CN106192064B - Medical material - Google Patents

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Publication number
CN106192064B
CN106192064B CN201610495789.1A CN201610495789A CN106192064B CN 106192064 B CN106192064 B CN 106192064B CN 201610495789 A CN201610495789 A CN 201610495789A CN 106192064 B CN106192064 B CN 106192064B
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minutes
mass ratio
medical material
fibre
fiber
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CN106192064A (en
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胡剑锋
黄镜澳
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Hu Jianfeng
Huang Jingao
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Individual
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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
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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 medical materials, using surface of the fibroin fiber as medical material, it is with excellent biocompatibility, available for treatment of wounds, tissue wrapping, while by the use of synthetic fibers as backing material, overcome the defects of fibroin fiber mechanical strength is poor, fibroin fiber with support fiber is combined by adhesive, becomes stable entirety, while also there is iris action after adhesive film forming, on the one hand fibroin fiber is prevented to be contaminated, in addition prevents the infiltrations such as tissue fluid, blood.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 10,000 times or more；Fracture strength is more than 60MPa.

Description

Medical material
Technical field
The invention belongs to technical field of macromolecules, and in particular 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 all for 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 it needs to be modified it, using new technology, in alkene On the basis of prepare good biocompatibility, wearability are strong, at low cost composite fiber product as medical material.
Invention content
The object of the present invention is to provide a kind of medical materials, have 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 uniformly mixed, added through screw rod melting extrusion Olefin particles are prepared in work；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acids, uncle Butyl lithium, isomerous tridecanol polyoxyethylene ether are uniformly 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 Afterwards using melt spinning method, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 matter Amount is more blended than carrying out, 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 in three shrinks Oil base cyamelide ester monomer is warming up to 120~125 DEG C, adds in nonylphenol polyoxyethylene ether and australene, reaction 30~35 Minute prepares epoxy prepolymer；
(2) it is dissolved in mixed liquor after natural silk degumming, infra-red drying obtains film after 1~1.5 hour；Then film is placed in carbon It in sour hydrogen sodium water solution, is placed in clear water again 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 nonylphenol polyoxyethylene ether, tetraethoxysilane and acrylic acid fourth are added in Ester stirs 40~55 minutes；Then chitosan is added in, stirring obtains spinning solution in 10 minutes, silk fibroin is obtained using Static Spinning Dimension；The mixed liquor is made of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, stirring 15~25 Polyethylene glycol and modified Nano oyster shell whiting are added in after minute, stirring adds in trifluoromethanesulfonic acid lanthanum and imidazoles after 35~55 minutes, It is stirred 1 hour in 80 DEG C, obtains adhesive；
The modified Nano oyster shell whiting is prepared by the following manner：Raw oyster shell whiting is existed after mixing with titanium dioxide 700 DEG C are sintered 45~55 minutes, are then comminuted into the powder that average grain diameter is 40 nanometers；Powder is put into container, adds in powder The ethyl alcohol of last 10 times of weight and the hydroxy-terminated polysiloxane of powder weight 0.6% stir 35~45 minutes, then add in powder The methyl p-hydroxybenzoate of weight 0.4% stirs 55~65 minutes, last drying to obtain modified Nano oyster shell whiting；
(4) adhesive is 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 medical material；The adhesive is located 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 It is 315~330 DEG C to spend, 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 acids, uncle Butyl lithium, isomerous tridecanol polyoxyethylene ether mass ratio be 1: 0.002: 0.2: 0.005: 0.15；Polytetrafluoroethylparticle particle with Five nitric hydrate bismuths, disodium hydrogen phosphate, uramit, acrylamide, potassium carbonate mass ratio be 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, chitosan mass ratio be 1: 0.4: 0.3: 0.1: 0.3；First Acid, water, lithium bromide and TRIS buffer mass ratio be 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, half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, poly- second two Alcohol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, imidazoles mass ratio be 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 can enhance the compatibility of inorganic matter and remaining organic principle；The present invention requires the molecular weight of polysiloxanes, molecular weight The too low adhesion properties that can influence adhesive, it is excessively high, influence the dispersing uniformity of modified oyster shell whiting.The present invention is fine using fibroin The surface as medical material is tieed up, with excellent biocompatibility, available for treatment of wounds, tissue wrapping, is utilized simultaneously Synthetic fibers overcome the defects of fibroin fiber mechanical strength is poor, by adhesive by fibroin fiber with propping up as backing material It supports fiber to combine, becomes stable entirety, while also there is iris action after adhesive film forming, on the one hand prevent fibroin fiber quilt Pollution, in addition prevents the infiltrations such as tissue fluid, blood.
Since 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 to the human body either harmless existing polyethylene or poly- of overcoming of animal body Additive existing for propylene modified particle reveals intoxicating problem；Epoxy prepolymer is granulated, and improves the strand of olefin polymer Rigidity improves its mechanical property and heat resistance, can increase the compatible of alkene and epoxy prepolymer using methine succinic acid Property puies forward the stability of entire polymer；Small molecule modifier is recycled, 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 increases its surface-active, is solved It has determined existing polytetrafluoroethylene fibre strong inert, can not be compatible with other fibers the problem of, adhesive can penetrate into micropore, It improves fibroin fiber and supports the binding force of fiber, increase the stability and stress balance of medical material.
(3) for medical material of the invention by reasonably designing, functional surfaces have excellent biocompatibility, assist mask There are good mechanical property and wearability；And prepare conveniently, pass through melt-spun, electrostatic spinning equipment, you can easily prepare；It is conducive to Industrial applications.
Specific 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 uniformly mixed, olefin particles is obtained 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 It closes uniformly, obtains 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 Using melt spinning method after sour potassium mixing, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre according to 4: 1 mass ratio progress is blended, 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 in, is warming up to 125 DEG C, adds in nonylphenol polyoxyethylene ether 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 mixed liquor after natural silk degumming, infra-red drying obtains film after 1 hour；Then it is film merging quality is dense It spends in the sodium bicarbonate aqueous solution for 8%, is placed in clear water again after 30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；Adjustment The mass concentration of silk fibroin protein solution is 35%；Then nonylphenol polyoxyethylene ether, tetraethoxysilane and acrylic acid are added in Butyl ester stirs 55 minutes；Then chitosan is added in, stirring obtains spinning solution in 10 minutes, silk fiber is obtained using Static Spinning； The mixed liquor is made of formic acid, water, lithium bromide and the TRIS buffer that mass ratio is 1: 5: 0.6: 2； Fibroin albumen, nonylphenol polyoxyethylene ether, tetraethoxysilane, butyl acrylate, chitosan mass ratio be 1: 0.4: 0.3: 0.1∶0.3；The technological parameter of above-mentioned Static Spinning is：15 kilovolts of voltage receives 12 centimetres of distance, liquid inventory 0.3mL/h；
(3) hyaluronic acid is added in half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, stirred 15 minutes Polyethylene glycol and modified Nano oyster shell whiting are added in afterwards, and stirring adds in trifluoromethanesulfonic acid lanthanum and imidazoles after~55 minutes, in 80 DEG C Stirring 1 hour, obtains adhesive；Hyaluronic acid, half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, poly- second two Alcohol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, imidazoles mass ratio be 1: 5: 0.6: 0.01: 0.005: 0.1；
The life oyster shell whiting that mass ratio is 5: 2 with titanium dioxide at 700 DEG C is sintered 55 minutes after mixing, is then crushed Into the powder that average grain diameter is 40 nanometers；Powder is put into container, adds in the ethyl alcohol and powder weight of 10 times of powder weight 0.6% hydroxy-terminated polysiloxane stirs 35 minutes, then adds in 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) adhesive is 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 located 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 uniformly mixed, is 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 uniformly 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 Using melt spinning method after amine, potassium carbonate mixing, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, fibrillated polytetrafluoroethylene Dimension is blended according to 4: 1 mass ratio progress, and be supported fiber；Bisphenol A cyanate ester monomer is added in reactor, 90 DEG C Reaction 12 minutes adds in triglycidyl group cyamelide ester monomer, is warming up to 120 DEG C, adds in nonylphenol polyoxyethylene ether With australene, reaction prepares epoxy prepolymer in 30 minutes；Bisphenol A cyanate ester monomer, triglycidyl group isocyanuric acid ester The mass ratio of monomer, nonylphenol polyoxyethylene ether 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 mixed liquor after natural silk degumming, infra-red drying obtains film after 1 hour；Then it is film merging quality is dense It spends in the sodium bicarbonate aqueous solution for 8%, is placed in clear water again after 30 minutes, dialysis obtains silk fibroin protein solution in 1 hour；Adjustment The mass concentration of silk fibroin protein solution is 40%；Then nonylphenol polyoxyethylene ether, tetraethoxysilane and acrylic acid are added in Butyl ester stirs 40 minutes；Then chitosan is added in, stirring obtains spinning solution in 10 minutes, silk fiber is obtained using Static Spinning； The mixed liquor is made of formic acid, water, lithium bromide and the TRIS buffer that mass ratio is 1: 5: 0.6: 2； Fibroin albumen, nonylphenol polyoxyethylene ether, tetraethoxysilane, butyl acrylate, chitosan mass ratio be 1: 0.4: 0.3: 0.1∶0.3；The technological parameter of above-mentioned Static Spinning is：25 kilovolts of voltage receives 8 centimetres of distance, liquid inventory 0.4mL/h；
(3) hyaluronic acid is added in half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, after 15 points of stirring Polyethylene glycol and modified Nano oyster shell whiting are added in, stirring adds in trifluoromethanesulfonic acid lanthanum and imidazoles after 55 minutes, 80 DEG C of stirrings 1 are small When obtain adhesive；Hyaluronic acid, half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, polyethylene glycol, modification are received Rice oyster shell whiting, trifluoromethanesulfonic acid lanthanum, imidazoles mass ratio be 1: 5: 0.6: 0.01: 0.005: 0.1；By the life that mass ratio is 5: 2 Oyster shell whiting is sintered 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 in the ethyl alcohol 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 in the methyl p-hydroxybenzoate of powder weight 0.4%, is stirred 65 minutes, dry To modified Nano oyster shell whiting；
(4) adhesive is 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) for 99% with On；It is wear-resisting up to 10,000 times or more；Fracture strength is more than 60MPa.

Claims (6)

1. a kind of medical material, is prepared by the following manner：
(1) polyethylene, polypropylene, methine succinic acid and epoxy prepolymer are uniformly mixed, are 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, tertiary butyl Lithium, isomerous tridecanol polyoxyethylene ether are uniformly mixed, and obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning；It 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 Carry out blended, be supported fiber；
Bisphenol A cyanate ester monomer is added in reactor, 90~95 DEG C are reacted 10~12 minutes, add in triglycidyl group Cyamelide ester monomer is warming up to 120~125 DEG C, adds in nonylphenol polyoxyethylene ether and australene, reacts 30~35 minutes Prepare epoxy prepolymer；
(2) it is dissolved in mixed liquor after natural silk degumming, infra-red drying obtains film after 1~1.5 hour；Then film is placed in bicarbonate It in sodium water solution, is placed in clear water again 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 nonylphenol polyoxyethylene ether, tetraethoxysilane and butyl acrylate are added in, is stirred It mixes 40~55 minutes；Then chitosan is added in, stirring obtains spinning solution in 10 minutes, silk fiber is obtained using Static Spinning；Institute Mixed liquor is stated to be made of formic acid, water, lithium bromide and TRIS buffer；
(3) hyaluronic acid is added in half sodium salt buffer solution of 4- (2- ethoxys) -1- piperazine ethanesulfonic acids, stirred 15~25 minutes Polyethylene glycol and modified Nano oyster shell whiting are added in afterwards, and stirring adds in 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：By raw oyster shell whiting with titanium dioxide after mixing 700 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 in powder weight The ethyl alcohol of 10 times of amount and the hydroxy-terminated polysiloxane of powder weight 0.6%, stir 35~45 minutes, then add in powder weight 0.4% methyl p-hydroxybenzoate stirs 55~65 minutes, last drying to obtain modified Nano oyster shell whiting；
(4) adhesive is 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 located 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. medical material according to claim 1, it is characterised in that：In step (1), the reaction of screw rod melting extrusion processing Extrusion temperature is 180~200 DEG C, and screw speed control is 110~115 revs/min, and residence time of the material in screw rod is 5~6 Minute；It is 210~220 DEG C that melt spinning, which obtains temperature during olefin(e) fibre, and spinning speed is 800~900 ms/min；Melt spinning It is 315~330 DEG C to obtain temperature during polytetrafluoroethylene fibre, and spinning speed is 600~700 ms/min.
3. medical material 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- acrylamides Base -2- methyl propane sulfonic acids, tert-butyl lithium, isomerous tridecanol polyoxyethylene ether mass ratio be 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 The mass ratio of monomer, nonylphenol polyoxyethylene ether and australene is 1: 1.6: 0.3: 0.1.
4. medical material according to claim 1, it is characterised in that：In step (2), the technological parameter of the Static Spinning For：15~25 kilovolts of voltage, receives 8~12 centimetres of distance, and liquid inventory is 0.3~0.4mL/h.
5. medical material according to claim 1, it is characterised in that：In step (2), the quality of sodium bicarbonate aqueous solution is dense Spend is 8%；Fibroin albumen, nonylphenol polyoxyethylene ether, tetraethoxysilane, butyl acrylate, chitosan mass ratio be 1: 0.4∶0.3∶0.1∶0.3；Formic acid, water, lithium bromide and TRIS buffer mass ratio be 1: 5: 0.6: 2.
6. medical material according to claim 1, it is characterised in that：In step (3), the matter of raw oyster shell whiting and titanium dioxide Amount is than being 5: 2；The molecular weight of hydroxy-terminated polysiloxane is 900~1100；Hyaluronic acid, 4- (2- ethoxys) -1- piperazines Half sodium salt buffer solution of sulfonic acid, polyethylene glycol, modified Nano oyster shell whiting, trifluoromethanesulfonic acid lanthanum, imidazoles mass ratio be 1: 5: 0.6: 0.01∶0.005∶0.1。
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