CN104387655A - Medical nano-zinc oxide antibacterial PE and preparation method thereof - Google Patents

Medical nano-zinc oxide antibacterial PE and preparation method thereof Download PDF

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Publication number
CN104387655A
CN104387655A CN201410676248.XA CN201410676248A CN104387655A CN 104387655 A CN104387655 A CN 104387655A CN 201410676248 A CN201410676248 A CN 201410676248A CN 104387655 A CN104387655 A CN 104387655A
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parts
antibacterial
zinc oxide
oxide
medical
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徐勤霞
李苏杨
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Suzhou Bec Biological Technology Co Ltd
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Suzhou Bec Biological Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Abstract

The invention discloses medical nano-zinc oxide antibacterial PE and a preparation method thereof. The method comprises the following steps: weighing PE, calcium carbonate, cerium oxide, HDPE, nano-zinc oxide, DCP, an antioxidant, calcium stearate, EBS, POE, a coupling agent, CPE, barium stearate, stearic acid and zinc stearate according to the parts by weight; mixing evenly; and then extruding and pelletizing, so as to prepare medical nano-zinc oxide antibacterial PE. According to the medical nano-zinc oxide antibacterial PE product, the tensile strength is 25-35MPa; the elongation at break is 40-80%; the antibacterial ratio of escherichia coli is 99.5-99.9%; the antibacterial ratio of staphylococcus aureus is 99.6-99.9%; the impact strength is 13-17kJ/m<2>; the vicat softening point is 125-145 DEG C; the shore hardness is 75-79; and the tear strength is 36-40N/mm.

Description

Antibacterial PE of a kind of medical nano zinc oxide and preparation method thereof
Technical field
The application belongs to medical new material technology field, particularly relates to antibacterial PE of a kind of medical nano zinc oxide and preparation method thereof.
Background technology
Biomedical material refers to a class and has property, features, for artificial organs, surgical repair, physiotherapy and rehabilitation, diagnosis, treatment illness, and can not produce dysgenic material to tissue.Present various synthetic materials and natural macromolecular material, metal and alloy material, pottery and carbon materials and various matrix material, it is made product and has been widely used in clinical and scientific research.Along with the development of biotechnology, the scientist of different subject has carried out broad co-operation, thus the artificial organs making manufacture have complete biological function shows fine prospect.The reparation in tissue and device palace, will fixedly develop into regeneration from simply utilizing appliance mechanisms and rebuild lived tissue and device palace; Permanent reparation and replacement is developed to from the reparation of short-life tissue and organ.This Medical Revolution (particularly surgery), proposes many demands to the development of the related disciplines such as life profit and material, creates important promoter action to the development of biomedical material.The suggestion bio-medical material bio-medical material of developing china biomedical material is the important branch of Materials Science and Engineering, and its maximum feature is that subject crossing is extensive, application potential is huge, challenge is strong.Along with novel material, new technology, the continuing to bring out of new opplication, attract many scientists to throw the research in this field of people, become current materialogy and study one of most active field.In China, although the research of biomedical material obtains the achievement that some attract people's attention, integral level is not high, and follow-up study is many, and source treatment is few.In industrialization, biomedical material and goods thereof account for the share of world market less than 2%, mainly rely on import, and product technology structure and level are in the junior stage substantially.In conjunction with China's actual conditions and discipline development trend, according to the principle of " doing something more important by leaving the others undone, key breakthrough ", we advise, should carry out primary study in five.
One is the design of biological structure and biological function and builds principle research.Study emphatically the design of the base materials such as bone, cartilage and the tendon with inducing tissue regeneration and skeleton construction and bionical assembling thereof; Two is the interaction mechanism research of surface/interface process-between material and body.From cell and molecular level further investigation material and specific cells, organize between surface/interface effect, announcement affects factor and the essence of biocompatibility.Three is controlled release study mechanism of bio-guide and biologically active substance.Study design and the bio-guide principle of the material of the specific bioactive materials such as self controllable or Targeting delivery albumen, gene; For the design of the semi-permeable polymeric film of histocyte and gene therapy, self-assembly and specific cell packing technique; Four be biological degradation/absorption regulatory mechanism research.The impact that the molecular structure of research biological degradation/absorbing material and coenocorrelation are degraded on it, the regulation and control of degraded/absorption rate, degraded/absorption and metabolism mechanism, and degraded product is on the impact of body.Its target is for the having of one's own of engineered artificial organs biomaterial and drug release material, method of modifying are provided fundamental basis, and realizes the object that material participates in vital process and builds vital tissues.Five is preparation method and the quality control system research of material.The computer aided design (CAD) of main research bio-medical material and dummy; By carrying out of above-mentioned research, will the research level of Chinese biological material be improved a lot, for solid basis is established in the development of Chinese biological medical material science and industry thereof.
Medical macromolecular materials are the polymer materialss manufacturing human body viscera, vitro in organ, pharmaceutical dosage form and medicine equipment.Over 20 years, the macromolecular material for this respect has polyvinyl chloride, natural rubber, polyethylene, polymeric amide, polypropylene, polystyrene, silicon rubber, polyester, tetrafluoroethylene, polymethylmethacrylate and urethane etc.Medical macromolecular materials are used for human body, are directly connected to the life and health of people, to the requirement of its performance are generally: 1. security: must be nontoxic or side effect is few.This just requires that polymer purity is high, and production environment is very clean, and remaining of reagent and additive in polymerization is few, and foreign matter content is ppm level, guarantees anosis, nontoxic propagation conditions.2. physics, chemistry and mechanical property: the requirement that need meet medical required Design and Features.As aging in hardness, elasticity, physical strength, fatigue strength, creep, abrasion, water-absorbent, stripping property, resistance to enzymatic and body etc.For heart valve, preferably can use 250,000 hours, require that fatigue resistance is good especially.In addition, also require to be convenient to sterilization, damp and hot sterilization (120 ~ 140 ° of C), dry heat sterilization (160 ~ 190 ° of C), radiation sterilization or chemical treatment sterilization can be tolerated, and do not reduce the performance of material.Require good processability, required different shape can be processed into, and not damage its proper property.3. adaptability: comprise the adaptability with other materials in medical treatment product, the adaptability of material and the various tissue of human body.Medicine equipment, general curative and nurse apparatus, as eye band, casing flusher, entry needle, stethoscope, rectoscope, eye lotion dropper, abdominal belt and connecting piece etc.; Anesthesia and operating room furniture, as suction pump, suture, pharynx mirror, intravascular injection apparatus etc.; Check and inspection chamber apparatus, as the electrode, developmental tube, culture dish etc. of heparin tube, blood collecting bottle, electrocardiogram(ECG.Pharmaceutical dosage form, the auxiliary agent of medicine: macromolecular material itself is inertia, does not participate in the effect of medicine, only plays the effects such as thickening, surfactivity, disintegration, bonding, figuration, lubrication and packaging, or in human body, play " Drug Storage " effect, drug slow is released and prolong drug action time.Polymeric medicine: by low-molecule drug, makes molecular vehicle with inertia water-soluble polymers, the low molecular compound with the property of medicine, is connected, makes polymeric medicine by covalent linkage or ionic linkage with the side base of carrier.
Antibiotic plastic be a class in environment for use itself to stain bacterium on plastics, mould, the female bacterium of alcohol, algae even virus etc. rise and suppress or the plastics of killing action, keep itself clean by suppressing the breeding of microorganism.At present, antibiotic plastic obtains mainly through the method for adding a small amount of antiseptic-germicide in common plastics.First antibiotic plastic will meet the exclusive requirement to performances such as its physics, chemistry, machineries when plastics use as basic material in using, will consider to possess the requirement of this specific function antibacterial and consequent additional factor simultaneously.The research of Chinese medical macromolecular material starts to walk comparatively early, development is very fast.About You50Duo Ge unit is engaged in the research of this respect at present, existing medical macromolecular materials kind more than 60, and goods reach more than 400 and plant, and the polymethylmethacrylate for medical treatment reaches 300t every year.But the research of Chinese medical macromolecular material is still in experience and semiempirical stage at present, does not also have can be based upon on the basis of molecular designing.Therefore, should with the structure and theory of material, the chemical constitution of material, the pass between surface properties and the consistency of life entity tissue are according to researching and developing novel material.Medical macromolecular materials will be applied to organism must will meet the strict requirement such as biological functionality, biocompatibility, chemical stability and workability simultaneously.
Polyethylene English name: Poly (ethylene) Chinese another name: high-pressure polyethylene; LDPE; High-pressure polyethylene injection molding material; Type low density polyethylene resin; Linear polyethylene; LLDPE; Low pressure Low Density Polyethylene; PE; Polyvinyl resin; Polyethylene wax; Low molecular weight polyethylene; PE wax; Low Density Polyethylene; For making agricultural, food and industrial packaging film, the coated and coating of electric wire, composed paper etc.; Keep storage sealing, be stored in cool place, dry place, guarantee that workplace has good ventilation or gas barrier.Polyethylene (polyethylene is called for short PE) is that ethene is through being polymerized obtained a kind of thermoplastic resin.Industrially, the multipolymer of ethene and a small amount of alpha-olefin is also comprised.Polyethylene odorless, nontoxic, feel ceraceous, have excellent resistance to low temperature (minimum use temperature can reach-100 ~-70 ° of C), chemical stability is good, the erosion (the not resistance to acid with oxidizing property) of the most of soda acid of ability.Be insoluble to common solvent under normal temperature, water-absorbent is little, and electrical insulating property is excellent.Poly performance depends on its polymerization methods.That under middle pressure (15-30 normal atmosphere) organic compound catalytic condition, carry out that Ziegler-Natta is polymerized is high density polyethylene(HDPE) (HDPE).The polyethylene molecule be polymerized under this condition is linear, and molecular chain is very long, and molecular weight is up to hundreds of thousands of.If at high pressure (100-300MPa), high temperature (190 – 210C), radical polymerization under peroxide catalyzed condition, that produce is then Low Density Polyethylene (LDPE), and it is side chain chemical combination structure.Polyethylene is typical thermoplastics, is odorless, tasteless, nontoxic flammable white powder.The PE resin of forming process is all the wax-like particulate material through extruding pelletization, and outward appearance is creamy white.Its molecular weight is in 10,000 one loa ten thousand scopes.Molecular weight is then ultrahigh molecular weight polyethylene(UHMWPE) f UHMWPE3 more than 100,000.Molecular weight is higher, and its physical and mechanical property is better, more close to the requirement level of engineering materials.But molecular weight is higher, the difficulty of its processing also increases thereupon.Polyethylene fusing point is that its resistance to low temperature of 10-130C is excellent.At-60 DEG C, still can keep good mechanical property, but use temperature is at 80 ~ 110 DEG C.Polyethylene chemical stability is better, can the solution such as hydrochloric acid, hydrofluoric acid, phosphoric acid, formic acid, acetic acid, ammoniacal liquor, amine, hydrogen peroxide, sodium hydroxide, potassium hydroxide of resistance to dust technology, dilute sulphuric acid and any concentration under room temperature.But the not corrosion of powerful oxidation corrosion resistance, as the mixed solution of oleum concentrated nitric acid, chromic acid and sulfuric acid.At room temperature above-mentioned solvent can produce erosion action slowly to polyethylene, and at 90-100 DEG C, the vitriol oil and concentrated nitric acid can corrode polyethylene rapidly, make it destroy or decompose.Polyethylene, under the effect of air, sunlight and oxygen, can occur aging, variable color, chaps, becomes fragile or efflorescence, loses its mechanical property.At forming process temperature, also can, because of oxygenizement, its melt degree of killing be declined, variable color occur, occurs striped, so should give attention when forming process and use procedure or selection.Just because of polyethylene has as above speciality, easy machine-shaping, therefore poly regeneration is reclaimed and is had very far-reaching value.And popularizing along with humanity concept, and the formation of novel harmonious society, design high antibacterial PE of medical nano zinc oxide of a kind of intestinal bacteria antibiotic rate, streptococcus aureus antibiotic rate, tensile strength and shock strength and preparation method thereof and be very important.
Summary of the invention
the technical problem solved:
The application, for above-mentioned technical problem, provides antibacterial PE of a kind of medical nano zinc oxide and preparation method thereof, solves the technical problems such as existing medical novel material intestinal bacteria antibiotic rate, streptococcus aureus antibiotic rate, shock strength and tensile strength are low.
technical scheme:
The antibacterial PE of a kind of medical nano zinc oxide, the raw materials by weight portion proportioning of the antibacterial PE of described medical nano zinc oxide is as follows: PE100 part; Calcium carbonate 45-65 part; Cerium oxide 1-3 part; HDPE40-60 part; Nano zine oxide 1-5 part; DCP1-20 part; Oxidation inhibitor 0.05-0.2 part; Calcium stearate 0.3-0.7 part; EBS1.5-3.5 part; POE is 10-30 part; Coupling agent 2.5-4.5 part; CPE is 20-40 part; Barium stearate 0.5-2.5 part; Stearic acid 1-10 part; Zinic stearas is 1-3 part.
As a preferred technical solution of the present invention: the raw materials by weight portion proportioning of the antibacterial PE of described medical nano zinc oxide is as follows: PE100 part; Calcium carbonate 50-60 part; Cerium oxide 1.5-2.5 part; HDPE45-55 part; Nano zine oxide 2-4 part; DCP5-15 part; Oxidation inhibitor 0.1-0.15 part; Calcium stearate 0.4-0.6 part; EBS2-3 part; POE is 15-25 part; Coupling agent 3-4 part; CPE is 25-35 part; Barium stearate 1-2 part; Stearic acid 3-7 part; Zinic stearas is 1.5-2.5 part.
As a preferred technical solution of the present invention: the raw materials by weight portion proportioning of the antibacterial PE of described medical nano zinc oxide is as follows: PE100 part; 55 parts, calcium carbonate; Cerium oxide 2 parts; HDPE50 part; Nano zine oxide 3 parts; DCP10 part; 0.12 part, oxidation inhibitor; Calcium stearate 0.5 part; EBS2.5 part; POE is 20 parts; Coupling agent 3.5 parts; CPE is 30 parts; Barium stearate 1.5 parts; Stearic acid 5 parts; Zinic stearas is 2 parts.
As a preferred technical solution of the present invention: described oxidation inhibitor adopts antioxidant CA or anti-oxidant DLTP.
As a preferred technical solution of the present invention: described coupling agent adopts silane coupling agent or titanate coupling agent.
As a preferred technical solution of the present invention: the preparation method of the antibacterial PE of described medical nano zinc oxide, comprises the steps:
The first step: take PE, calcium carbonate, cerium oxide, HDPE, nano zine oxide, DCP, oxidation inhibitor, calcium stearate, EBS, POE, coupling agent, CPE, barium stearate, stearic acid and Zinic stearas according to parts by weight proportioning;
Second step: PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and is heated to 80-120 DEG C, stirring and drying 4-8h, stirring velocity 200-300 rev/min;
3rd step: then add surplus stock, be warming up to 100-140 DEG C, stirs 8-12h, stirring velocity 200-600 rev/min;
4th step: mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 100-120 rev/min, extruding pelletization, pellet 80-100 DEG C of oven dry.
beneficial effect:
Antibacterial PE of a kind of medical nano zinc oxide of the present invention and preparation method thereof adopts above technical scheme compared with prior art, has following technique effect: 1, product tensile strength 25-35MPa, elongation at break 40-80%; 2, intestinal bacteria antibiotic rate 99.5-99.9%, streptococcus aureus antibiotic rate 99.6-99.9%; 3, shock strength 13-17kJ/m 2, Vicat softening point 125-145 DEG C; 4, shore hardness 75-79, tear strength 36-40N/mm, the widespread production not division of history into periods can replace current material.
Embodiment
embodiment 1:
PE100 part is taken according to parts by weight proportioning; Carbonic acid Ca45 part; Cerium oxide 1 part; HDPE40 part; Nano zine oxide 1 part; DCP1 part; Anti-oxidant DLTP 0.05 part; Calcium stearate 0.3 part; EBS1.5 part; POE is 10 parts; Titanate coupling agent 2.5 parts; CPE is 20 parts; Barium stearate 0.5 part; Stearic acid 1 part; Zinic stearas is 1 part.
PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and be heated to 80 DEG C, stirring and drying 4h, stirring velocity 200 revs/min, then adds surplus stock, is warming up to 100 DEG C, stirs 8h, stirring velocity 200 revs/min.
Mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 100 revs/min, extruding pelletization, pellet 80 DEG C oven dry.
Product tensile strength 25MPa, elongation at break 40%; Intestinal bacteria antibiotic rate 99.5%, streptococcus aureus antibiotic rate 99.6%; Shock strength 13kJ/m 2, Vicat softening point 125 DEG C; Shore hardness 75, tear strength 36N/mm.
embodiment 2:
PE100 part is taken according to parts by weight proportioning; 65 parts, calcium carbonate; Cerium oxide 3 parts; HDPE60 part; Nano zine oxide 5 parts; DCP20 part; Anti-oxidant DLTP 0.2 part; Calcium stearate 0.7 part; EBS3.5 part; POE is 30 parts; Titanate coupling agent 4.5 parts; CPE is 40 parts; Barium stearate 2.5 parts; Stearic acid 10 parts; Zinic stearas is 3 parts.
PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and be heated to 120 DEG C, stirring and drying 8h, stirring velocity 300 revs/min, then adds surplus stock, is warming up to 140 DEG C, stirs 12h, stirring velocity 600 revs/min.
Mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 120 revs/min, extruding pelletization, pellet 100 DEG C oven dry.
Product tensile strength 28MPa, elongation at break 50%; Intestinal bacteria antibiotic rate 99.6%, streptococcus aureus antibiotic rate 99.7%; Shock strength 14kJ/m 2, Vicat softening point 130 DEG C; Shore hardness 76, tear strength 37N/mm.
embodiment 3:
PE100 part is taken according to parts by weight proportioning; 50 parts, calcium carbonate; Cerium oxide 1.5 parts; HDPE45 part; Nano zine oxide 2 parts; DCP5 part; Anti-oxidant DLTP 0.1 part; Calcium stearate 0.4 part; EBS2 part; POE is 15 parts; Silane coupling agent 3 parts; CPE is 25 parts; Barium stearate 1 part; Stearic acid 3 parts; Zinic stearas is 1.5 parts.
PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and be heated to 80 DEG C, stirring and drying 4h, stirring velocity 200 revs/min, then adds surplus stock, is warming up to 100 DEG C, stirs 8h, stirring velocity 200 revs/min.
Mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 105 revs/min, extruding pelletization, pellet 85 DEG C oven dry.
Product tensile strength 30MPa, elongation at break 60%; Intestinal bacteria antibiotic rate 99.7%, streptococcus aureus antibiotic rate 99.8%; Shock strength 15kJ/m 2, Vicat softening point 135 DEG C; Shore hardness 77, tear strength 38N/mm.
embodiment 4:
PE100 part is taken according to parts by weight proportioning; 60 parts, calcium carbonate; Cerium oxide 2.5 parts; HDPE55 part; Nano zine oxide 4 parts; DCP15 part; Antioxidant CA 0.15 part; Calcium stearate 0.6 part; EBS3 part; POE is 25 parts; Silane coupling agent 4 parts; CPE is 35 parts; Barium stearate 2 parts; Stearic acid 7 parts; Zinic stearas is 2.5 parts.
PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and be heated to 110 DEG C, stirring and drying 7h, stirring velocity 280 revs/min, then adds surplus stock, is warming up to 130 DEG C, stirs 11h, stirring velocity 500 revs/min.
Mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 115 revs/min, extruding pelletization, pellet 95 DEG C oven dry.
Product tensile strength 33MPa, elongation at break 70%; Intestinal bacteria antibiotic rate 99.8%, streptococcus aureus antibiotic rate 99.8%; Shock strength 16kJ/m 2, Vicat softening point 140 DEG C; Shore hardness 78, tear strength 39N/mm.
embodiment 5:
PE100 part is taken according to parts by weight proportioning; 55 parts, calcium carbonate; Cerium oxide 2 parts; HDPE50 part; Nano zine oxide 3 parts; DCP10 part; Antioxidant CA 0.12 part; Calcium stearate 0.5 part; EBS2.5 part; POE is 20 parts; Silane coupling agent 3.5 parts; CPE is 30 parts; Barium stearate 1.5 parts; Stearic acid 5 parts; Zinic stearas is 2 parts.
PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and be heated to 100 DEG C, stirring and drying 6h, stirring velocity 250 revs/min, then adds surplus stock, is warming up to 120 DEG C, stirs 10h, stirring velocity 400 revs/min.
Mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 110 revs/min, extruding pelletization, pellet 90 DEG C oven dry.
Product tensile strength 35MPa, elongation at break 80%; Intestinal bacteria antibiotic rate 99.9%, streptococcus aureus antibiotic rate 99.9%; Shock strength 17kJ/m 2, Vicat softening point 145 DEG C; Shore hardness 79, tear strength 40N/mm.
Composition all components in above embodiment all can business be bought.
Above-described embodiment is just for setting forth content of the present invention, instead of restriction, and any change therefore in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.

Claims (6)

1. the antibacterial PE of medical nano zinc oxide, is characterized in that the raw materials by weight portion proportioning of the antibacterial PE of described medical nano zinc oxide is as follows: PE100 part; Calcium carbonate 45-65 part; Cerium oxide 1-3 part; HDPE40-60 part; Nano zine oxide 1-5 part; DCP1-20 part; Oxidation inhibitor 0.05-0.2 part; Calcium stearate 0.3-0.7 part; EBS1.5-3.5 part; POE is 10-30 part; Coupling agent 2.5-4.5 part; CPE is 20-40 part; Barium stearate 0.5-2.5 part; Stearic acid 1-10 part; Zinic stearas is 1-3 part.
2. the antibacterial PE of a kind of medical nano zinc oxide according to claim 1, is characterized in that described medical nano zinc oxide antibacterial PE raw materials by weight portion proportioning is as follows: PE100 part; Calcium carbonate 50-60 part; Cerium oxide 1.5-2.5 part; HDPE45-55 part; Nano zine oxide 2-4 part; DCP5-15 part; Oxidation inhibitor 0.1-0.15 part; Calcium stearate 0.4-0.6 part; EBS2-3 part; POE is 15-25 part; Coupling agent 3-4 part; CPE is 25-35 part; Barium stearate 1-2 part; Stearic acid 3-7 part; Zinic stearas is 1.5-2.5 part.
3. the antibacterial PE of a kind of medical nano zinc oxide according to claim 1, is characterized in that the raw materials by weight portion proportioning of the antibacterial PE of described medical nano zinc oxide is as follows: PE100 part; 55 parts, calcium carbonate; Cerium oxide 2 parts; HDPE50 part; Nano zine oxide 3 parts; DCP10 part; 0.12 part, oxidation inhibitor; Calcium stearate 0.5 part; EBS2.5 part; POE is 20 parts; Coupling agent 3.5 parts; CPE is 30 parts; Barium stearate 1.5 parts; Stearic acid 5 parts; Zinic stearas is 2 parts.
4. the antibacterial PE of a kind of medical nano zinc oxide according to claim 1, is characterized in that: described oxidation inhibitor adopts antioxidant CA or anti-oxidant DLTP.
5. the antibacterial PE of a kind of medical nano zinc oxide according to claim 1, is characterized in that: described coupling agent adopts silane coupling agent or titanate coupling agent.
6. a preparation method of the antibacterial PE of medical nano zinc oxide described in claim 1, is characterized in that, comprise the steps:
The first step: take PE, calcium carbonate, cerium oxide, HDPE, nano zine oxide, DCP, oxidation inhibitor, calcium stearate, EBS, POE, coupling agent, CPE, barium stearate, stearic acid and Zinic stearas according to parts by weight proportioning;
Second step: PE, calcium carbonate, cerium oxide, HDPE and nano zine oxide are dropped in reactor and is heated to 80-120 DEG C, stirring and drying 4-8h, stirring velocity 200-300 rev/min;
3rd step: then add surplus stock, be warming up to 100-140 DEG C, stirs 8-12h, stirring velocity 200-600 rev/min;
4th step: mixed material is dropped in twin screw extruder, barrel temperature 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C, screw speed 100-120 rev/min, extruding pelletization, pellet 80-100 DEG C of oven dry.
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WO2017138716A1 (en) * 2016-02-11 2017-08-17 주식회사 아폴론 Composition for catheter and production method therefor
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KR102163875B1 (en) 2016-02-11 2020-10-12 (주)아폴론 Foley for Catheter
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KR20170094757A (en) * 2016-02-11 2017-08-21 (주)아폴론 Composition for Catheter Foley
KR20170094755A (en) * 2016-02-11 2017-08-21 (주)아폴론 Method for manufacturing Foley Catheter
CN108463489B (en) * 2016-02-11 2022-01-04 阿波罗恩有限公司 Composition for catheter and method for producing the same
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