to dry the lenses obtained after the last wash with water in a mold where they were previously cast, although this method is not necessary. but also be sterilized by dry drying at a temperature up to 120 C.
    In this way, the manufacturing sequence is completed (then it is possible to check, if necessary, faceting, packaging and sterilization, etc.) to obtain flexible contact lenses, transparent as water, having physical properties and the same remarkable permeability with respect to gas in a wet state as in a dry con. standing nii Among these advantages, it is possible to note almost immediate hydration in water (-3 minutes compared with 1-2 hours or more in the case of contact flexible lenses made of synthetic polymers) as well as a high value of permeability with respect to gaseous oxygen.
    Example 2: AGO is heated to a ml of clear gel consisting of 300 ml of 0% gelatin and 100 ml of edible, partially hydrolyzed bovine collagen (molecular weight about 100,000) with a concentration of 1%. To this mixture, when it is slowly and continuously stirred, k drops Yun are added. hydrochloric acid to obtain a pH of 65. Immediately thereafter, 8 ml of formalin or about 0.52 "is added with vigorous stirring.
    lo formaldehyde in relation to the protein, maintaining a temperature of 6.0 ± 5 C.
    An initial casting of the 5. hydrogel, pretreated in accordance with the foregoing, is carried out to obtain a water-stable product immediately after the addition of the crosslinking agent.
    O Conventional flexible contact lenses
    Using a burette for a calibrated pipette with precautions, insert k drops of the above mixture into a polymethacrylate standard form.
    5 with a diameter of 11 mm, at an ordinary temperature. The thickness of the contact lens, as well as its refractive properties, are determined by the concavity of the shape and the number of drops,.: Administered at a given concentration.
    Air drying, bleaching, washing, dehydrating, washing, and final air drying are carried out as in Example 1.
    5 Get water-clear contact lines that form flexible contact lenses that can be worn continuously. Making these lines in a series is quite economical, so that they can be used as ejected lenses after they are covered with sediment, etc. These contact lenses allow reuse of the expensive cleaning solution and suppress the risk of infection associated with the extra manipulation they undergo every day when they are removed for cleaning.
    PRI me R 3. Heated to 60 ° C
    400 ml of a clear gel consisting of kOO ml of 10 gelatin solution (having a molecular weight of about 50,000 and opalescence 225). To this transparent mixture at a slow constant
    5 drops of K hydrochloric 10 N are added with stirring. acid in order to set the pH to 4.76. Immediately thereafter, 80 drops are added with vigorous stirring - t ml
    formalin or about 3.7 formaldehyde-in relation to gelatin, maintaining the temperature.
    Flexible contact lenses, forming a cie of the removed cornea With the help of a burette or a calibrated pipette with precautions, k drops of the above mixture are introduced into special glass dia- dia forms;
    710
    mm in normal temperature. The thickness of contact lenses, as well as their refractive properties, depend on the concavity of the shape and the number of droplets injected at a given concentration.
    Perfume drying, clarification, washing, dehydration, washing and final air drying are carried out as in Example 1.
    This completes the manufacturing sequence (then checks, if necessary, edge cutting, packaging, sterilization, etc.) of flexible water-clear lenses that have wet properties that make them ideal for
    Comparative data for protein lenses obtained by the proposed method and conventional lenses based on synthetic polymers
    2 .8
    as a removed ophthalmic cornea. For example, lenses prepared in this way have low abrasiveness when
    they are placed on the eye along with the medication, the movement of the eyelids over the shell gradually erodes the shell so that it is washed off with tears for 10-16 hours. In addition, these lenses are made of hydrogel or of captivity.
    When they are saturated with a drug for treating glaucoma such as pilocarpine or a composition based on thymol, very viscous drops can be substituted for the eye.
    block.
    Physico-chemical properties of the obtained lenses are shown in the table.
    Refractive index (water)
    Contact angle (hydrated)
    Permeability (visible area 100-600, hydrated),%
    Tension, g / mm
    Module,
    Stretching

    Tensile strength, g / mm
    initial
    common
    Glass transition temperature (dehydrated in the left installation), €
    Hydrate water,%
    Thickness 0.25 mm
    , 50-60
    96-98
    30-50
    2ijO-280
    6-6.6, 8-5,2
    105-112 45-50
    Yes,
    SS (STP): cm
    with .- cm mm
    6) Speed of apparent transfer,
    ss (8tr)
    from h cm T (air
    Thickness 0.12 mm. Permeability of oxygen (subjected to further transformation)
    Thickness 0.075 mm. Permeability of oxygen (subjected to further conversion. Example: 00 ml of a transparent gel consisting of a 10% gelatin solution (having a molecular weight of about 50,000 and about 275) and 200 ml of partially hydrolyzed bovine collagen having molecular weight of about YuOOOO). With slow and constant stirring, k drops of salt 4 o 10 n are added to this mixture. acid, you for pH 5, Yu. Immediately thereafter, 8 ml {160 capel) formalin or about 12.3% of the aldehyde forms with respect to the protein are added to the mixture with vigorous stirring, maintaining the temperature at 60 ± 5 ° C. Primary casting of a natural hydrogel pretreated to obtain a product that is stable with respect to water must be carried out immediately after the addition of the structuring agent, i.e. before the crosslinking reaction makes the gel irreversibly hard and not possible for casting. Ophthalmic membranes and corneas of long-acting With the help of a burette or a calibrated pipette, with precautions, 3 drops of the above mixture are introduced.
    25-30
    5-6
    -7
    4,0-t, 2 "10
    12-20
    -:
    i 0-50
    8.0-8.5 10
    one
    60-65
    10-12-10 in standard forms of polymethacrylate with a diameter of 11 mm at ordinary temperature. The thickness of the contact lens as well as its refractive properties are determined by the concavity of the forms and the number of drops that are inserted there at a given concentration. Air drying, bleaching, washing, dehydrating, washing, and final air drying are carried out as in Example 1. Example 5. 00 C is heated to 60 ml of a clear gel consisting of jOO ml of a 10% gelatin solution (having a molecular weight of about 50,000 and opalescence 225). With this stirring, k drops of 10 n are added to this light mixture. hydrochloric acid to obtain a pH of 35- Immediately thereafter, with vigorous stirring, kQ drops (2 ml) of formalin or about 1.85% formaldehyde relative to gelatin are added, maintaining a temperature of 60 ± 5 ° C. Hydrogels with selectable viscosity Leave oh-t this product at normal temperature (), for at least 15. minutes, subjecting it to agitation to achieve maximum uniformity during the structuring process. The hydrogel is then dried, preferably instant dried by spraying, in order to transpose it into fine particles. Or you can pour the hydrogel on a flat surface and slowly air dry. Whatever the method of drying used, it is necessary to reduce the moisture content in the drying stages using a maximum temperature of 30–3 ° C at atmospheric pressure to a value not exceeding 10 and preferably below 1%. Then, the dried hydrogel particles from natural protein polymer are immersed in a usual diluted aqueous solution of hydrogen peroxide (3 rd for at least 1 c at a normal temperature of 25 ° C). This step is particularly effective for removing the natural yellow-brown or light brown color of natural proteins with relatively low molecular weight, whether they are structured or not. The swollen hydrogel particles are then subjected to vigorous thorough washing with water, preferably distilled water, in order to remove any small residues of crosslinking and hydrogen peroxide. After thorough washing above, water-saturated hydrogel particles are introduced into denatured or non-denatured commercial ethanol of 95% by volume, where it is left for at least 2 hours. At the end of dehydration, by washing in ethyl alcohol, the hydrogel particles are thoroughly washed with distillation distillate a bath to remove traces of ethyl alcohol and denaturation components, in case of using denatured alcohol. At this stage it is important to thoroughly rinse, preferably with repeated rinsing, in distilled water. At the same time, the mass of a transparent, highly swollen hydrogel is slowly dried in air, which has been thoroughly washed according to the drying steps described above, which consist either in their drying by pulverization or in air to an octa4: 4 moisture content not exceeding 10% and preferably below 7 The product obtained is particularly useful when it is swollen in an ophthalmic aqueous solution (for example, in pilocarpine hydrochloride solutions for treating glaucoma) in order to select viscosity and outflow properties. The significantly saturated internal structure of the hydrogel particles allows the action of the components of the drug to which it is connected to continue. Example 6: A 800 ml clear gel is heated up to 600 ml of a solution of 10 gelatins and 200 ml of food grade partially hydrolyzed bovine collagen (having a molecular weight of about 100,000) at 1%. Under slow and constant stirring, 10 drops of 10 N are added to this mixture. hydrochloric acid to obtain pH t, 8. Immediately thereafter, 18 ml of formalin or about 10.7% formaldehyde in relation to the protein is added to the mixture with vigorous stirring, maintaining the temperature of eotB C. The film and skin for burns and wounds Immediately after thoroughly mixing the above composition, it is degassed in a desiccator with a vacuum of 710-736 mm Hg. Art. in order to remove the bubbles. Then the mixture is washed in a flat dish made of pyrex, the dimensions of which correspond to the desired size of the films. For example, a petri dish may be used to prepare a round film or shell, while rectangular glassware may be used to prepare a rectangular film. The hydrogel is allowed to slowly desiccate at ambient temperature of about 20 ° C for at least 2 hours, during which the structuring reaction is almost complete. According to the thickness of the film to be produced, it is possible to continue the slow, friable drying in air for a week or more until the total moisture content does not exceed 10% and preferably less than 7%. In order to shorten the drying time, it is possible, after hours, to place the mold containing the preform in an air-circulating oven. If they wish to obtain a Pleckoo, a clad fabric or incorporated into a fabric with such a hydrogel, they knit the fabric evenly into the mold before pouring the liquid hydrogel there. The cast film is then subjected to sequential processing consisting of oxidation with an oxidizing agent CH2P2., Then dehydration with ethyl alcohol, etc., as described in the preparation of contact lenses in Example 1. Tubes, arteries and other structures. Example 7. Dehydrated hydrogel having the composition , described in example 6, is poured into a concentric fopma to form a tube (or arteries, containing or not containing a tissue matrix. The structuring reaction is performed at a normal temperature of 25 ° C and at a relative humidity of 58% for Allow 2 hours before the moisture content exceeds 10%. The solid hydrogel is removed from the concentric form to obtain a tube suitable for use as an arterial prosthesis. The tubes are then clarified, washed, dehydrated, washed and finally dried. as described in example 1. Bone prostheses Example 8. The starting material used for the manufacture of mesh and cortical prostheses from stabilized natural protein hydrogels has a composition very similar to that described in example 6. Od One of the main differences is the use of phosphoric acid instead of hydrochloric acid in order to adjust the acidity of the hydrogel before adding the structuring agent. Particles or crystals of calcium phosphate, associated or unassociated with other ions, usually present in the bone and cartilage, are thoroughly mixed with a solution of natural non-crystalline, water-soluble proteins. The resulting product is a very fine and homogeneous mixture of various constituents, and various io can be added there to increase the potency of the semi-ion before adding the agent of protein constructing protein, as described in previous examples. Calcium phosphate can be formed by mixing a soluble calcium salt such as acetate, and soluble phosphate such as sodium phosphate. In the event that other salts and / or other ions, such as fluorine or carbonate ions, are added, a saline solution can be added, while calcium phosphate is formed, dissolved Salts such as calcium fluoride or sodium carbonate. The exact formula of a calcium phosphate compound is complex and in the present description the term calcium phosphate encompasses dicalcium phosphate, tricalcium phosphate, octacalcium phosphate, hydroxyapatite, carbonate apatite, chlorapatite, fluoroapatite, and mixtures thereof. A modification of Example 6, which appears to be desirable for the preparation of highly porous, reticulated network products, is the replacement of water used as a solvent for proteins diluted with an aqueous solution of hydrogen peroxide, for example 1% by volume after dissolving the protein in a dilute aqueous solution of hydrogen peroxide to a protein the solution is injected with a 25% aqueous calcium phosphate suspension in quantities sufficient to produce approximately equal amounts of protein and calcium phosphate. The pH is then adjusted with phosphoric acid and the crosslinking agent is added, then the mixture is vigorously stirred, maintaining it at 6-5 ° C. The use of a hydrogen peroxide solution as a solvent causes the formation of small uniformly dispersed bubbles during the pH adjustment and the addition of a structuring agent, which causes a uniformly porous structure during the structuring and drying, in some cases it may be preferable to carry out the vacuum drying of the hydrogel calcium phosphate, instead of air drying as described in previous examples. In all subsequent cases of initial drying, the moisture content does not exceed 10%, preferably 7% or less, at least when drying, following sublimation, hydrogen peroxide (3 wt.%) And dehydration with ethyl alcohol, as described in the examples 1,2 and 3, it remains desirable to obtain a bone structure with sufficient mechanical strength properties in the wet state. For example, when these structures are placed in water, they swell, but remain bound and do not disintegrate, 1510 These products form new compositions, allowing tues Obtain structures such as cartilage, bone, or ivory .. Fibers, textiles, and sutures ExampleCh. Sosta water soluble protein hydrogel; as described in example 6, is the starting material for the production of new fibers that can be converted to produce various textiles such as fabrics, sheets, etc. Before adding a streaming agent, the gel is injected into a chamber associated with a mechanism capable of extruding a hydrogel through filters to produce ultrafine fibers or even monofilaments, which equipment is often used to obtain viscose fibers. 2 .16 The temperature of the fibers is maintained at the level before they are introduced into the mixing pump, where a certain amount of structuring agent is added to them. The filaments are continuously extruded into a long cylindrical vertical drying chamber, where they are dried to a moisture content not exceeding 0% and preferably 7% or less, and then they are collected in reels or skeins. After the initial drying stage described above, the yarns are subjected to oxidation (H () j, dehydration with ethyl alcohol, final washing and final drying, according to the steps given in the preceding examples. These fibers are convenient for various medical and clothing applications. When they are extruded as small diameter threads, they can be used as surgical suture filaments.
    权利要求:
    Claims (2)
    [1]
    1. A METHOD FOR PRODUCING A HYDROGEL, including dissolving an animal protein in water by heating and processing with formaldehyde, characterized in that, in order to obtain a medical hydrogel with improved physicochemical properties, gelatin or a mixture of gelatin with hydrolyzed bovine collagen is used as protein molecular weight of 50,000-100,000, while an aqueous solution of a protein of concentration 5 _ 10% by weight is acidified to pH 4-6.5 with hydrochloric or phosphoric acid At 55–65 ° C, formaldehyde is added in an amount of 1.5 ~ 12.5% of weights and dried at 2035 ° C to a residual moisture content not exceeding 10%, followed by washing with water and dried under the same conditions.
    [2]
    2. The method according to π. 1, ci I, in that before the acidification and / or after the first drying, the gel is treated with a dilute aqueous solution of hydrogen peroxide.
    ZS0UUT ,,, _ n§
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    同族专利:
    公开号 | 公开日
    CA1139511A|1983-01-18|
    EP0011523B1|1982-07-14|
    AU532385B2|1983-09-29|
    AU5187079A|1980-04-24|
    JPS5556132A|1980-04-24|
    EP0011523A1|1980-05-28|
    DE2963348D1|1982-09-02|
    JPS5827813B2|1983-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR475504A|
    DE610933C|1930-08-20|1935-03-19|Emilie Engel|Process for the production of molded articles|
    DE1617804A1|1966-12-13|1972-01-05|Soehnges Optik Wilhelm P Sohng|Visual aid|
    JPS555089B2|1976-12-22|1980-02-04|US4268131A|1979-04-11|1981-05-19|Opticol Corporation|Fiber collagen contact lens|
    US4532267A|1984-02-15|1985-07-30|Board Of Regents, University Of Washington|Vision correction lens made from an aminopolysaccharide compound or an ether or ester thereof|
    FR2570606A1|1984-09-26|1986-03-28|Landanger Laboratoire|Obturator in particular for the cavity of the femur or the bottom of the acetabulum |
    JPH0235136Y2|1984-11-27|1990-09-21|
    FR2617763B1|1987-07-07|1989-12-01|Essilor Int|METHOD OF MANUFACTURING CONTACT LENS IN A NATURAL PROTEIN POLYMER, BY MOLDING BEFORE CROSS-LINKING|
    CA2872905C|2011-05-13|2020-09-01|Governors Of The University Of Alberta|Polymers and plastics derived from animal proteins|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US95230378A| true| 1978-10-18|1978-10-18|
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