CN106192064A - Medical material - Google Patents

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Publication number
CN106192064A
CN106192064A CN201610495789.1A CN201610495789A CN106192064A CN 106192064 A CN106192064 A CN 106192064A CN 201610495789 A CN201610495789 A CN 201610495789A CN 106192064 A CN106192064 A CN 106192064A
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China
Prior art keywords
minutes
medical material
mass ratio
acid
fibre
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Granted
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CN201610495789.1A
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CN106192064B (en
Inventor
彭代信
宋晓静
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Huang Jingao
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SUZHOU YIKETAI ELECTRONIC MATERIAL CO Ltd
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Priority to CN201711163724.8A priority Critical patent/CN108130620A/en
Priority to CN201711163725.2A priority patent/CN107881591A/en
Priority to CN201610495789.1A priority patent/CN106192064B/en
Publication of CN106192064A publication Critical patent/CN106192064A/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)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of medical material, use fibroin fiber as the surface of medical material, it has the biocompatibility of excellence, can be used for treatment of wounds, tissue wrapping, utilizes synthetic fibers as backing material simultaneously, overcome the defect of fibroin fiber mechanical strength difference, by adhesive, fibroin fiber is combined with support fiber, becomes stable entirety, after adhesive film forming, also there is iris action simultaneously, on the one hand prevent fibroin fiber to be contaminated, additionally prevent tissue fluid, blood etc. from permeating.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%；Wear-resisting reach more than 10,000 times；Fracture strength is more than 60MPa.

Description

Medical material
Technical field
The invention belongs to technical field of macromolecules, be specifically related to a kind 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 Be cotton fiber be all short fibre, mechanical property is poor, and wearability is low.Olefin(e) fibre yield is relatively big, and cost is the lowest, but due to Its inertia is strong, poor biocompatibility, and is not used as medical material.It is thus desirable to modified to it, utilize new technology, at alkene On the basis of prepare that good biocompatibility, wearability be strong, the composite fiber product of low cost is as medical material.
Summary of the invention
It is an object of the invention to provide a kind of medical material, there is the biocompatibility of excellence.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of medical material, is prepared by the following manner:
(1) by polyethylene, polypropylene, methine succinic acid and epoxy prepolymer mix homogeneously, melt extrude through screw rod and add Work, prepares olefin particles；Then by olefin particles and dimethyl tin oxide, 2-acrylamide-2-methylpro panesulfonic acid, uncle Butyl lithium, isomerous tridecanol polyoxyethylene ether mix homogeneously, obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning； By polytetrafluoroethylparticle particle and five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, potassium carbonate mixing Rear employing melt spinning method, prepares polytetrafluoroethylene fibre；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 matter Amount ratio carries out blending, and be supported fiber；
Joining in reactor by bisphenol A cyanate ester monomer, 90～95 DEG C are reacted 10～12 minutes, add three shrinks sweet Oil base isocyanuric acid ester monomer, is warming up to 120～125 DEG C, adds NPE and australene, reacts 30～35 Minute prepare epoxy prepolymer；
(2) being dissolved in after natural silk degumming in mixed liquor, after 1～1.5 hour, infrared drying obtains film；Then film is inserted carbon In acid hydrogen sodium water solution, insert again in clear water after 20～30 minutes, dialyse and obtain silk fibroin protein solution in 1 hour；Adjust fibroin egg The mass concentration of white solution is 35～40%；It is subsequently adding NPE, tetraethoxysilane and acrylic acid fourth Ester, stirs 40～55 minutes；It is subsequently adding chitosan, stirs and obtain spinning liquid in 10 minutes, then obtain silk fibroin through Static Spinning Dimension；Described mixed liquor is made up of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, stir 15～25 Add Polyethylene Glycol and modified Nano conch meal after minute, after stirring 35～55 minutes, add trifluoromethanesulfonic acid lanthanum and imidazoles, Stir 1 hour in 80 DEG C, obtain adhesive；
Described modified Nano conch meal is prepared by the following manner: will raw conch meal mix homogeneously with titanium dioxide after 700 DEG C sinter 45～55 minutes, are then comminuted into the powder that mean diameter is 40 nanometers；Powder is put in container, add powder The ethanol of end weight 10 times and the hydroxy-terminated polysiloxane of powder weight 0.6%, stir 35～45 minutes, be subsequently adding powder The methyl parahydroxybenzoate of weight 0.4%, stirs 55～65 minutes, last drying to obtain modified Nano conch meal；
(4) adhesive being coated on support fiber surface, 70 DEG C are heated 5～8 minutes；Then it is combined with silk fiber, heat Pressure obtains composite fibre, finally composite fibre is carried out sterilization treatment and obtains medical material；Described adhesive is positioned at support fiber And between silk fiber；The pressure of described hot pressing is 0.1MPa, and temperature is 85 DEG C, and the time is 18～22 minutes.
In technique scheme, in step (1), it is 180～200 DEG C that screw rod melt extrudes the reactive extrursion temperature of processing, It is 110～115 revs/min that screw speed controls, and the material time of staying in screw rod is 5～6 minutes；Melt spinning obtains alkene During fiber, temperature is 210～220 DEG C, and spinning speed is 800～900 ms/min；Melt spinning obtains temperature during polytetrafluoroethylene fibre Degree is 315～330 DEG C, and 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 acid, 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 isocyanuric acid ester monomer, Nonyl pheno Ether is 1: 1.6: 0.3: 0.1 with the mass ratio of australene.
In technique scheme, in step (2), the technological parameter of described Static Spinning is: voltage 15～25 kilovolts, 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 The mass ratio of acid, water, lithium bromide and TRIS buffer is 1: 5: 0.6: 2.
In technique scheme, in step (3), raw conch meal is 5: 2 with the mass ratio of titanium dioxide；The poly-silica of terminal hydroxy group The molecular weight of alkane is 900～1100；Hyaluronic acid, 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, poly-second two Alcohol, modified Nano conch meal, 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 two ends are contained hydroxyl, had excellent adhesion property, in order to the surface to inorganic material Reason, can strengthen the compatibility of inorganic matter and remaining organic principle；The molecular weight of polysiloxanes is required by the present invention, molecular weight The too low adhesion properties that can affect adhesive, the dispersing uniformity of the too high modified conch meal of then impact.The present invention uses fibroin fine Tieing up the surface as medical material, it has the biocompatibility of excellence, can be used for treatment of wounds, tissue wrapping, utilizes simultaneously Synthetic fibers, as backing material, overcome the defect of fibroin fiber mechanical strength difference, and are propped up fibroin fiber by adhesive Support fiber combines, and becomes stable entirety, also has iris action after adhesive film forming simultaneously, on the one hand prevents fibroin fiber quilt Pollute, additionally prevent tissue fluid, blood etc. from permeating.
Owing to technique scheme is used, the present invention compared with prior art has the advantage that
(1) present invention uses with polyethylene, polypropylene as primary raw material, and by adding rational material, melt spinning obtains To olefin(e) fibre, solving the existing problem that olefin(e) fibre processability is poor, mechanical strength is low, the most modified alkene is fine Dimension has certain biocompatibility, and additive is harmless to human body or animal body, overcomes existing polyethylene or gathers The additive that propylene modified particle exists reveals intoxicating problem；Epoxy prepolymer pelletize, improves the strand of olefin polymer Rigidity, improves its mechanical property and thermostability, utilizes methine succinic acid can increase the compatible of alkene and epoxy prepolymer Property, put forward the stability of whole polymer；Recycle small molecule-modified dose when melt-spun to olefin-modified, alkene can not reduced Its biocompatibility and resistance to ag(e)ing is improved on the basis of mechanical property.
(2) present invention utilizes polytetrafluoroethylene fibre to greatly improve the wearability of medical material, simultaneously in melt-spun mistake Journey utilizes adding ingredient on the one hand form micropore on polytetrafluoroethylene fibre surface, on the one hand add its surface activity, solve The problem that existing polytetrafluoroethylene fibre inertia of having determined is strong, cannot be compatible with other fibers, adhesive can penetrate into micropore, The adhesion that improve fibroin fiber and support fiber, adds stability and the stress balance of medical material.
(3) medical material of the present invention has the biocompatibility of excellence by reasonably design, functional surfaces, assists mask There are good mechanical property and wearability；And prepare conveniently, by melt-spun, Static Spinning equipment, can easily prepare；It is beneficial to Industrial applications.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
One one kinds of medical materials of embodiment, are prepared by the following manner:
(1) by polyethylene, polypropylene, methine succinic acid and epoxy prepolymer that mass ratio is 1: 0.6: 0.32: 0.22 Mix homogeneously, melt extrudes through screw rod and obtains olefin particles；Then it is the alkene of 1: 0.002: 0.2: 0.005: 0.15 by mass ratio Hydrocarbon particle, dimethyl tin oxide, 2-acrylamide-2-methylpro panesulfonic acid, tert-butyl lithium, isomerous tridecanol polyoxyethylene ether are mixed Close uniformly, obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning；It is 1: 0.08: 0.12: 0.18 by mass ratio: The polytetrafluoroethylparticle particle of 0.22: 0.11, five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, carbon Use melt spinning method after acid potassium mixing, prepare polytetrafluoroethylene fibre；By olefin(e) fibre, polytetrafluoroethylene fibre according to The mass ratio of 4: 1 carries out blending, and be supported fiber；Bisphenol A cyanate ester monomer is joined in reactor, 95 DEG C of reactions 10 Minute, add triglycidyl group isocyanuric acid ester monomer, be warming up to 125 DEG C, add NPE and australene Alkene, reacts and prepares epoxy prepolymer in 30 minutes；Bisphenol A cyanate ester monomer, triglycidyl group isocyanuric acid ester monomer, nonyl Base phenol polyethenoxy ether is 1: 1.6: 0.3: 0.1 with the mass ratio of australene；Above-mentioned screw rod melt extrudes the reactive extrursion of processing Temperature is 180～200 DEG C, and it is 110 revs/min that screw speed controls, and the material time of staying in screw rod is 6 minutes；Melt and spin It is 210～220 DEG C that silk obtains temperature during olefin(e) fibre, and spinning speed is 800 ms/min；Melt spinning obtains fibrillated polytetrafluoroethylene During dimension, temperature is 315～330 DEG C, and spinning speed is 700 ms/min；
(2) being dissolved in after natural silk degumming in mixed liquor, after 1 hour, infrared drying obtains film；Then film is inserted quality dense Degree is in the sodium bicarbonate aqueous solution of 8%, inserts in clear water after 30 minutes again, dialyses and obtains silk fibroin protein solution in 1 hour；Adjust The mass concentration of silk fibroin protein solution is 35%；It is subsequently adding NPE, tetraethoxysilane and acrylic acid Butyl ester, stirs 55 minutes；It is subsequently adding chitosan, stirs and obtain spinning liquid in 10 minutes, then obtain silk fiber through Static Spinning； Described mixed liquor is made up of the formic acid that mass ratio is 1: 5: 0.6: 2, water, lithium bromide and TRIS buffer； 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: voltage 15 kilovolts, receiving range 12 centimetres, and liquid inventory is 0.3mL/h；
(3) hyaluronic acid is added in 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, stir 15 minutes Rear addition Polyethylene Glycol and modified Nano conch meal, stirring～addition trifluoromethanesulfonic acid lanthanum and imidazoles after 55 minutes, in 80 DEG C Stir 1 hour, obtain adhesive；Hyaluronic acid, 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, poly-second two Alcohol, modified Nano conch meal, 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 raw conch meal that mass ratio is 5: 2 is mixed homogeneously with titanium dioxide, then pulverize The powder becoming mean diameter to be 40 nanometers；Powder is put in container, add ethanol and the powder weight of powder weight 10 times The hydroxy-terminated polysiloxane of 0.6%, stirs 35 minutes, is subsequently adding the methyl parahydroxybenzoate of powder weight 0.4%, stirring 65 minutes, last drying to obtain modified Nano conch meal；The molecular weight of hydroxy-terminated polysiloxane is 900～1100；
(4) adhesive being coated on support fiber surface, 70 DEG C are heated 8 minutes；Then being combined with silk fiber, hot pressing obtains To composite fibre, sterilization treatment obtains medical material；Described adhesive is supporting between fiber and silk fiber；Described hot pressing Pressure 0.1MPa, temperature 85 DEG C, 18 minutes time.
21 kinds of medical materials of embodiment, are prepared by the following manner:
(1) by polyethylene, polypropylene, methine succinic acid and epoxy prepolymer that mass ratio is 1: 0.6: 0.32: 0.22 Mix homogeneously, melt extrudes processing through screw rod, prepares olefin particles；Then it is 1: 0.002: 0.2: 0.005 by mass ratio: The olefin particles of 0.15, dimethyl tin oxide, 2-acrylamide-2-methylpro panesulfonic acid, tert-butyl lithium, isomerous tridecanol polyoxy Vinyl Ether mix homogeneously, obtains compositions of olefines, then obtains olefin(e) fibre through melt spinning；It is 1: 0.08: 0.12 by mass ratio: The polytetrafluoroethylparticle particle of 0.18: 0.22: 0.11, five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acryloyl Use melt spinning method after the mixing of amine, potassium carbonate, prepare polytetrafluoroethylene fibre；By olefin(e) fibre, fibrillated polytetrafluoroethylene Dimension carries out blending according to the mass ratio of 4: 1, and be supported fiber；Bisphenol A cyanate ester monomer is joined in reactor, 90 DEG C React 12 minutes, add triglycidyl group isocyanuric acid ester monomer, be warming up to 120 DEG C, add NPE With australene, react and prepare epoxy prepolymer in 30 minutes；Bisphenol A cyanate ester monomer, triglycidyl group isocyanuric acid ester Monomer, NPE are 1: 1.6: 0.3: 0.1 with the mass ratio of australene；Above-mentioned screw rod melt extrudes the anti-of processing Answering extrusion temperature is 180～200 DEG C, and it is 115 revs/min that screw speed controls, and the material time of staying in screw rod is 6 minutes； It is 210～220 DEG C that melt spinning obtains temperature during olefin(e) fibre, and spinning speed is 800 ms/min；Melt spinning obtains polytetrafluoro During vinyl fiber, temperature is 315～330 DEG C, and spinning speed is 600 ms/min；
(2) being dissolved in after natural silk degumming in mixed liquor, after 1 hour, infrared drying obtains film；Then film is inserted quality dense Degree is in the sodium bicarbonate aqueous solution of 8%, inserts in clear water after 30 minutes again, dialyses and obtains silk fibroin protein solution in 1 hour；Adjust The mass concentration of silk fibroin protein solution is 40%；It is subsequently adding NPE, tetraethoxysilane and acrylic acid Butyl ester, stirs 40 minutes；It is subsequently adding chitosan, stirs and obtain spinning liquid in 10 minutes, then obtain silk fiber through Static Spinning； Described mixed liquor is made up of the formic acid that mass ratio is 1: 5: 0.6: 2, water, lithium bromide and TRIS buffer； 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: voltage 25 kilovolts, receiving range 8 centimetres, and liquid inventory is 0.4mL/h；
(3) hyaluronic acid is added in 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, after stirring 15 points Adding Polyethylene Glycol and modified Nano conch meal, add trifluoromethanesulfonic acid lanthanum and imidazoles after stirring 55 minutes, 80 DEG C of stirrings 1 are little Time obtain adhesive；Hyaluronic acid, 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, Polyethylene Glycol, modification are received Rice conch meal, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles are 1: 5: 0.6: 0.01: 0.005: 0.1；It is the life of 5: 2 by mass ratio Conch meal sinters 55 minutes at 700 DEG C after mixing with titanium dioxide, is then comminuted into the powder that mean diameter is 40 nanometers；By powder End is put in container, adds ethanol and the hydroxy-terminated polysiloxane of powder weight 0.6% of powder weight 10 times, and molecular weight is 900～1100, stir 35 points, be subsequently adding the methyl parahydroxybenzoate of powder weight 0.4%, stir 65 minutes, be dried To modified Nano conch meal；
(4) adhesive being coated on support fiber surface, 70 DEG C are heated 8 minutes；Then being combined with silk fiber, hot pressing obtains To composite fibre, sterilization treatment obtains medical material；The pressure of described 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；Wear-resisting reach more than 10,000 times；Fracture strength is more than 60MPa.

Claims (6)

1. a medical material, is prepared by the following manner:
(1) by polyethylene, polypropylene, methine succinic acid and epoxy prepolymer mix homogeneously, processing is melt extruded through screw rod, system For obtaining olefin particles；Then by olefin particles and dimethyl tin oxide, 2-acrylamide-2-methylpro panesulfonic acid, the tert-butyl group Lithium, isomerous tridecanol polyoxyethylene ether mix homogeneously, obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning；Will be poly- Adopt after tetrafluoroethene particle and five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, potassium carbonate mixing With melt spinning method, prepare polytetrafluoroethylene fibre；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 mass ratio Carrying out blending, be supported fiber；
Joining in reactor by bisphenol A cyanate ester monomer, 90～95 DEG C are reacted 10～12 minutes, add triglycidyl group Isocyanuric acid ester monomer, is warming up to 120～125 DEG C, adds NPE and australene, reacts 30～35 minutes Prepare epoxy prepolymer；
(2) being dissolved in after natural silk degumming in mixed liquor, after 1～1.5 hour, infrared drying obtains film；Then film is inserted bicarbonate In sodium water solution, insert again in clear water after 20～30 minutes, dialyse and obtain silk fibroin protein solution in 1 hour；Adjustment fibroin albumen is molten The mass concentration of liquid is 35～40%；It is subsequently adding NPE, tetraethoxysilane and butyl acrylate, stirs Mix 40～55 minutes；It is subsequently adding chitosan, stirs and obtain spinning liquid in 10 minutes, then obtain silk fiber through Static Spinning；Institute State mixed liquor to be made up of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in 4-(2-ethoxy)-1-piperazine ethanesulfonic acid half sodium salt buffer, stir 15～25 minutes Rear addition Polyethylene Glycol and modified Nano conch meal, add trifluoromethanesulfonic acid lanthanum and imidazoles, in 80 after stirring 35～55 minutes DEG C stirring 1 hour, obtain adhesive；
Described modified Nano conch meal is prepared by the following manner: 700 after being mixed homogeneously with titanium dioxide by raw conch meal DEG C sintering 45～55 minutes, be then comminuted into the powder that mean diameter is 40 nanometers；Powder is put in container, add powder weight Measure ethanol and the hydroxy-terminated polysiloxane of powder weight 0.6% of 10 times, stir 35～45 minutes, be subsequently adding powder weight The methyl parahydroxybenzoate of 0.4%, stirs 55～65 minutes, last drying to obtain modified Nano conch meal；
(4) adhesive being coated on support fiber surface, 70 DEG C are heated 5～8 minutes；Then being combined with silk fiber, hot pressing obtains To composite fibre, finally composite fibre is carried out sterilization treatment and obtain medical material；Described adhesive is positioned at support fiber and silkworm Between silk fiber；The pressure of described hot pressing is 0.1MPa, and temperature is 85 DEG C, and the time is 18～22 minutes.
Medical material the most according to claim 1, it is characterised in that: in step (1), screw rod melt extrudes the reaction of processing Extrusion temperature is 180～200 DEG C, and it is 110～115 revs/min that screw speed controls, and the material time of staying in screw rod is 5～6 Minute；It is 210～220 DEG C that melt spinning obtains temperature during olefin(e) fibre, and spinning speed is 800～900 ms/min；Melt spinning Obtaining temperature during polytetrafluoroethylene fibre is 315～330 DEG C, and spinning speed is 600～700 ms/min.
Medical material the most according to claim 1, it is characterised in that: in step (1), polyethylene, polypropylene, methine fourth The mass ratio of diacid and epoxy prepolymer is 1: 0.6: 0.32: 0.22；Olefin particles and dimethyl tin oxide, 2-acrylamide Base-2-methyl propane sulfonic acid, 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, potassium carbonate Mass ratio is 1: 0.08: 0.12: 0.18: 0.22: 0.11；Bisphenol A cyanate ester monomer, triglycidyl group isocyanuric acid ester Monomer, NPE are 1: 1.6: 0.3: 0.1 with the mass ratio of australene.
Medical material the most according to claim 1, it is characterised in that: in step (2), the technological parameter of described Static Spinning For: voltage 15～25 kilovolts, receiving range 8～12 centimetres, liquid inventory is 0.3～0.4mL/h.
Medical material the most according to claim 1, it is characterised in that: in step (2), the quality of sodium bicarbonate aqueous solution is dense Degree is 8%；Fibroin albumen, NPE, tetraethoxysilane, butyl acrylate, the mass ratio of chitosan are 1: 0.4∶0.3∶0.1∶0.3；The mass ratio of formic acid, water, lithium bromide and TRIS buffer is 1: 5: 0.6: 2.
Medical material the most according to claim 1, it is characterised in that: in step (3), raw conch meal and the matter of titanium dioxide Amount ratio is 5: 2；The molecular weight of hydroxy-terminated polysiloxane is 900～1100；Hyaluronic acid, 4-(2-ethoxy)-1-piperazine Sulfonic acid half sodium salt buffer, Polyethylene Glycol, modified Nano conch meal, trifluoromethanesulfonic acid lanthanum, the mass ratio of imidazoles are 1: 5: 0.6: 0.01∶0.005∶0.1。
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