CN107881591A - The preparation method of medical material - Google Patents

The preparation method of medical material Download PDF

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Publication number
CN107881591A
CN107881591A CN201711163725.2A CN201711163725A CN107881591A CN 107881591 A CN107881591 A CN 107881591A CN 201711163725 A CN201711163725 A CN 201711163725A CN 107881591 A CN107881591 A CN 107881591A
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minutes
mass ratio
medical material
obtains
fibre
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彭代信
宋晓静
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SUZHOU YIKETAI ELECTRONIC MATERIAL CO Ltd
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SUZHOU YIKETAI ELECTRONIC MATERIAL CO Ltd
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Publication of CN107881591A publication Critical patent/CN107881591A/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C09J105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • D01F4/02—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08—Animal fibres, e.g. hair, wool, silk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of preparation method of medical material, using surface of the fibroin fiber as medical material, it has excellent biocompatibility, available for treatment of wounds, tissue wrapping, simultaneously backing material is used as by the use of synthetic fibers, the defects of overcoming fibroin fiber mechanical strength difference, fibroin fiber is combined with support fiber by adhesive, as stable entirety, also there is iris action after adhesive film forming simultaneously, on the one hand prevent fibroin fiber to be contaminated, prevent tissue fluid, blood etc. from permeating in addition.The medical material VOC of the present invention is less than 0.5g/L；Adhesive force is 1 grade；24 hours sterilizing rate (Escherichia coli) be more than 99%；It is wear-resisting up to more than 10,000 times；Fracture strength is more than 60MPa.

Description

The preparation method of medical material
It is 201610495789.1 the invention belongs to number of patent application, patent application day is on June 21st, 2016, proprietary term The referred to as divisional application of medical material, belong to the preparation method portion of techniques scheme of product.
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of preparation method of medical material.
Background technology
The preparation of macromolecular fibre generally comprises material modification and obtains modifier, then carries out spinning；Or modifier again with Spinning is carried out again after the mixing of other additives.Existing medical material is generally cotton fiber, because its biocompatibility is preferable；But It is that cotton fiber is all short fibre, mechanical property is poor, and wearability is low.Olefin(e) fibre yield is larger, and cost is very low, but due to Its strong inert, poor biocompatibility, and it is not used as medical material.Therefore need to be modified it, using new technology, in alkene On the basis of prepare good biocompatibility, wearability are strong, cost is low composite fiber product as medical material.
The content of the invention
It is an object of the invention to provide a kind of medical material, has excellent biocompatibility.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of medical material, is prepared by the following manner：
(1) polyethylene, polypropylene, methine succinic acid and epoxy prepolymer are well mixed, added through screw rod melting extrusion Work, olefin particles are prepared；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, uncle Butyl lithium, isomerous tridecanol polyoxyethylene ether are well mixed, and obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning； Polytetrafluoroethylparticle particle is mixed with five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, potassium carbonate Melt spinning method is used afterwards, and polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 matter Amount is than carrying out blending, and be supported fiber；
Bisphenol A cyanate ester monomer is added in reactor, 90~95 DEG C are reacted 10~12 minutes, and it is sweet to add three shrinks Oil base cyamelide ester monomer, 120~125 DEG C are warming up to, add NPE and australene, reaction 30~35 Minute prepares epoxy prepolymer；
(2) it is dissolved in after natural silk degumming in mixed liquor, infra-red drying obtains film after 1~1.5 hour；Then film is inserted into carbon In sour hydrogen sodium water solution, inserted again in clear water after 20~30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；Adjust fibroin egg The mass concentration of white solution is 35~40%；Then NPE, tetraethoxysilane and acrylic acid fourth are added Ester, stir 40~55 minutes；Then chitosan is added, stirring obtains spinning solution in 10 minutes, then obtains silk fibroin by Static Spinning Dimension；The mixed liquor is made up of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, stirring 15~25 Polyethylene glycol and modified Nano oyster shell whiting are added after minute, stirring adds trifluoromethanesulfonic acid lanthanum and imidazoles after 35~55 minutes, Stirred 1 hour in 80 DEG C, obtain adhesive；
The modified Nano oyster shell whiting is prepared by the following manner：Will raw oyster shell whiting be well mixed with titanium dioxide after 700 DEG C sinter 45~55 minutes, are then comminuted into the powder that average grain diameter is 40 nanometers；Powder is put into container, adds powder The ethanol of last 10 times of weight and the hydroxy-terminated polysiloxane of powder weight 0.6%, stir 35~45 minutes, then add powder The methyl p-hydroxybenzoate of weight 0.4%, stir 55~65 minutes, last drying to obtain modified Nano oyster shell whiting；
(4) by adhesive coated on support fiber surface, 70 DEG C are heated 5~8 minutes；Then it is compound with silk fiber, heat Pressure obtains composite fibre, and composite fibre progress sterilization treatment finally is obtained into medical material；The adhesive is positioned at support fiber Between silk fiber；The pressure of the hot pressing is 0.1MPa, and temperature is 85 DEG C, and the time is 18~22 minutes.
In above-mentioned technical proposal, in step (1), the reactive extrursion temperature of screw rod melting extrusion processing is 180~200 DEG C, Screw speed control is 110~115 revs/min, and residence time of the material in screw rod is 5~6 minutes；Melt spinning obtains alkene Temperature is 210~220 DEG C during fiber, and spinning speed is 800~900 ms/min；Melt spinning obtains temperature during polytetrafluoroethylene fibre Spend for 315~330 DEG C, spinning speed is 600~700 ms/min；Polyethylene, polypropylene, methine succinic acid and epoxy prepolymer Mass ratio be 1: 0.6: 0.32: 0.22；Olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, uncle Butyl lithium, the mass ratio of isomerous tridecanol polyoxyethylene ether are 1: 0.002: 0.2: 0.005: 0.15；Polytetrafluoroethylparticle particle with Five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, the mass ratio of potassium carbonate are 1: 0.08: 0.12: 0.18∶0.22∶0.11；Bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, Nonyl pheno The mass ratio of ether and australene is 1: 1.6: 0.3: 0.1.
In above-mentioned technical proposal, in step (2), the technological parameter of the Static Spinning is：15~25 kilovolts of voltage, receive away from From 8~12 centimetres, liquid inventory is 0.3~0.4mL/h；The mass concentration of sodium bicarbonate aqueous solution is 8%；Fibroin albumen, nonyl Base phenol polyethenoxy ether, tetraethoxysilane, butyl acrylate, the mass ratio of chitosan are 1: 0.4: 0.3: 0.1: 0.3；First Acid, water, the mass ratio of lithium bromide and TRIS buffer are 1: 5: 0.6: 2.
In above-mentioned technical proposal, in step (3), the mass ratio of raw oyster shell whiting and titanium dioxide is 5: 2；The poly- silica of terminal hydroxy group The molecular weight of alkane is 900~1100；Hyaluronic acid, the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, poly- second two Alcohol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles are 1: 5: 0.6: 0.01: 0.005: 0.1.The present invention's Hydroxy-terminated polysiloxane is linear structure, and hydroxyl is contained at both ends, has excellent adhesion property, at the surface to inorganic material Reason, the compatibility of inorganic matter and remaining organic principle can be strengthened；The present invention requires to the molecular weight of polysiloxanes, molecular weight The too low adhesion properties that can influence adhesive, the too high dispersing uniformity for then influenceing modified oyster shell whiting.The present invention is fine using fibroin The surface as medical material is tieed up, it has excellent biocompatibility, available for treatment of wounds, tissue wrapping, utilizes simultaneously Synthetic fibers are as backing material, the defects of overcoming fibroin fiber mechanical strength difference, by adhesive by fibroin fiber and branch Support fiber to combine, turn into stable entirety, while also there is iris action after adhesive film forming, on the one hand prevent fibroin fiber quilt Pollution, prevent tissue fluid, blood etc. from permeating in addition.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
(1) present invention is used using polyethylene, polypropylene as primary raw material, and by adding rational material, melt spinning obtains To olefin(e) fibre, solve the problems, such as that existing olefin(e) fibre processability is poor, mechanical strength is low, particularly modified alkene is fine Dimension has certain biocompatibility, and additive is harmless to human body or animal body, overcomes existing polyethylene or poly- Additive existing for propylene modified particle reveals intoxicating problem；Epoxy prepolymer is granulated, and improves the strand of olefin polymer Rigidity, its mechanical property and heat resistance are improved, can increase the compatible of alkene and epoxy prepolymer using methine succinic acid Property, put forward the stability of whole polymer；Recycle small molecule modifier, to olefin-modified, alkene can not reduced in melt-spun Its biocompatibility and resistance to ag(e)ing are improved on the basis of mechanical property.
(2) present invention greatly improves the wearability of medical material using polytetrafluoroethylene fibre, while in melt-spun mistake Micropore on the one hand is formed on polytetrafluoroethylene fibre surface using adding ingredient in journey, on the one hand adds its surface-active, is solved To determine existing polytetrafluoroethylene fibre strong inert, can not be compatible with other fibers the problem of, adhesive can penetrate into micropore, Improve fibroin fiber and support the adhesion of fiber, add the stability and stress balance of medical material.
(3) for medical material of the invention by reasonably designing, functional surfaces have excellent biocompatibility, aid in mask There are good mechanical property and wearability；And prepare conveniently, pass through melt-spun, electrostatic spinning equipment, you can easily prepare；It is beneficial to Industrial applications.
Embodiment
With reference to embodiment, the invention will be further described：
A kind of one medical material of embodiment, is prepared by the following manner：
(1) by mass ratio be 1: 0.6: 0.32: 0.22 polyethylene, polypropylene, methine succinic acid and epoxy prepolymer It is well mixed, obtain olefin particles through screw rod melting extrusion；Then by mass ratio be 1: 0.002: 0.2: 0.005: 0.15 alkene Hydrocarbon particle, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, tert-butyl lithium, isomerous tridecanol polyoxyethylene ether mix Close uniformly, obtain compositions of olefines, then olefin(e) fibre is obtained through melt spinning；It is 1: 0.08: 0.12: 0.18 by mass ratio: 0.22: 0.11 polytetrafluoroethylparticle particle, five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, carbon Melt spinning method is used after sour potassium mixing, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 mass ratio carries out blending, and be supported fiber；Bisphenol A cyanate ester monomer is added in reactor, 95 DEG C of reactions 10 Minute, triglycidyl group cyamelide ester monomer is added, is warming up to 125 DEG C, adds NPE and australene Alkene, reaction prepare epoxy prepolymer in 30 minutes；Bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, nonyl The mass ratio of base phenol polyethenoxy ether and australene is 1: 1.6: 0.3: 0.1；The reactive extrursion of above-mentioned screw rod melting extrusion processing Temperature is 180~200 DEG C, and screw speed control is 110 revs/min, and residence time of the material in screw rod is 6 minutes；Melting is spun It is 210~220 DEG C that silk, which obtains temperature during olefin(e) fibre, and spinning speed is 800 ms/min；Melt spinning obtains fibrillated polytetrafluoroethylene Temperature is 315~330 DEG C during dimension, and spinning speed is 700 ms/min；
(2) it is dissolved in after natural silk degumming in mixed liquor, infra-red drying obtains film after 1 hour；Then it is dense film to be inserted into quality Spend in the sodium bicarbonate aqueous solution for 8%, inserted again in clear water after 30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；Adjustment The mass concentration of silk fibroin protein solution is 35%；Then NPE, tetraethoxysilane and acrylic acid are added Butyl ester, stir 55 minutes；Then chitosan is added, stirring obtains spinning solution in 10 minutes, then obtains silk fiber by Static Spinning； The mixed liquor is made up of formic acid, water, lithium bromide and the TRIS buffer that mass ratio is 1: 5: 0.6: 2； Fibroin albumen, NPE, tetraethoxysilane, butyl acrylate, the mass ratio of chitosan are 1: 0.4: 0.3: 0.1∶0.3；The technological parameter of above-mentioned Static Spinning is：15 kilovolts of voltage, receive 12 centimetres of distance, liquid inventory 0.3mL/h；
(3) hyaluronic acid is added in the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, stirred 15 minutes Polyethylene glycol and modified Nano oyster shell whiting are added afterwards, and stirring adds trifluoromethanesulfonic acid lanthanum and imidazoles after~55 minutes, in 80 DEG C Stirring 1 hour, obtains adhesive；Hyaluronic acid, the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, poly- second two Alcohol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles are 1: 5: 0.6: 0.01: 0.005: 0.1；
Sinter 55 minutes at 700 DEG C after the life oyster shell whiting that mass ratio is 5: 2 is well mixed with titanium dioxide, then crush Into the powder that average grain diameter is 40 nanometers；Powder is put into container, adds the ethanol and powder weight of 10 times of powder weight 0.6% hydroxy-terminated polysiloxane, stir 35 minutes, then add the methyl p-hydroxybenzoate of powder weight 0.4%, stirring 65 minutes, last drying to obtain modified Nano oyster shell whiting；The molecular weight of hydroxy-terminated polysiloxane is 900~1100；
(4) by adhesive coated on support fiber surface, 70 DEG C are heated 8 minutes；Then compound with silk fiber, hot pressing obtains To composite fibre, sterilization treatment obtains medical material；The adhesive is between support fiber and silk fiber；The hot pressing Pressure 0.1MPa, 85 DEG C of temperature, 18 minutes time.
A kind of two medical material of embodiment, is prepared by the following manner：
(1) by mass ratio be 1: 0.6: 0.32: 0.22 polyethylene, polypropylene, methine succinic acid and epoxy prepolymer It is well mixed, processed through screw rod melting extrusion, olefin particles are prepared；Then it is 1: 0.002: 0.2: 0.005 by mass ratio: 0.15 olefin particles, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, tert-butyl lithium, isomerous tridecanol polyoxy Vinethene is well mixed, and obtains compositions of olefines, then obtain olefin(e) fibre through melt spinning；It is 1: 0.08: 0.12 by mass ratio: 0.18: 0.22: 0.11 polytetrafluoroethylparticle particle, five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acryloyl Melt spinning method is used after amine, potassium carbonate mixing, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, fibrillated polytetrafluoroethylene Dimension carries out blending according to 4: 1 mass ratio, and be supported fiber；Bisphenol A cyanate ester monomer is added in reactor, 90 DEG C Reaction 12 minutes, triglycidyl group cyamelide ester monomer is added, be warming up to 120 DEG C, add NPE With australene, reaction prepares epoxy prepolymer in 30 minutes；Bisphenol A cyanate ester monomer, triglycidyl group isocyanuric acid ester The mass ratio of monomer, NPE and australene is 1: 1.6: 0.3: 0.1；Above-mentioned screw rod melting extrusion is processed anti- It is 180~200 DEG C to answer extrusion temperature, and screw speed control is 115 revs/min, and residence time of the material in screw rod is 6 minutes； It is 210~220 DEG C that melt spinning, which obtains temperature during olefin(e) fibre, and spinning speed is 800 ms/min；Melt spinning obtains polytetrafluoro Temperature is 315~330 DEG C during vinyl fiber, and spinning speed is 600 ms/min；
(2) it is dissolved in after natural silk degumming in mixed liquor, infra-red drying obtains film after 1 hour；Then it is dense film to be inserted into quality Spend in the sodium bicarbonate aqueous solution for 8%, inserted again in clear water after 30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；Adjustment The mass concentration of silk fibroin protein solution is 40%；Then NPE, tetraethoxysilane and acrylic acid are added Butyl ester, stir 40 minutes；Then chitosan is added, stirring obtains spinning solution in 10 minutes, then obtains silk fiber by Static Spinning； The mixed liquor is made up of formic acid, water, lithium bromide and the TRIS buffer that mass ratio is 1: 5: 0.6: 2； Fibroin albumen, NPE, tetraethoxysilane, butyl acrylate, the mass ratio of chitosan are 1: 0.4: 0.3: 0.1∶0.3；The technological parameter of above-mentioned Static Spinning is：25 kilovolts of voltage, receive 8 centimetres of distance, liquid inventory 0.4mL/h；
(3) hyaluronic acid is added in the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, after 15 points of stirring Polyethylene glycol and modified Nano oyster shell whiting are added, stirring adds trifluoromethanesulfonic acid lanthanum and imidazoles after 55 minutes, 80 DEG C of stirrings 1 are small When obtain adhesive；Hyaluronic acid, the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, polyethylene glycol, modification are received Rice oyster shell whiting, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles are 1: 5: 0.6: 0.01: 0.005: 0.1；By the life that mass ratio is 5: 2 Oyster shell whiting sinters 55 minutes after being mixed with titanium dioxide at 700 DEG C, is then comminuted into the powder that average grain diameter is 40 nanometers；By powder End is put into container, adds the ethanol of 10 times of powder weight and the hydroxy-terminated polysiloxane of powder weight 0.6%, molecular weight are 900~1100,35 points are stirred, then adds the methyl p-hydroxybenzoate of powder weight 0.4%, is stirred 65 minutes, dry To modified Nano oyster shell whiting；
(4) by adhesive coated on support fiber surface, 70 DEG C are heated 8 minutes；Then compound with silk fiber, hot pressing obtains To composite fibre, sterilization treatment obtains medical material；The pressure of the hot pressing is 0.1MPa, and temperature is 85 DEG C, and the time is 18 points Clock.
Above-mentioned medical material VOC is less than 0.5g/L；Adhesive force is 1 grade；24 hours sterilizing rate (Escherichia coli) be 99% with On；It is wear-resisting up to more than 10,000 times；Fracture strength is more than 60MPa.

Claims (6)

1. a kind of preparation method of medical material, comprises the following steps：
(1) polyethylene, polypropylene, methine succinic acid and epoxy prepolymer are well mixed, processed through screw rod melting extrusion, system It is standby to obtain olefin particles；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, the tert-butyl group Lithium, isomerous tridecanol polyoxyethylene ether are well mixed, and obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning；Will be poly- Tetrafluoroethene particle is adopted after being mixed with five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, potassium carbonate With melt spinning method, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 mass ratio Blending is carried out, be supported fiber；
Bisphenol A cyanate ester monomer is added in reactor, 90~95 DEG C are reacted 10~12 minutes, add triglycidyl group Cyamelide ester monomer, 120~125 DEG C are warming up to, add NPE and australene, reacted 30~35 minutes Prepare epoxy prepolymer；
(2) it is dissolved in after natural silk degumming in mixed liquor, infra-red drying obtains film after 1~1.5 hour；Then film is inserted into bicarbonate In sodium water solution, inserted again in clear water after 20~30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；It is molten to adjust fibroin albumen The mass concentration of liquid is 35~40%；Then NPE, tetraethoxysilane and butyl acrylate are added, is stirred Mix 40~55 minutes；Then chitosan is added, stirring obtains spinning solution in 10 minutes, then obtains silk fiber by Static Spinning；Institute Mixed liquor is stated to be made up of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in the sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids half, stirred 15~25 minutes Polyethylene glycol and modified Nano oyster shell whiting are added afterwards, and stirring adds trifluoromethanesulfonic acid lanthanum and imidazoles after 35~55 minutes, in 80 DEG C stirring 1 hour, obtain adhesive；
The modified Nano oyster shell whiting is prepared by the following manner：700 after raw oyster shell whiting is well mixed with titanium dioxide DEG C sintering 45~55 minutes, it is 40 nanometers of powder to be then comminuted into average grain diameter；Powder is put into container, adds powder weight The ethanol of 10 times of amount and the hydroxy-terminated polysiloxane of powder weight 0.6%, stir 35~45 minutes, then add powder weight 0.4% methyl p-hydroxybenzoate, stir 55~65 minutes, last drying to obtain modified Nano oyster shell whiting；
(4) by adhesive coated on support fiber surface, 70 DEG C are heated 5~8 minutes；Then compound with silk fiber, hot pressing obtains To composite fibre, composite fibre progress sterilization treatment is finally obtained into medical material；The adhesive is positioned at support fiber and silkworm Between silk fiber；The pressure of the hot pressing is 0.1MPa, and temperature is 85 DEG C, and the time is 18~22 minutes.
2. the preparation method of medical material according to claim 1, it is characterised in that：In step (1), screw rod melting extrusion The reactive extrursion temperature of processing is 180~200 DEG C, and screw speed control is 110~115 revs/min, stop of the material in screw rod Time is 5~6 minutes；It is 210~220 DEG C that melt spinning, which obtains during olefin(e) fibre temperature, spinning speed is 800~900 meters/ Point；It is 315~330 DEG C that melt spinning, which obtains temperature during polytetrafluoroethylene fibre, and spinning speed is 600~700 ms/min.
3. the preparation method of medical material according to claim 1, it is characterised in that：In step (1), polyethylene, poly- third The mass ratio of alkene, methine succinic acid and epoxy prepolymer is 1: 0.6: 0.32: 0.22；Olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, tert-butyl lithium, the mass ratio of isomerous tridecanol polyoxyethylene ether are 1: 0.002: 0.2: 0.005∶0.15；Polytetrafluoroethylparticle particle and five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, carbon The mass ratio of sour potassium is 1: 0.08: 0.12: 0.18: 0.22: 0.11；Bisphenol A cyanate ester monomer, triglycidyl group trimerization are different The mass ratio of cyanate ester monomer, NPE and australene is 1: 1.6: 0.3: 0.1.
4. the preparation method of medical material according to claim 1, it is characterised in that：In step (2), the Static Spinning Technological parameter is：15~25 kilovolts of voltage, 8~12 centimetres of distance is received, liquid inventory is 0.3~0.4mL/h.
5. the preparation method of medical material according to claim 1, it is characterised in that：In step (2), sodium acid carbonate is water-soluble The mass concentration of liquid is 8%；Fibroin albumen, NPE, tetraethoxysilane, butyl acrylate, chitosan Mass ratio is 1: 0.4: 0.3: 0.1: 0.3；Formic acid, water, the mass ratio of lithium bromide and TRIS buffer are 1 ∶5∶0.6∶2。
6. the preparation method of medical material according to claim 1, it is characterised in that：In step (3), raw oyster shell whiting and two The mass ratio of titanium oxide is 5: 2；The molecular weight of hydroxy-terminated polysiloxane is 900~1100；Hyaluronic acid, 4- (2- ethoxys)- The sodium salt buffer solution of 1- piperazine ethanesulfonic acids half, polyethylene glycol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles For 1: 5: 0.6: 0.01: 0.005: 0.1.
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