CN113480799A - Medical EVA catheter material with surface frosted effect and preparation method and application thereof - Google Patents

Medical EVA catheter material with surface frosted effect and preparation method and application thereof Download PDF

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Publication number
CN113480799A
CN113480799A CN202110981422.1A CN202110981422A CN113480799A CN 113480799 A CN113480799 A CN 113480799A CN 202110981422 A CN202110981422 A CN 202110981422A CN 113480799 A CN113480799 A CN 113480799A
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eva
parts
ethylene
vinyl acetate
catheter
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CN113480799B (en
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刘永焯
龙木娣
黄健
诸泉
蒋文真
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Hecheng Technology Co ltd
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Hecheng Technology Co ltd
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    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a medical EVA catheter material with a surface frosted effect, and a preparation method and application thereof. The EVA is used as a main material, so that the material obtains proper flexibility and resilience; the antioxidant and the slipping agent are mixed with the polyolefin component for granulation, and then are mixed with the EVA in a master batch mode, so that the dispersing effect of the auxiliary agent is improved, and the uniform dispersion is ensured; the polyolefin material has a frosted effect and meets the market requirement; the long-chain nylon improves the corrosion resistance of the material and has better mechanical property; the graft of the ethylene-vinyl acetate copolymer improves the compatibility of the ethylene-vinyl acetate copolymer and the long-chain nylon. The medical EVA catheter material prepared by the invention has good flexibility and rebound resilience, is safe and nontoxic without adding a plasticizer, meets the requirements of catheters for conveying infusion medicines such as water aqua, fat emulsion, protein and the like, has better drug compatibility and application range than similar products made of PVC and TPE materials, and ensures the health and safety of patients.

Description

Medical EVA catheter material with surface frosted effect and preparation method and application thereof
Technical Field
The invention belongs to the technical field of modification of medical high polymer materials, and particularly relates to a medical EVA catheter material with a surface frosting effect, and a preparation method and application thereof.
Background
The current traditional medical infusion catheter material is polyvinyl chloride (PVC), and a plasticizer is required to be added, and researches show that the plasticizer can be separated out in the use process, and the plasticizer has definite or potential toxicity to a human body. In addition, PVC generates toxic gas of vinyl chloride in the production and recovery processes, and incineration treatment is adopted for waste treatment to easily generate highly toxic dioxin, so that the PVC material is not environment-friendly and is gradually prohibited from being used in developed countries. In addition, non-PVC TPE materials and TPU medical catheters are developed in the market at present, but the TPE materials are not resistant to corrosion of fat and protein solutions and are only suitable for aqueous infusion; the TPU material has high price and low yield, and is not suitable for general application at present.
EVA is ethylene-vinyl acetate copolymer, is a novel material which has soft touch, does not contain plasticizer, is environment-friendly and nontoxic, and has good weather resistance and chemical corrosion resistance. The EVA material has increased rebound resilience, flexibility and transparency along with the increase of the content of Vinyl Acetate (VA), and conversely, the rigidity and wear resistance are improved. Therefore, according to the difference of VA content of the material, the required performance can be obtained. Compared with PVC and TPE materials, the EVA catheter has the characteristic of chemical corrosion resistance, and is more suitable for fat and protein infusion than the PVC and TPE materials. The EVA material has high transparency, but the market also has great demand for products with frosted appearance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a medical EVA catheter material with a surface frosted effect.
The invention further aims to provide a preparation method of the medical EVA catheter material.
The invention also aims to provide application of the medical EVA catheter material.
The purpose of the invention is realized by the following technical scheme:
a medical EVA catheter material with a surface frosting effect comprises the following components in parts by mass: 70-95 parts of ethylene-vinyl acetate copolymer (EVA), 1-10 parts of ethylene-vinyl acetate copolymer graft, 1-10 parts of long carbon chain nylon, 1-20 parts of polyolefin, 0-1 part of slipping agent and 0.01-2 parts of antioxidant; preferably comprises the following components in parts by mass: 74-95 parts of ethylene-vinyl acetate copolymer, 1-8 parts of ethylene-vinyl acetate copolymer graft, 1-10 parts of long carbon chain nylon, 2-20 parts of polyolefin, 0.5 part of slipping agent and 0.2 part of antioxidant; more preferably comprises the following components in parts by mass: 78-95 parts of ethylene-vinyl acetate copolymer, 1-8 parts of ethylene-vinyl acetate copolymer graft, 2-7 parts of long carbon chain nylon, 2-10 parts of polyolefin, 0.5 part of slipping agent and 0.2 part of antioxidant.
The ethylene-vinyl acetate copolymer (EVA) is medical grade ethylene-vinyl acetate copolymer commonly used in the field, and can be prepared by mixing one or at least two ethylene-vinyl acetate. Wherein the EVA is EVA with the average mass percentage of ethyl acetate of 15-30% and the melt index of 1-10 g/10min at 190 ℃ and 2160 g; preferably, the EVA has the average mass percentage of 18-28% of ethyl acetate and the melt index of 2-7 g/10min at 190 ℃ and 2160 g; most preferably, the EVA has the average mass percentage of ethyl acetate of 20-25% and the melt index of 3-6 g/10min at 190 ℃ and 2160 g.
The ethylene-vinyl acetate copolymer graft is a graft of Maleic Anhydride (MAH) or Glycidyl Methacrylate (GMA) of an ethylene-vinyl acetate copolymer. Wherein the grafting rate of the ethylene-vinyl acetate copolymer graft is 0.3-2.0%, and the melt index is 1-10 g/10min at 190 ℃ and 2160 g; preferably, the grafting rate is 0.5-1.5%, and the melt index is 1.6-4.8 g/10min at 190 ℃ and 2160 g.
The long carbon chain nylon is a polyamide copolymer containing 10 or more carbon atoms of amide monomers commonly used in the field, or a polyester copolymer of long chain nylon containing 10 or more carbon atoms, and preferably one or more of nylon 11, nylon 12 or a polyester copolymer.
The long carbon chain nylon is preferably long carbon chain nylon with Shore hardness less than or equal to 72D; more preferably, the Shore hardness is 35-72D long carbon chain nylon.
The polyolefin is one or at least two of Polyethylene (PE), styrene elastomer (TPS), propenyl elastomer (POP) and vinyl elastomer (POE).
The polyethylene is preferably polyethylene with a melt index of 0.5-5 g/10min at 190 ℃ and 2160 g; more preferably polyethylene having a melt index of 2g/10min at 190 ℃ and 2160 g.
When the polyolefin is polyethylene, the amount of the polyethylene added is preferably 10 parts by mass.
The styrene elastomer is preferably a styrene-butadiene-styrene block copolymer; more preferably one or both of a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) and a hydrogenated styrene isoprene styrene block copolymer (SEPS).
The styrene elastomer is preferably a styrene elastomer with a molecular weight of 5-30 ten thousand; more preferably a styrene-based elastomer having a molecular weight of 9 to 10 ten thousand.
When the polyolefin is a styrene elastomer, the addition amount of the styrene elastomer is preferably 1-3 parts by mass; more preferably 2 parts by mass.
The propylene-based elastomer is a copolymer of propylene and ethylene, and preferably has a melt index of 2.2-8.3 g/10min at 230 ℃ and 2160 g.
When the polyolefin is an acryl-based elastomer, the amount of the acryl-based elastomer added is preferably 10 to 20 parts by mass.
The vinyl elastomer is a copolymer of ethylene and alpha-olefin; preferably, the melt index is 0.5-5 g/10min and the density is 0.880-0.908 g/cm under the conditions of 190 ℃ and 2160g3The vinyl elastomer of (1); more preferably at 190 ℃ and 2160gThe melt index under the part is 1-3 g/10min, and the density is 0.880-0.908 g/cm3The vinyl elastomer of (1).
When the polyolefin is a vinyl elastomer, the addition amount of the vinyl elastomer is preferably 3-13 parts by mass; more preferably 3 to 6 parts by mass.
The slipping agent is one or a mixture obtained by compounding at least two of amide slipping agents, organosilicon slipping agents and organic fluorine slipping agents.
The amide slipping agent is preferably one or two of erucamide and oleamide.
The organosilicon slipping agent is preferably graft modified organosilicon.
The grafted modified organic silicone is a special assistant for grafting a special functional group by silicone molecule reaction.
The organic fluorine slipping agent is preferably polytetrafluoroethylene particles; more preferably polytetrafluoroethylene fine particles having an average particle diameter of 5 μm or less; the polytetrafluoroethylene fine particles having an average particle diameter of 4 μm are most preferred.
The slipping agent is preferably a mixture obtained by compounding oleic acid amide, grafted modified organic silicone and polytetrafluoroethylene; most preferably, the mixture is prepared by mixing oleamide, grafted modified organic silicone and polytetrafluoroethylene according to the mass ratio of 1:7: 2.
The antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant; preferably a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168); more preferably a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1:1 to 1: 2; most preferably a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1: 1.
The preparation method of the medical EVA catheter material with the surface frosting effect comprises the following steps:
(1) uniformly mixing an antioxidant, a slipping agent and polyolefin to obtain a mixture;
(2) melting and mixing the mixture obtained in the step (1), and granulating to obtain an auxiliary agent master batch;
(3) uniformly mixing the auxiliary agent master batch obtained in the step (2), the ethylene-vinyl acetate copolymer graft and the long carbon chain nylon;
(4) and (4) melting and mixing the mixed material obtained in the step (3), granulating and drying to obtain the medical EVA catheter material with the surface frosted effect.
The rotation speed of the mixing in the step (1) and the step (3) is preferably 300-1500 r/min; more preferably 500-1000 r/min; most preferably 800 r/min.
The mixing time in the step (1) is preferably 3-6 min.
The melt-mixing described in step (2) is preferably carried out by means of a twin-screw extruder.
The melt mixing conditions are preferably as follows: controlling the temperature of a feeding section to be 120-160 ℃, a compression section to be 160-200 ℃, a metering section to be 170-210 ℃, the temperature of a neck ring mold to be 180-220 ℃, and the rotating speed of an extruder to be 150-300 rpm; more preferably as follows: the temperature is 130-150 ℃ in the feeding section, 170-190 ℃ in the compression section, 190-210 ℃ in the metering section, 180-200 ℃ in the neck ring mold, and the rotating speed of the extruder is 200-250 rpm.
The mixing time in the step (3) is preferably 2-5 min.
The melt-mixing described in step (4) is preferably carried out by means of a twin-screw extruder.
The melt mixing conditions are preferably as follows: controlling the temperature to be 90-150 ℃ in a feeding section, 150-220 ℃ in a compression section, 190-230 ℃ in a metering section, 190-220 ℃ in a neck ring mold, and controlling the rotating speed of an extruder to be 200-400 rpm; the preferable temperature is 90-110 ℃ in the feeding section, 160-180 ℃ in the compression section, 190-200 ℃ in the metering section, 200-210 ℃ in the neck ring mold, and 250-350 rpm in the rotating speed of the extruder.
The granulation mode in the step (2) and the step (4) is preferably an underwater granulation mode.
The medical EVA catheter material with the surface frosting effect has a melt index of 2.2-6.8 g/10min at 190 ℃ and 2160 g; more preferably 2.2 to 5.6g/10 min.
The medical EVA catheter material with the surface frosted effect is applied to preparation of medical EVA catheters.
A medical EVA catheter is prepared from the medical EVA catheter material with the surface frosted effect; preferably prepared by the following steps: and extruding the medical EVA catheter material with the surface frosted effect through a tube extruding machine to obtain the medical EVA catheter.
The temperature of the pipe extruding machine is preferably 100-110 ℃ in a feeding section, 140-150 ℃ in a compression section, 160-170 ℃ in a metering section, 150-160 ℃ in a flange, 155-165 ℃ in a machine head and 145-155 ℃ in a die.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts medical grade ethylene-vinyl acetate copolymer with proper VA content as main material, so that the material obtains proper flexibility and rebound resilience. The antioxidant and the slipping agent are mixed with the polyolefin component for granulation, and then are mixed with the EVA in a master batch mode, so that the dispersing effect of the auxiliary agent is improved, and the uniform dispersion is ensured. The added polyolefin material has good compatibility with the EVA material, ensures that the material has good performance, has higher melting point than the EVA material, can form a frosted effect in the pipe extruding process, and meets the market requirement. Because the polyolefin material is added, the protein and fat resistant infusion product is degraded, so that the corrosion resistance of the material is improved by adopting the long-chain nylon with better organic solvent resistance, and the adverse effect caused by adding the polyolefin material is compensated. Meanwhile, the long-chain nylon has better rebound resilience and toughness, so that the mechanical property of the material is improved. The compatibility of the ethylene-vinyl acetate copolymer and the long-chain nylon is improved by adopting the graft of the ethylene-vinyl acetate copolymer.
The double-screw extruder requires good temperature and screw rotating speed control in the pipe extruding process, so that good material plasticization is ensured, and the degree of oxidative decomposition is small. In addition, the temperature needs to be strictly controlled in the pipe extruding process, if the temperature is too high, the polyolefin material is well plasticized, the transparency of the conduit is high, and the sanding effect is poor; conversely, lower temperatures result in poor plasticization of the material, larger crystal points and possibly poor performance. The medical EVA catheter material prepared by the invention has good flexibility and rebound resilience, is safe and nontoxic without adding a plasticizer, meets the requirements of catheters for conveying infusion medicines such as water aqua, fat emulsion, protein and the like, has better drug compatibility and application range than similar products made of PVC and TPE materials, and ensures the health and safety of patients.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Polyester graft modified silicone TEGOMER H-Si 6441P, Germany winning industry group;
polytetrafluoroethylene (PTFE) MP1100E, american mu, average particle size 4 μm;
EVA (a) has a melt index of 7g/10min and a VA content of 18% measured at 190 ℃ and 2160 g;
EVA (b) has a melt index of 2g/10min and a VA content of 28% measured at 190 ℃ and 2160 g;
the grafting rate of the ethylene-vinyl acetate copolymer graft (EVA-g-MAH) is 0.5-1.8%, and the melt index is 1-5 g/10min under the conditions of 190 ℃ and 2160 g; preferably, the grafting rate is 0.8-1.5%, and the melt index is 2-5 g/10min at 190 ℃ and 2160 g.
Example 1:
(1) preparation of ethylene-vinyl acetate copolymer graft: 100 parts of EVA with the melt index of 7g/10min (190 ℃ and 2160g) is added with 0.06 part of ditertiary butyl peroxide DTBP and 0.62 part of maleic anhydride MAH, the mixture is melted and mixed by a double-screw extruder after being uniformly mixed, the temperature of the extruder is set to be 160 ℃, an underwater granulator is used for cooling and granulating, and then dehydration and drying are carried out, thus obtaining the ethylene-vinyl acetate copolymer maleic anhydride graft with the melt index of 4.8g/10min and the grafting rate of 0.5 percent under the conditions of 190 ℃ and 2160 g.
(2) 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (obtained by mixing the oleamide, the polyester grafted modified organic silicone and the polytetrafluoroethylene in a mass ratio of 1:7:2) and 10 parts of polyethylene (with a melt index of 2g/10min measured at 190 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion and granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 78 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 6g/10min (190 ℃, 2160g), the VA content is 20 percent, 6 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 0.5 percent), 6 parts of nylon 11 (France Acoma Rilsan BMNO MED, the Shore hardness is 68D) are uniformly mixed at a high speed (800r/min), and the mixture is put into a double-screw extruder, subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 2:
(1) preparation of ethylene-vinyl acetate copolymer graft: 100 parts of EVA with the melt index of 7g/10min (190 ℃ and 2160g) is added with 0.08 part of di-tert-butyl peroxide DTBP and 1.4 parts of maleic anhydride MAH, the mixture is melted and mixed by a double-screw extruder after being uniformly mixed, the temperature of the extruder is set to be 160 ℃, an underwater granulator is used for cooling and granulating, and then dehydration and drying are carried out, so as to obtain the EVA-g-MAH with the melt index of 3.5g/10min and the grafting rate of 1.0 percent under the conditions of 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (obtained by mixing the oleamide, the polyester grafted modified organic silicone and the polytetrafluoroethylene in a mass ratio of 1:7:2) and 7 parts of propenyl elastomer (with a melt index of 2.2g/10min measured at 230 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 86 parts of ethylene-vinyl acetate materials (EVA (a) and EVA (b)), the overall melt index of the mixture is 4.5g/10min, the VA content is 23 percent, 4 parts of ethylene-vinyl acetate copolymer graft (the melt index is 3.5g/10min and the grafting rate is 1.0 percent under the conditions of 190 ℃ and 2160g), 3 parts of nylon 12 (Arkema rilsamidanesed MED, France, the Shore hardness is 72D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder, and is subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 3:
(1) preparation of ethylene-vinyl acetate copolymer graft: 100 parts of EVA with the melt index of 7g/10min (190 ℃ and 2160g) is added with 0.07 part of di-tert-butyl peroxide DTBP and 1.1 parts of maleic anhydride, the mixture is melted and mixed by a double-screw extruder after being uniformly mixed, the temperature of the extruder is set to be 160 ℃, an underwater granulator is used for cooling and granulating, and then dehydration and drying are carried out to obtain EVA-g-MAH with the melt index of 4.3g/10min and the grafting rate of 0.8 percent under the conditions of 190 ℃ and 2160 g.
(2) By mass, the amount of the solvent to be added,0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (obtained by mixing oleamide, polyester graft modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 3 parts of vinyl elastomer (with the density of 0.908 g/cm)3Melt index of 1g/10min measured at 190 ℃ and 2160g), weighing at high speed (800r/min), uniformly mixing, putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary agent master batch is mixed with 88 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 3.5g/10min, the VA content is 25 percent, 4 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.3g/10min and the grafting rate is 0.8 percent under the conditions of 190 ℃ and 2160g), 5 parts of nylon and polyester copolymer (French Achima Pebax 4033SA01MED and the Shore hardness is 35D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 4:
(1) preparation of ethylene-vinyl acetate copolymer graft: 100 parts of EVA with the melt index of 7g/10min are added with 0.12 part of di-tert-butyl peroxide DTBP and 2.6 parts of maleic anhydride, the mixture is melted and mixed by a double-screw extruder after being uniformly mixed, the temperature of the extruder is set to be 160 ℃, an underwater granulator is used for cooling and granulating, and then dehydration and drying are carried out, so as to obtain the EVA-g-MAH with the melt index of 1.6g/10min and the grafting rate of 1.5 percent under the conditions of 190 ℃ and 2160 g.
(2) According to the mass ratio, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 6 parts of vinyl elastomer (with a melt index of 3g/10min and a density of 0.880g/cm measured at 190 ℃ and 2160g)3) Weighing, uniformly mixing at a high speed (800r/min), putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch and 79 parts of ethylene-vinyl acetate material (the melt index is 2g/10min under the conditions of 190 ℃ and 2160g, the VA content is 28%), 8 parts of ethylene-vinyl acetate copolymer graft (the melt index is 1.6g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 1.5%), 7 parts of nylon 11 (France Acoma Rilsan BMNO MED, the Shore hardness is 68D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder, and subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 5:
(1) preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 1, the obtained ethylene-vinyl acetate copolymer graft had a melt index of 4.8g/10min and a graft ratio of 0.5% EVA-g-MAH at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 2 parts of SEBS (molecular weight of about 9-10 ten thousand) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion and granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch and 95 parts of ethylene-vinyl acetate material (melting index is 7g/10min under 190 ℃ and 2160g, VA content is 18%), 1 part of ethylene-vinyl acetate copolymer graft (melting index is 4.8g/10min under 190 ℃ and 2160g, grafting ratio is 0.5%), 2 parts of nylon and polyester copolymer (France Achima Pebax 4033SA01MED, Shore hardness is 35D) are uniformly mixed at high speed (800r/min), and then the mixture is put into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 6:
(1) preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 1, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 4.8g/10min and a graft ratio of 0.5% at 190 ℃ and 2160 g.
(2) According to the mass ratio, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 13 parts of vinyl elastomer (with a melt index of 2.5g/10min measured at 190 ℃ and 2160g, and a density ofThe degree is 0.885g/cm3) Weighing, uniformly mixing at a high speed (800r/min), putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 74 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 3.0g/10min, the VA content is 26 percent, 3 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 0.5 percent), 10 parts of long carbon nylon and polyester copolymer (French Achima Pebax 4033SA01MED, the Shore hardness is 35D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Example 7:
(1) preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 3, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 4.3g/10min and a graft ratio of 0.8% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 20 parts of propenyl elastomer (with a melt index of 8.3g/10min measured at 230 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then placed in a double-screw extruder to be subjected to melt extrusion and granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 78 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the mixture is integrally molten for 5g/10min, the VA content is 22 percent, 1 part of ethylene-vinyl acetate copolymer graft (the melt index is 4.3g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 0.8 percent), 1 part of long carbon nylon 12 (Arkema Rilsamid AESNO MED, France, the Shore hardness is 72D), the mixture is uniformly mixed at a high speed (800r/min), and the mixture is placed into a double-screw extruder, and is subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 1
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 1, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 4.8g/10min and a graft ratio of 0.5% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 10 parts of polyethylene (with a melt index of 8.5g/10min measured at 190 ℃ and 2160g) are weighed, uniformly mixed at a high speed (800r/min), placed in a double-screw extruder and subjected to melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary agent master batch is mixed with 78 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 6g/10min, the VA content is 20 percent, 6 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 0.5 percent), 6 parts of long carbon nylon 11 (France Acoma Rilsan BMNO MED, the Shore hardness is 68D) is uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder, and is subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 2
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 2, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 3.5g/10min and a graft ratio of 1.0% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 15 parts of propenyl elastomer (with a melt index of 2.2g/10min measured at 230 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 78 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the mixture is integrally melted for 5g/10min, the VA content is 22 percent, 4 parts of ethylene-vinyl acetate copolymer graft (the melt index is 3.5g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 1.0 percent), 3 parts of nylon 12 (Arkema Rilsamid AESNO MED, France, the Shore hardness is 72D), the mixture is uniformly mixed at a high speed (800r/min), and the mixture is placed into a double-screw extruder, and is subjected to melt extrusion and underwater dicing to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 3
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 1, the obtained ethylene-vinyl acetate copolymer graft had a melt index of 4.8g/10min and a graft ratio of 0.5% at 190 ℃ and 2160 g.
(2) According to the mass ratio, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 13 parts of vinyl elastomer (with a melt index of 1.2g/10min measured at 190 ℃ and 2160g and a density of 0.862 g/cm)3) Weighing, uniformly mixing at a high speed (800r/min), putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 74 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)) to obtain a mixture, the overall melt index of the mixture is 3g/10min, the VA content is 26 percent, 3 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting rate is 0.5 percent), 10 parts of long carbon nylon and polyester copolymer (France Achima Pebax 4033SA01MED, the Shore hardness is 35D), the mixture is uniformly mixed at a high speed (800r/min), and the mixture is placed into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 4
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 4, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 1.6g/10min and a graft ratio of 1.5% at 190 ℃ and 2160 g.
(2) 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester graft modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 0.5 part of vinyl elastomer (with a melt index of 3g/10min measured at 190 ℃ and 2160g and a density of 0.880 g/cm)3) Weighing, uniformly mixing at a high speed (800r/min), putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary agent master batch is mixed with 84.5 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 4.5g/10min, the VA content is 23 percent, 8 parts of ethylene-vinyl acetate copolymer graft (the melt index is 1.6g/10min and the grafting rate is 1.5 percent under the conditions of 190 ℃ and 2160g), 7 parts of long carbon nylon 11 (Arkema Rilsan BMNO MED, France has Shore hardness of 68D) is uniformly mixed at high speed (800r/min), and then the mixture is put into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 5
(1) Preparation of ethylene-vinyl acetate copolymer graft: 100 parts of EVA with melt index of 7g/10min, 0.04 part of di-tert-butyl peroxide DTBP and 0.36 part of maleic anhydride are added, the mixture is melted and mixed by a double-screw extruder after being uniformly mixed, the temperature of the extruder is set to be 160 ℃, an underwater granulator is used for cooling and granulating, and then dehydration and drying are carried out, so as to obtain EVA-g-MAH with melt index of 5.4g/10min and grafting rate of 0.3% under the conditions of 190 ℃ and 2160 g.
(2) According to the mass ratio, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 3 parts of vinyl elastomer (with a density of 0.908 g/cm)3Melt index 1g/10min at 190 ℃ under 2.16 kg), weighing, uniformly mixing at high speed (800r/min), putting into a double-screw extruder, and performing melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary agent master batch is mixed with 88 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 3.5g/10min, the VA content is 25 percent, 4 parts of ethylene-vinyl acetate copolymer graft (the melt index is 5.4g/10min and the grafting rate is 0.3 percent under the conditions of 190 ℃ and 2160g), 5 parts of nylon and polyester copolymer (French Achima Pebax 4033SA01MED and the Shore hardness is 35D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder to be subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 6
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 3, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 4.3g/10min and a graft ratio of 0.8% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 7 parts of propenyl elastomer (with a melt index of 2.2g/10min measured at 230 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 86 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 4.5G/10min, the VA content is 23 percent, 4 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.3G/10min and the grafting rate is 0.8 percent under the conditions of 190 ℃ and 2160G), 3 parts of long carbon nylon 12 (Archama Rilsamid Clear G850 Rnmew D, France hardness is 78D), the mixture is uniformly mixed at a high speed (800r/min), and the mixture is placed into a double-screw extruder and subjected to melt extrusion and underwater dicing to obtain a required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 7
(1) Preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 3, the ethylene-vinyl acetate copolymer graft obtained had a melt index of 4.8g/10min and a graft ratio of 0.5% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 2 parts of SEBS (molecular weight of about 30-40 ten thousand) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion and granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary agent master batch is mixed with 95 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)), the overall melt index of the mixture is 7g/10min, the VA content is 18 percent, 1 part of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting ratio is 0.5 percent), 2 parts of nylon and polyester copolymer (France Achima Pebax 4033SA01MED, the Shore hardness is 35D) are uniformly mixed at a high speed (800r/min), and then the mixture is put into a double-screw extruder, and is subjected to melt extrusion and underwater grain cutting to obtain the required sample. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 100-110 ℃, the compression section is 140-150 ℃, the metering section is 160-170 ℃, the flange is 150-160 ℃, the machine head is 155-165 ℃ and the die is 145-155 ℃.
The above parts are all parts by mass.
Comparative example 8:
(1) preparation of ethylene-vinyl acetate copolymer graft: in the same manner as in example 1, the obtained ethylene-vinyl acetate copolymer graft had a melt index of 4.8g/10min and a graft ratio of 0.5% at 190 ℃ and 2160 g.
(2) According to the mass, 0.2 part of antioxidant (obtained by mixing the antioxidant 1010 and the antioxidant 168 in a mass ratio of 1: 1), 0.5 part of slipping agent (oleamide, polyester grafted modified organic silicone and polytetrafluoroethylene in a mass ratio of 1:7:2) and 10 parts of polyethylene (the melt index is 2g/10min measured at 190 ℃ and 2160g) are weighed and uniformly mixed at a high speed (800r/min), and then the mixture is placed into a double-screw extruder to be subjected to melt extrusion and granulation to obtain the auxiliary master batch. The parameters of the double-screw extruder are 140 ℃ in the feeding section, 180 ℃ in the compression section, 200 ℃ in the metering section, 190 ℃ in the neck mold, and the rotating speed of the extruder is 220rpm, so that the auxiliary master batch is obtained.
(3) The auxiliary master batch is mixed with 78 parts of ethylene-vinyl acetate material (EVA (a) and EVA (b)) to obtain a mixture, the overall melt index of the mixture is 6g/10min, the VA content is 20 percent, 6 parts of ethylene-vinyl acetate copolymer graft (the melt index is 4.8g/10min under the conditions of 190 ℃ and 2160g, the grafting rate is 0.5 percent), 6 parts of nylon 11 (Arkema Rilsan BMNO MED, France, the Shore hardness is 68D), the mixture is uniformly mixed at a high speed (800r/min), and the mixture is placed into a double-screw extruder to obtain a required sample after melt extrusion and underwater dicing. The parameters of the double-screw extruder are that the feeding section is 100 ℃, the compression section is 170 ℃, the metering section is 200 ℃, the neck mold temperature is 200 ℃, and the rotating speed of the extruder is 320 rpm. And granulating by underwater granulation and then drying to prepare the EVA catheter material sample.
(4) Processing the obtained sample in a tube extruding machine to obtain the EVA catheter, wherein the operation parameters are as follows: the feeding section is 125-135 ℃, the compression section is 175-185 ℃, the metering section is 175-185 ℃, the flange is 170-180 ℃, the nose is 175-185 ℃ and the die is 165-175 ℃.
The above parts are all parts by mass.
The materials prepared in the examples and comparative examples were injection molded into a template and a catheter having a 4mm inner diameter and 6.5mm outer diameter. The results of the performance test are shown in Table 1. The tensile strength is tested according to the method GB/T1040-2006, and the speed is 500 mm/min; the hardness is according to GB/T531.1-2008; separating out n-hexane according to GB/T5009.64-2003; the appearance of the catheter was observed using visual observation.
TABLE 1 parts by weight of the components and Process control
Figure BDA0003229156500000151
As can be seen from Table 1, the samples of examples 1-7 all have proper melt index, tensile strength, hardness and low n-hexane precipitate, are balanced in rigidity and toughness, meet the use requirements of EVA catheters, do not contain plasticizers in the components, and are high in safety. From the examples, the higher the content of PE/POE/POP/TPS, the higher the sanding level, wherein example 1 is the sanding level greater than example 7, and close to example 6, it can be seen that polyethylene is easier to produce the sanding effect than the propylene-based elastomer and the ethylene-based elastomer, while example 5 has the better sanding effect using only 2 parts of SEBS, indicating that the styrene-based elastomer has a very good function of producing the sanding effect. As can be seen from example 6, the higher the polyolefin component added, the greater the n-hexane precipitation, but at the same time the material hardness is lower; on the other hand, it is seen from examples 5 and 7 that when the content of the long carbon chain nylon is low, the precipitation of n-hexane is large and the hardness is low. Thus, the ratio of long carbon chain nylon to polyolefin can be increased or decreased depending on the requirements of the application.
The samples of comparative examples 1 to 8 have a problem that they are not suitable for preparing EVA catheters in various aspects. Comparative example 1 used a PE material with a large melt index, the material had a poor sanding effect, and the roundness of the molded catheter was insufficient; in comparative example 2, the POP material with an excessive proportion (15 parts) is added, the extruded conduit is excessively frosted obviously, the n-hexane precipitation amount is large, the tensile strength and the hardness are low, and the mechanical properties are not consistent; in comparative example 3, the POE material with lower density is used, so that the sanding effect is poor; comparative example 4, in which only 0.5 part of POE was added, the sanding effect was very poor; comparative example 5 used an EVA graft with a lower degree of grafting (0.30%) and the processability was poor. When the grafting degree of the EVA graft is lower, the compatibility of the EVA and the nylon elastomer is poor, so that the extrusion processability of the catheter is deteriorated; comparative example 6 long carbon chain nylon 12 with added hardness 78D, which has too high tensile strength and hardness, does not meet the mechanical performance requirements of the product; comparative example 7 used a high molecular weight (30 ten thousand) SEBS material with a matte surface that was too rough and had a strong grainy feel, again not meeting the requirements; comparative example 8 is based on example 1 and increases the processing temperature, again with insufficient sanding of the extruded tubing.
As can be seen from examples 1-7 and comparative examples 1-8, the medical EVA catheter material with the surface frosting effect, which is prepared by the method disclosed by the invention, has appropriate processability, mechanical property and solvent resistance. Under proper process parameters, the surface of the conduit produced by using the material has obvious and uniform frosting effect, no obvious crystal points, no sticky surface and less precipitation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A medical EVA catheter material with a surface frosting effect is characterized by comprising the following components in parts by mass: 70-95 parts of ethylene-vinyl acetate copolymer, 1-10 parts of ethylene-vinyl acetate copolymer graft, 1-10 parts of long carbon chain nylon, 1-20 parts of polyolefin, 0-1 part of slipping agent and 0.01-2 parts of antioxidant;
the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer which has the average mass percentage content of ethyl acetate of 15-30% and has the melt index of 1-10 g/10min at 190 ℃ and 2160 g;
the grafting rate of the ethylene-vinyl acetate copolymer graft is 0.3-2.0%, and the melt index is 1-10 g/10min at 190 ℃ and 2160 g;
the long carbon chain nylon is a polyamide copolymer with amide monomers containing 10 or more carbons or a polyester copolymer of long chain nylon with 10 or more carbons;
the slipping agent is one or a mixture obtained by compounding at least two of amide slipping agents, organosilicon slipping agents and organic fluorine slipping agents.
2. The medical EVA catheter material with surface frosting effect of claim 1, wherein:
the ethylene-vinyl acetate copolymer graft is a graft of maleic anhydride or glycidyl methacrylate of an ethylene-vinyl acetate copolymer;
the long carbon chain nylon has Shore hardness less than or equal to 72D;
the polyolefin is one or at least two of polyethylene, styrene elastomer, propenyl elastomer and vinyl elastomer.
3. The medical EVA catheter material with surface frosting effect of claim 2, wherein:
the polyethylene has a melt index of 0.5-5 g/10min at 190 ℃ and 2160 g;
the styrene elastomer is a styrene-butadiene-styrene block copolymer;
the styrene elastomer is a styrene elastomer with a molecular weight of 5-30 ten thousand;
the propylene-based elastomer is a copolymer of propylene and ethylene, and has a melt index of 2.2-8.3 g/10min at 230 ℃ and 2160 g;
the vinyl elastomer is a copolymer of ethylene and alpha-olefin at 190The melt index is 0.5-5 g/10min under the conditions of the temperature and 2160g, and the density is 0.880-0.908 g/cm3。
4. The medical EVA catheter material with surface frosting effect of claim 3, wherein:
the addition amount of the polyethylene is 10 parts by mass;
the addition amount of the styrene elastomer is 1-3 parts by mass;
the addition amount of the propylene-based elastomer is 10-20 parts by mass;
the addition amount of the vinyl elastomer is 3-13 parts by mass.
5. The medical EVA catheter material with surface frosting effect of claim 1, wherein:
the amide slipping agent is one or two of erucamide and oleamide;
the organic silicon slipping agent is graft modified organic silicone;
the organic fluorine slipping agent is polytetrafluoroethylene particles;
the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant.
6. The preparation method of the medical EVA catheter material with the frosted surface effect of any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) uniformly mixing an antioxidant, a slipping agent and polyolefin to obtain a mixture;
(2) melting and mixing the mixture obtained in the step (1), and granulating to obtain an auxiliary agent master batch;
(3) uniformly mixing the auxiliary agent master batch obtained in the step (2), the ethylene-vinyl acetate copolymer graft and the long carbon chain nylon;
(4) and (4) melting and mixing the mixed material obtained in the step (3), granulating and drying to obtain the medical EVA catheter material with the surface frosted effect.
7. The preparation method of the medical EVA catheter material with the frosted surface effect of claim 6, wherein the preparation method comprises the following steps:
the melting and mixing in the step (2) are carried out by a double-screw extruder; the melt mixing conditions were as follows: controlling the temperature of a feeding section to be 120-160 ℃, a compression section to be 160-200 ℃, a metering section to be 170-210 ℃, the temperature of a neck ring mold to be 180-220 ℃, and the rotating speed of an extruder to be 150-300 rpm;
the melt mixing in the step (4) is carried out by a twin-screw extruder: the melt mixing conditions were as follows: the temperature is controlled to be 90-150 ℃ in the feeding section, 150-220 ℃ in the compression section, 190-230 ℃ in the metering section, 190-220 ℃ in the neck ring mold, and the rotating speed of the extruder is 200-400 rpm.
8. The use of the medical EVA catheter material with frosted surface effect of any one of claims 1 to 5 in the preparation of a medical EVA catheter.
9. A medical EVA catheter is characterized in that: the medical EVA catheter material with the frosted surface effect is prepared from any one of claims 1-5.
10. The medical EVA catheter according to claim 9, characterized in that: the medical EVA catheter is prepared by the following steps: extruding the medical EVA catheter material with the frosted surface effect of any one of claims 1-5 through a tube extruding machine to obtain a medical EVA catheter;
the temperature of the pipe extruding machine is 100-110 ℃ in the feeding section, 140-150 ℃ in the compression section, 160-170 ℃ in the metering section, 150-160 ℃ in the flange, 155-165 ℃ in the machine head and 145-155 ℃ in the die.
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