CN111499988B - Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle - Google Patents

Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle Download PDF

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CN111499988B
CN111499988B CN202010397323.4A CN202010397323A CN111499988B CN 111499988 B CN111499988 B CN 111499988B CN 202010397323 A CN202010397323 A CN 202010397323A CN 111499988 B CN111499988 B CN 111499988B
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polyvinyl chloride
calcium
zinc
indwelling needle
soap
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CN111499988A (en
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杨华伟
栾世方
孙振龙
殷敬华
石恒冲
闫顺杰
张德海
黄尉
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Weigao Holding Co ltd
Changchun Institute of Applied Chemistry of CAS
Weihai Jierui Medical Products Co Ltd
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Weigao Holding Co ltd
Changchun Institute of Applied Chemistry of CAS
Weihai Jierui Medical Products 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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M39/00—Tubes, tube connectors, tube couplings, valves, access sites or the like, specially adapted for medical use
    • A61M39/10—Tube connectors; Tube couplings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/14—Infusion devices, e.g. infusing by gravity; Blood infusion; Accessories therefor
    • A61M5/158—Needles for infusions; Accessories therefor, e.g. for inserting infusion needles, or for holding them on the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/14—Infusion devices, e.g. infusing by gravity; Blood infusion; Accessories therefor
    • A61M5/158—Needles for infusions; Accessories therefor, e.g. for inserting infusion needles, or for holding them on the body
    • A61M2005/1587—Needles for infusions; Accessories therefor, e.g. for inserting infusion needles, or for holding them on the body suitable for being connected to an infusion line after insertion into a patient
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides modified polyvinyl chloride, a preparation method thereof, an irradiation-resistant sterilized venous indwelling needle connecting hose and an indwelling needle. According to the invention, polyvinyl chloride is used as a substrate, amorphous calcium silicate is used as an acid absorbent, triazine hindered amine is used, calcium soap, zinc soap, phosphite ester, a plasticizer, epoxy vegetable oil and an auxiliary stabilizer are matched and combined according to a certain proportion, the radiation resistance of the venous indwelling needle can be improved under the combined action of the components, and the problems of large pH change and large color yellowing of a product after radiation sterilization are solved. Meanwhile, the vein indwelling needle can be ensured not to be dissolved out of aluminum.

Description

Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle
Technical Field
The invention relates to the technical field of medical materials, in particular to modified polyvinyl chloride and a preparation method thereof, an irradiation-resistant sterilized venous indwelling needle connecting hose and an indwelling needle.
Background
The venous indwelling needle can greatly reduce the workload of venipuncture of nursing staff and reduce the pain of repeated venipuncture of patients, and becomes a medical instrument widely used by inpatients. At present, the venous indwelling needle is generally sterilized by ethylene oxide, and the ethylene oxide sterilization has the advantages of mild temperature condition and no or only small loss of the performance of high polymer materials. However, the venous indwelling needle is a mechanically sealed medical instrument (the structure is shown in fig. 1), the problem that ethylene oxide is difficult to completely resolve and attach after ethylene oxide sterilization exists, and the residual ethylene oxide inside the indwelling needle can cause potential harm to health of medical staff and patients.
Another safe and efficient sterilization method is to treat medical instruments with high-energy rays (such as gamma rays and electron beams), which can completely avoid the problem of ethylene oxide residues, but can cause great changes in the mechanical properties, chemical properties and appearance color of the polymer material.
The high polymer material for producing the venous retention needle mainly comprises polycarbonate, polyvinyl chloride, polyurethane, polyester, a perfluoroethylene propylene copolymer and butyl rubber, wherein the polycarbonate, the butyl rubber, the polyurethane, the polyester and the perfluoroethylene propylene copolymer have better high-energy ray irradiation resistance, only slight or less obvious changes of color and mechanical property are realized after irradiation sterilization, and the material with irradiation resistance can be purchased in the market. However, the high-energy ray irradiation resistance of the polyvinyl chloride extension hose is poor, and two problems exist after irradiation sterilization, firstly, the polyvinyl chloride is changed into dark yellow from transparent or light yellow and is gradually deepened into red, and the appearance of the product is seriously influenced; secondly, the polyvinyl chloride can release a large amount of hydrogen chloride after irradiation, and the hydrogen chloride is remained in the polyvinyl chloride hose and slowly released after meeting water, so that the pH value of water-soluble substances of the vein retention needle product is reduced more and exceeds the limit of national standards.
Modification of the raw materials for making the connection hose is generally considered first to make an irradiation resistant venous retention needle, such as using thermoplastic polyolefin elastomer materials and thermoplastic polyurethane materials with excellent irradiation resistance properties in place of soft polyvinyl chloride. However, this presents three problems: firstly, in the aspect of raw material cost, the price of the two materials is 4-20 times of that of the soft polyvinyl chloride; secondly, in the bonding between the pipes/joints, the thermoplastic polyolefin elastomer has low surface energy and is difficult to bond, and the geometric structure of the joint must be redesigned in order to obtain a satisfactory bonding force; finally, these two materials place high demands on the professional level of the processing and pipe extrusion technicians. Therefore, the improvement of the radiation-resistant sterilization performance of the soft polyvinyl chloride raw material is the best choice for preparing the radiation-resistant venous indwelling needle.
In view of the importance of the medical polyvinyl chloride with radiation-resistant sterilization, various published technical schemes are provided at home and abroad. U.S. Pat. No. US2014/0162045 teaches that decreasing the amount of calcium/zinc stabilizer added and adding a small amount of inorganic blue pigment at the same time can increase the radiation coloration of polyvinyl chloride, but this method is not favorable for controlling the pH change of polyvinyl chloride at a low level after radiation sterilization, and in addition, the inorganic blue pigment may contain heavy metals, and China has begun to limit its use in medical polymer materials. U.S. patent publication No. US7053139 teaches that the use of phthalide and its derivatives can reduce the yellowness index of polyvinyl chloride after irradiation. U.S. patent publication No. US5955519 teaches the use of aliphatic plasticizers to increase the radiation resistance of polyvinyl chloride. Chinese patent application publication No. CN102827437A proposes to use hindered phenols and phosphites in combination to increase the radiation resistance of polyvinyl chloride. Chinese patent application publication No. CN101962460A proposes the use of 2-nitro-2 '-hydroxy-5' -methylazobenzene as a high-energy radiation absorber to improve the radiation resistance of polyvinyl chloride. The Chinese patent application with the publication number of CN104072915A proposes that the radiation resistance of polyvinyl chloride is improved by compounding an ultraviolet absorbent, a hindered phenol antioxidant and a phosphite antioxidant. However, none of the above-disclosed techniques solves the problem of pH reduction after polyvinyl chloride irradiation. In addition, the existing acid absorbent suitable for polyvinyl chloride comprises magnesium aluminum hydrotalcite, magnesium aluminum zinc hydrotalcite, magnesium calcium carbonate and magnesium calcium silicate (US 6288155). Among them, hydrotalcite acid absorbent does not affect transparency of polyvinyl chloride, but has a problem of dissolution of aluminum (aluminum has high nephrotoxicity), while calcium magnesium carbonate and calcium magnesium silicate affect transparency of polyvinyl chloride, and are not suitable for preparing a connection hose.
Therefore, the above prior art cannot solve the problems of large pH value change and large yellowing of appearance after polyvinyl chloride irradiation sterilization and aluminum dissolution well at the same time.
Disclosure of Invention
In view of the above, the invention aims to provide modified polyvinyl chloride and a preparation method thereof, an irradiation-resistant sterilized venous indwelling needle connecting hose and an indwelling needle. The modified polyvinyl chloride provided by the invention can effectively improve the irradiation resistance of the venous indwelling needle, overcomes the problems of large pH change and large color yellowing of products after irradiation sterilization, and does not dissolve out aluminum.
The invention provides modified polyvinyl chloride which is prepared from the following materials in parts by mass:
Figure BDA0002488075130000031
the hindered amine is a hindered amine having a triazine structure.
Preferably, in the amorphous calcium silicate, the molar ratio of silicon to calcium is (1-3) to 1;
the particle size of the amorphous calcium silicate is below 50 mu m.
Preferably, the amorphous calcium silicate is obtained by:
mixing sodium metasilicate nonahydrate and calcium nitrate tetrahydrate in water for reaction to generate amorphous calcium silicate.
Preferably, the calcium soap is selected from one or more of C4-C22 fatty acid calcium;
the zinc soap is selected from one or more of C4-C22 fatty acid zinc;
the molar ratio of the calcium soap to the zinc soap is 1: 1.5-3.0.
Preferably, the auxiliary stabilizer is stearoylbenzoylmethane and 1, 4-dihydro-3, 5-diacetic acid lauryl ester-2, 6-dimethylpyridine;
the hindered amine is selected from one or more of light stabilizer 944, Chiguard 106, Chiguard 228 and Chiguard 088.
Preferably, the primary plasticizer is selected from one or more of alkyl acid ester plasticizer and polyester plasticizer;
the alkyl acid ester plasticizer is selected from one or more of phthalate, terephthalate, trimellitate, citrate, cyclohexane diformate, adipate and sebacate;
the calcium soap is selected from one or more of calcium isooctanoate, calcium neodecanoate, calcium naphthenate, calcium stearate and calcium octadecanoxystearate;
the zinc soap is selected from one or more of zinc isooctanoate, zinc neodecanoate, zinc naphthenate, zinc stearate and zinc octohydroxystearate.
Preferably, the epoxidized vegetable oil is epoxidized soybean oil and/or epoxidized linseed oil;
the phosphite ester is alkylphenol phosphite ester.
The invention also provides a preparation method of the modified polyvinyl chloride in the technical scheme, which comprises the following steps:
and (2) carrying out melt extrusion granulation on polyvinyl chloride, a main plasticizer, epoxy vegetable oil, calcium soap, zinc soap, hindered amine, phosphite ester, amorphous calcium silicate and an auxiliary stabilizer to obtain modified polyvinyl chloride granules.
The invention also provides an irradiation-resistant venous indwelling needle connecting hose which is prepared from the modified polyvinyl chloride in the technical scheme or the modified polyvinyl chloride prepared by the preparation method in the technical scheme.
The invention also provides an irradiation-resistant venous indwelling needle, wherein the connecting hose in the indwelling needle is the connecting hose in the technical scheme.
According to the invention, polyvinyl chloride is used as a substrate, amorphous calcium silicate is used as an acid absorbent, triazine hindered amine is used, calcium soap, zinc soap, phosphite ester, a plasticizer, epoxy vegetable oil and an auxiliary stabilizer are matched and combined according to a certain proportion, the radiation resistance of the venous indwelling needle can be improved under the combined action of the components, and the problems of large pH change and large color yellowing of a product after radiation sterilization are solved. Meanwhile, the vein indwelling needle can be ensured not to be separated out of aluminum.
Test results show that the modified polyvinyl chloride can improve the irradiation resistance of PVC products, and the yellowness index is obviously lower (below 8) and basically does not yellow after irradiation; meanwhile, the pH change of the connecting hose and the indwelling needle (the absolute value of the pH change of the connecting hose is less than 1.1, and the absolute value of the pH change of the indwelling needle is less than 1) can be effectively reduced, and no aluminum is dissolved out, so that the safety is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic structural view of a venous indwelling needle.
Detailed Description
The invention provides modified polyvinyl chloride which is prepared from the following materials in parts by mass:
Figure BDA0002488075130000051
the hindered amine is a hindered amine having a triazine structure.
According to the invention, polyvinyl chloride is used as a substrate, amorphous calcium silicate is used as an acid absorbent, triazine hindered amine is used in combination with calcium soap, zinc soap, phosphite ester, a plasticizer, epoxy vegetable oil and an auxiliary stabilizer according to a certain proportion, and under the combined action of the components, the radiation resistance of the venous retention needle can be improved on the basis of ensuring the basic thermal stability of a hose product, and the problems of large pH change and large color yellowing of the product after radiation sterilization are solved. Meanwhile, the vein indwelling needle can be ensured not to be separated out of aluminum.
In the present invention, the polyvinyl chloride is preferably suspended polyvinyl chloride powder, which is capable of rapidly absorbing the plasticizer. The polyvinyl chloride is not particularly limited in source, and can be a general commercial product.
In the invention, the main plasticizer is preferably one or more of alkyl acid ester plasticizer and polyester plasticizer, which can reduce the hardness of PVC and improve the resilience of the PVC. Wherein the alkyl acid ester plasticizer is selected from one or more of phthalate, terephthalate, trimellitate, citrate, cyclohexane diformate, adipate and sebacate; in some embodiments of the invention, specifically di-isooctyl phthalate. The polyester plasticizer is a low molecular weight polyester plasticizer, and specifically is a polyester plasticizer with the number average molecular weight of 1500-3000 g/mol. In the present invention, the source of the plasticizer is not particularly limited, and may be any commercially available product.
Based on 100 parts by mass of polyvinyl chloride, the amount of the main plasticizer is 30-80 parts. Although plasticizers are essential components of flexible polyvinyl chloride, increasing the amount of plasticizer added generally helps to reduce the yellowness index, possibly due to the dilution effect of the plasticizer, but is added in an amount that ensures that the mechanical properties of the flexible polyvinyl chloride meet the application requirements, in some embodiments of the invention the primary plasticizer is used in an amount of 55 parts.
In the present invention, the epoxidized vegetable oil is preferably epoxidized soybean oil and/or epoxidized linseed oil; the epoxy value of the epoxidized linseed oil is significantly higher than that of the epoxidized soybean oil, so when the epoxidized linseed oil is used, the addition amount is generally less than that of the epoxidized soybean oil, but the cost of the epoxidized linseed oil is more than four times that of the epoxidized soybean oil, and under the condition of the same addition amount of epoxy, the difference of the effects of the epoxidized soybean oil and the epoxidized soybean oil is not significant, and the epoxidized soybean oil is more preferable in terms of cost. The epoxy vegetable oil is introduced into the preparation system, so that the release amount of hydrogen chloride can be reduced, the pH change amplitude and yellowing property can be reduced, and the storage stability of PVC can be improved during irradiation sterilization.
The using amount of the epoxy vegetable oil is 2.0-10.0 parts by weight based on 100 parts by weight of the polyvinyl chloride; if the dosage is less than 2.0 parts, the yellowing is high after irradiation, and if the dosage is more than 10.0 parts, the risk of PVC surface precipitation is easily increased. In the invention, the amount is preferably 4.0-6.0 parts. In some embodiments of the invention, it is used in an amount of 5.0 parts.
In the invention, the calcium soap is selected from one or more of C4-C22 fatty acid calcium; more preferably one or more of calcium isooctanoate, calcium neodecanoate, calcium naphthenate, calcium stearate and calcium octadecanoxystearate. Among them, the synthetic fatty acid calcium soaps such as calcium iso-octoate, calcium neodecanoate and calcium naphthenate are generally highly viscous liquids, material taking is difficult in the mixing process, and the raw material residual rate is difficult to control in the synthesis process, so the invention most preferably adopts calcium stearate and/or calcium octadecanoxystearate based on the biological safety, purity, operation convenience and wide source of the raw materials. In the examples of the present invention, calcium stearate was used.
The using amount of the calcium soap is 0.05-0.30 part by weight based on 100 parts by weight of polyvinyl chloride. If the amount is less than 0.05 part, the long-term stability of polyvinyl chloride is deteriorated, and if it is more than 0.30 part, the initial transparency is lowered. In the present invention, the calcium soap is preferably used in an amount of 0.15 to 0.25 parts. In some embodiments of the invention, it is used in an amount of 0.18 parts.
In the invention, the zinc soap is selected from one or more of C4-C22 fatty acid zinc; more preferably one or more of zinc isooctanoate, zinc neodecanoate, zinc naphthenate, zinc stearate and zinc octohydroxystearate. Among them, zinc stearate and/or zinc octadecanoxystearate are most preferably used in the present invention based on the biological safety, purity, convenience of operation and wide source of raw materials. In some embodiments of the invention, zinc stearate is employed.
The zinc soap is used in an amount of 0.05-0.40 part, more preferably 0.20-0.30 part, based on 100 parts by mass of the polyvinyl chloride, and the release amount and yellowing of the polyvinyl chloride can be better reduced by adopting the higher addition amount, but the higher zinc soap addition amount can cause higher zinc ion elution amount, so that the zinc ion elution amount is ensured to meet the national standard GB/T15593 by controlling the zinc soap in the range. In some embodiments of the invention, it is used in an amount of 0.30 parts.
In the invention, the calcium soap and the zinc soap act synergistically to improve the irradiation resistance of the polyvinyl chloride. Wherein the molar ratio of the calcium soap to the zinc soap is 1 to (1.5-3.0), and preferably 1 to (1.5-2.0). If the molar ratio of the two components is higher than 1: 1.5, the initial yellowness index of the polyvinyl chloride hose is higher, and the yellowness index after irradiation is higher, and if the molar ratio is lower than 1: 3.0, the polyvinyl chloride hose has poor 180 ℃ thermal stability which is lower than 40min, and the requirements of national standard GB/T15593 are difficult to achieve. In some embodiments of the invention, the calcium soap: the molar ratio of the zinc soap is 1: 1.6.
in the invention, the hindered amine is the hindered amine with a triazine structure, and compared with other conventional light stabilizers or antioxidants, the radiation resistance of the polyvinyl chloride hose can be better improved only by adopting the triazine-based hindered amine, and in the system, the cascade oxidation reaction of free radicals generated by irradiation can be stopped, the continuous oxidative degradation reaction of polyvinyl chloride and a plasticizer during storage after irradiation is inhibited, and the radiation resistance of the polyvinyl chloride hose is improved; if carbonyl hindered amine (such as light stabilizer 622, light stabilizer 770, etc.) or hindered phenol antioxidant (such as antioxidant 1076, antioxidant 1010, etc.) is adopted, the yellowness index after irradiation is higher, and the problem of yellowing of polyvinyl chloride hose after irradiation cannot be solved. In the invention, the hindered amine is preferably high molecular weight triazine-based hindered amine, which can further reduce the release amount of hydrogen chloride and improve the pH value stability. More preferably, the hindered amine is one or more of a photostabilizer 944, Chiguard 106, Chiguard 228 and Chiguard 088. In an embodiment of the present invention, a light stabilizer 944 is used.
The amount of the hindered amine is 0.05-0.20 part by mass based on 100 parts by mass of the polyvinyl chloride. In the examples of the present invention, the hindered amine is used in an amount of 0.10 parts.
In the invention, the phosphite ester is preferably alkylphenol phosphite ester, compared with other conventional phosphite esters, the radiation yellowing of the polyvinyl chloride hose can be better improved and the long-term stability can be kept by adopting the alkylphenol phosphite ester, if the alkyl phosphite ester (such as tributyl phosphite, triisooctyl phosphite, trilauryl phosphite and the like) is adopted, the radiation yellowing of the polyvinyl chloride hose is not obviously improved, and the polyvinyl chloride hose is easy to separate out or volatilize, if the phenol phosphite ester (such as antioxidant 168 and the like) is adopted, the yellowness index of the polyvinyl chloride hose after radiation is obviously increased, and the radiation yellowing resistance is reduced. In the present invention, the alkylphenol-based phosphite is preferably one or more of 4, 4-diisopropybi (12-14) carbonate phosphite, diisooctyl monobenzophosphite, antioxidant 626 and ADK STAB HP-10, and most preferably 4, 4-diisopropybi (12-14) carbonate phosphite for reasons of cost and safety.
The amount of the phosphite ester is 0.1-1.0 part, preferably 0.3-0.6 part, based on 100 parts by mass of the polyvinyl chloride. If the amount is less than 0.1 part, it is difficult to control oxidative degradation of PVC and plasticizer by irradiation, and improvement of irradiation resistance cannot be achieved, and if it is more than 1.0 part, precipitation risk increases.
Compared with other conventional acid absorbents, the radiation resistance can be better improved only by adopting the amorphous calcium silicate, the polyvinyl chloride hose is prevented from generating larger pH value reduction after irradiation, and meanwhile, the metal ions can be prevented from being separated out and the transparency of the hose can be ensured. If the common hydrotalcite acid absorbent is adopted, the precipitation of toxic metal ions such as aluminum, zinc and the like is easy to occur, and if the magnesium calcium carbonate or magnesium calcium silicate acid absorbent is adopted, the transparency of the polyvinyl chloride hose is influenced.
In the amorphous calcium silicate, the molar ratio of silicon to calcium is preferably (1-3) to 1; if the molar ratio is higher than 3: 1, the acid absorption capacity is lowered.
In the present invention, the amorphous calcium silicate is preferably obtained by: mixing sodium metasilicate nonahydrate and calcium nitrate tetrahydrate in water for reaction to generate amorphous calcium silicate.
Wherein, the addition amount of the two reaction raw materials is based on the molar ratio of silicon to calcium in the target product. The mixing operation is particularly preferably as follows: dissolving sodium metasilicate nonahydrate in water to obtain a sodium metasilicate solution; dissolving calcium nitrate tetrahydrate in water to obtain a calcium nitrate solution; then, the calcium nitrate solution is dripped into the sodium metasilicate solution for reaction. The mass concentration of the sodium metasilicate solution is preferably 5-15%; the mass concentration of the calcium nitrate solution is preferably 5-15%. Stirring is preferably carried out in the dropping process; after the dropwise addition is finished, stirring and reacting are preferably continued for a period of time; the temperature of the dropwise adding process and the continuous reaction after the dropwise adding is finished is not particularly limited, and the reaction can be carried out at room temperature, specifically 5-35 ℃. After the dropwise addition is finished, the continuous stirring reaction time is preferably 2-6 h. In the course of the above-mentioned mixing reaction, amorphous calcium silicate is formed.
After the above reaction, it is preferable to further perform aging. The temperature of the aging is not particularly limited, and the aging can be carried out at room temperature, specifically 5-35 ℃. The aging time is preferably 2-6 h. After the above aging, preferably, solid-liquid separation is further performed; the solid-liquid separation is preferably centrifugal separation. After the above solid-liquid separation, it is preferable to further perform washing, drying and pulverization. The washing is preferably distilled water washing. The drying temperature is preferably 100-150 ℃. After drying and crushing, the particle size of amorphous calcium silicate is preferably controlled below 50 μm, and if the particle size is higher than 50 μm, the surface smoothness of the polyvinyl chloride hose is influenced; therefore, after being crushed, the amorphous calcium silicate with the required granularity is obtained by sieving with a 1000-mesh sieve.
The dosage of the amorphous calcium silicate is 0.1-1.0 part by weight, preferably 0.3-0.5 part by weight based on 100 parts by weight of polyvinyl chloride. If the amount is less than 0.1 part, it is difficult to sufficiently absorb hydrogen chloride released during irradiation sterilization, and it is impossible to effectively control the pH change, and if it is more than 0.50 part, it slightly increases the yellowness index of the polyvinyl chloride hose after irradiation sterilization. In some embodiments of the invention, the amorphous calcium silicate is used in an amount of 0.15 parts, 0.30 parts, or 0.60 parts.
In the invention, the auxiliary stabilizer is preferably stearoylbenzoylmethane and 1, 4-dihydro-3, 5-diacetic acid lauryl ester-2, 6-dimethylpyridine, so that the thermal stability of the polyvinyl chloride hose can be improved, and the initial coloring can be reduced.
The amount of the auxiliary stabilizer is 0.10-1.00 parts by weight, preferably 0.20-0.60 part by weight, based on 100 parts by weight of the polyvinyl chloride. The dosage of the stearoylbenzoylmethane is preferably 0.05-0.50 parts, and more preferably 0.10-0.30 parts; in some embodiments of the invention, it is used in an amount of 0.30 parts. The dosage of the 1, 4-dihydro-3, 5-diacetic acid lauryl alcohol ester-2, 6-dimethyl pyridine is 0.05 to 0.50 part, and the more preferable dosage is 0.10 to 0.30 part; in some embodiments of the invention, it is used in an amount of 0.30 parts.
The modified polyvinyl chloride provided by the invention takes polyvinyl chloride as a substrate, amorphous calcium silicate as an acid absorbent, triazine hindered amine as well as calcium soap, zinc soap, phosphite ester, plasticizer, epoxy vegetable oil and auxiliary stabilizer, and under the combined action of the components, the radiation resistance of the venous retention needle can be improved on the basis of ensuring the basic thermal stability of a hose product, and the problems of large pH change and large color yellowing of the product after radiation sterilization are solved. Meanwhile, the venous indwelling needle can be ensured not to be separated out and the transparency of the connecting hose can be ensured. The hose prepared from the modified polyvinyl chloride has the advantages of light color after irradiation, no pH change, no aluminum dissolution, no reduced ethane residue and the like, and is safer for human bodies.
The invention also provides a preparation method of the modified polyvinyl chloride in the technical scheme, which comprises the following steps:
and (2) carrying out melt extrusion granulation on polyvinyl chloride, a main plasticizer, epoxy vegetable oil, calcium soap, zinc soap, hindered amine, phosphite ester, amorphous calcium silicate and an auxiliary stabilizer to obtain modified polyvinyl chloride granules.
The types, the amounts, the sources and the like of the raw materials are consistent with those in the technical scheme, and are not described in detail herein.
In the invention, the materials are preferably mixed in a high-speed mixer, the mixing is stopped when the temperature is raised to 110-135 ℃, and then the mixture is cooled to below 60 ℃ to obtain the dry powder. Then, the obtained dry powder is subjected to melt extrusion granulation. Wherein the melt extrusion can be carried out by means of a twin-screw extruder. The extrusion temperature is preferably 160-175 ℃, and the die temperature is preferably 155-165 ℃. And obtaining the modified PVC granules after melt extrusion.
The invention also provides an irradiation-resistant venous indwelling needle connecting hose which is prepared from the modified polyvinyl chloride in the technical scheme or the modified polyvinyl chloride prepared by the preparation method in the technical scheme.
The invention also provides an irradiation-resistant venous indwelling needle, wherein the connecting hose in the indwelling needle is the connecting hose in the technical scheme.
In the present invention, the irradiation-resistant venous indwelling needle comprises: an indwelling needle sleeve, a sleeve seat, a puncture needle, a needle arranging device, a hemostatic plug, a connecting hose (or called an extension hose), a hemostatic clamp, a tee joint and a heparin cap. The structure is shown in fig. 1, and fig. 1 is a schematic structural view of a venous indwelling needle; wherein, 1 is a heparin cap, 2 is a tee joint, 3 is a connecting hose, 4 is a hemostatic clip, 5 is a protective cap, 6 is a needle handle, 7 is a hemostatic plug, 8 is a clockwise needle device, 9 is a cannula seat, 10 is an indwelling needle cannula, 11 is a puncture needle, and 12 is a protective sleeve.
In some embodiments, the cannula holder 9 is a polycarbonate cannula holder, the tee junction 2 is a polycarbonate tee junction, the tampon 7 is a butyl rubber tampon, the indwelling needle cannula 10 is a polyurethane cannula or a perfluoroethylene propylene copolymer cannula, the puncture needle 11 is a stainless steel puncture needle, the protective cap 5 is a polyethylene protective cap, the hemostatic clip 4 is a polyacrylonitrile-butadiene-styrene hemostatic clip, the needle handle 6 is a polyacrylonitrile-butadiene-styrene needle handle, the needle follower 8 is a stainless steel needle follower, and the heparin cap 1 is a butyl rubber heparin cap.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples and comparative examples, the raw materials were mainly commercially available, wherein the suspended polyvinyl chloride powder was Taiwan co-chemical company US-70, epoxidized soybean oil was obtained from Guangzhou Haima, stearoylbenzoylmethane was obtained from Anhui first functional adjuvant, 1, 4-dihydro-3, 5-diacetic acid lauryl ester-2, 6-lutidine was obtained from Tianjin Mao Sen chemical product, hindered amine 944 was obtained from Beijing very easily chemical product, phosphite was obtained from Taiwan Catharan chemical product, and hydrotalcite magnesium aluminum was obtained from Guangzhou province and science and technology company.
Example 1
1422.0g of sodium metasilicate nonahydrate and 1180.8g of calcium nitrate tetrahydrate are weighed according to the molar ratio of silicon to calcium of 1: 1 and respectively dissolved in 10L of distilled water to obtain a calcium nitrate solution and a sodium metasilicate nonahydrate solution. Slowly and dropwise adding the obtained calcium nitrate solution into a sodium metasilicate nonahydrate solution under high-speed stirring (400rpm), continuously stirring and reacting for 4 hours after dropwise adding is finished (the whole process is carried out at the room temperature of 20 +/-5 ℃), then aging for 6 hours at the room temperature, washing for three times by using distilled water after centrifugal separation, drying at the temperature of 110 ℃, and crushing and sieving by using a 1000-mesh sieve to obtain amorphous calcium silicate (Si/Ca is 1: 1).
On the basis of the preparation method, the raw material ratio is adjusted to prepare amorphous calcium silicate with other Si/Ca ratios for subsequent examples and comparative examples.
Example 2
1.1 starting materials
Figure BDA0002488075130000111
1.2 preparation
S1, putting the raw materials into a high-speed mixer, stopping mixing when the temperature rises to 130 ℃, discharging the materials into a cooling machine, and cooling the materials to below 60 ℃ to obtain dry powder.
S2, granulating the dry powder through a conical double-screw extruder, setting the extrusion temperature from a feeding port to a neck mold to be 160 ℃, 170 ℃, 175 ℃, 165 ℃ and 155 ℃, and performing melt extrusion to obtain the radiation-resistant modified PVC granules.
S3, preparing the modified PVC granules into a connecting hose with the outer diameter of 2.05 +/-0.05 mm and the inner diameter of 1.00 +/-0.05 mm by a tube drawing machine.
The venous indwelling needle was assembled according to fig. 1 using the above-described connecting hose. The results of the tests relating to the pH value, yellowness index, aluminium content, etc. of the water extract after radiation sterilization are shown in Table 1.
Example 3
1.1 starting materials
Figure BDA0002488075130000112
Figure BDA0002488075130000121
1.2 preparation: the same as in example 2.
Example 4
1.1 starting materials
Figure BDA0002488075130000122
1.2 preparation: the same as in example 2.
Example 5
1.1 starting materials
Figure BDA0002488075130000123
Figure BDA0002488075130000131
1.2 preparation: the same as in example 2.
Example 6
1.1 starting materials
Figure BDA0002488075130000132
1.2 preparation: the same as in example 2.
Example 7
1.1 starting materials
Figure BDA0002488075130000133
Figure BDA0002488075130000143
1.2 preparation: the same as in example 2.
Example 8
1.1 starting materials
Figure BDA0002488075130000141
1.2 preparation: the same as in example 2.
Example 9
1.1 starting materials
Figure BDA0002488075130000142
1.2 preparation: the same as in example 2.
Example 10
1.1 starting materials
Figure BDA0002488075130000151
1.2 preparation: the same as in example 2.
Example 11
1.1 starting materials
Figure BDA0002488075130000152
1.2 preparation: the same as in example 2.
Comparative example 1
The preparation of example 3 was followed except that: amorphous calcium silicate is not added in the raw materials, hindered phenol (antioxidant 1010) is used for replacing hindered amine (light stabilizer 944), and the dosage of the hindered phenol is slightly increased. The method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000153
Figure BDA0002488075130000161
1.2 preparation: the same as in example 2.
Comparative example 2
The preparation of example 3 was followed except that: the raw materials are not added with amorphous calcium silicate, hindered phenol (antioxidant 1010) is used for replacing hindered amine (light stabilizer 944), the dosage of the hindered phenol is slightly increased, and phenol phosphite (antioxidant 168) is used for replacing alkylphenol phosphite. The method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000162
1.2 preparation: the same as in example 2.
Comparative example 3
The preparation of example 3 was followed except that: amorphous calcium silicate and hindered amine are not added in the raw materials. The method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000163
Figure BDA0002488075130000171
1.2 preparation: the same as in example 2.
Comparative example 4
The preparation of example 3 was followed except that: amorphous calcium silicate is not added in the raw materials. The method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000172
1.2 preparation: the same as in example 2.
Comparative example 5
The preparation of example 3 was followed except that: the addition amount of calcium stearate in the raw materials is 0.30, and the calcium soap: the molar ratio of the zinc soap is 1.04: 1. the method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000173
Figure BDA0002488075130000181
1.2 preparation: the same as in example 2.
Comparative example 6
The preparation of example 2 was followed except that: amorphous calcium silicate in the raw material is replaced by other acid-absorbing agents (magnesium aluminum hydrotalcite), and the dosage is slightly increased. The method comprises the following specific steps:
1.1 starting materials
Figure BDA0002488075130000182
1.2 preparation: the same as in example 2.
Example 12
The venous indwelling needles were assembled from the connection hoses prepared in examples 2 to 11 and comparative examples 1 to 6, respectively, in accordance with fig. 1. The results of the tests relating to the pH value, yellowness index, aluminium content, etc. of the water extract after radiation sterilization are shown in Table 1. Wherein, various test methods are as follows:
1. measurement of pH of aqueous extract
(1) Preparation of leach liquors
S1, performing irradiation sterilization on the assembled complete set of venous indwelling needle:
performing irradiation sterilization by using an electron accelerator (10MeV), and setting the sterilization dose to be 30 kGy; and (5) immediately placing the needle in an aging oven at 40 ℃ after sterilization for accelerated aging for 48h to obtain the irradiated venous indwelling needle.
S2, detaching the connecting hose and the indwelling needle assembly:
and (3) disassembling the irradiated venous indwelling needle, taking the connecting hose, and cutting the connecting hose into small sections with the length of 0.5cm to obtain the connecting hose for the sample.
And removing the puncture needle, the protective sleeve and the hemostatic clamp from the 5 irradiated venous indwelling needles, and cutting the rest parts into small sections with the length of about 0.5cm to obtain an indwelling needle assembly for a test sample.
S3, leaching
Placing the connecting hose sample in a clean conical flask, adding distilled water according to the ratio of the total surface area of the inner wall and the outer wall of the hose section to the volume of water being 3: 1, leaching at 37 ℃ for 24h, and carrying out solid-liquid separation to obtain the connecting hose leaching liquor.
Placing the sample of the indwelling needle assembly into a clean conical flask, adding 50mL of distilled water, leaching for 24h at 37 ℃, and carrying out solid-liquid separation to obtain the leaching liquor of the indwelling needle assembly.
A blank control leach solution was prepared in the same manner by adding 50mL of distilled water to a clean Erlenmeyer flask.
(2) Determination of pH
According to GB/T14233.1 part 1 of the detection method of medical infusion, blood transfusion and injection instruments: chemical analysis method, using a pH meter to measure the pH value of each leaching solution for sample supply, and subtracting the pH value of the leaching solution for blank control to obtain the variation of the pH value of the connection hose and the variation of the pH of the indwelling needle assembly (i.e. the variation of the pH value is the pH value of the instrument or the leaching solution of the hose-the pH value of the distilled water).
2. Determination of aluminum dissolution content
The aluminium content of the connection hose leach liquor was tested using ICP-MS.
3. Yellowness index measurement
Pressing the irradiated connecting hose into a sheet with the thickness of 1.0 +/-0.05 mm, placing the sheet in a color difference meter, taking air as reference, and testing the yellowness index in a transmission mode.
And meanwhile, testing the yellowness indexes before and after irradiation, and calculating the yellowness index increment from the yellowness index after irradiation to the yellowness index before irradiation.
TABLE 1 results of performance test of examples and comparative examples
Figure BDA0002488075130000191
Figure BDA0002488075130000201
The test results in table 1 show that the modified polyvinyl chloride obtained in the embodiment of the present invention can improve the irradiation resistance of PVC products, and after irradiation, the yellowness index is significantly low (below 8), and the increase of the yellowness index is small, and no yellowing occurs basically; meanwhile, the pH change of the connecting hose and the indwelling needle (the absolute value of the pH change of the connecting hose is less than 1.1, and the absolute value of the pH change of the indwelling needle is less than 1) can be effectively reduced, and no aluminum is dissolved out, so that the safety is realized. In comparison of comparative example 4 with example 3, it can be seen that the pH of the product after irradiation changes greatly without the addition of amorphous calcium silicate. Comparing comparative example 3 with example 3, it can be seen that if amorphous calcium silicate and hindered amine are not added, the pH of the product after irradiation changes greatly and yellowing is severe. Comparing comparative examples 1-2 with example 3, it can be seen that if amorphous calcium silicate is not added and hindered amine and alkylphenol phosphite are replaced with hindered phenol antioxidant and phenol phosphite, the pH of the product after irradiation changes greatly and yellowing is severe. Comparing comparative example 5 with example 3, it can be seen that if a lime soap is added: the molar ratio of the zinc soap is that the yellowness index of the product is greatly changed after the product is irradiated.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The modified polyvinyl chloride is characterized by being prepared from the following materials in parts by mass:
100 parts of polyvinyl chloride;
30-80 parts of a primary plasticizer;
2.0-10.0 parts of epoxy vegetable oil;
0.05-0.30 parts of calcium soap;
0.05-0.40 parts of zinc soap;
0.05-0.20 part of hindered amine;
0.1-1.0 part of phosphite ester;
0.1-1.0 part of amorphous calcium silicate;
0.10-1.00 part of auxiliary stabilizer;
the hindered amine is a hindered amine with a triazine structure;
in the amorphous calcium silicate, the molar ratio of silicon to calcium is (1-3) to 1;
the particle size of the amorphous calcium silicate is below 50 mu m.
2. The modified polyvinyl chloride according to claim 1, wherein said amorphous calcium silicate is obtained by:
mixing sodium metasilicate nonahydrate and calcium nitrate tetrahydrate in water for reaction to generate amorphous calcium silicate.
3. The modified polyvinyl chloride according to claim 1, wherein the calcium soap is one or more selected from fatty acid calcium of C4-C22;
the zinc soap is selected from one or more of C4-C22 fatty acid zinc;
the molar ratio of the calcium soap to the zinc soap is 1: 1.5-3.0.
4. The modified polyvinyl chloride according to claim 1, wherein said secondary stabilizers are stearoylbenzoylmethane and 1, 4-dihydro-3, 5-diacetic acid lauryl ester-2, 6-lutidine;
the hindered amine is selected from one or more of light stabilizer 944, Chiguard 106, Chiguard 228 and Chiguard 088.
5. The modified polyvinyl chloride according to claim 1 or 3, wherein the primary plasticizer is selected from one or more of phthalate, terephthalate, trimellitate, citrate, cyclohexanedicarboxylate, adipate, sebacate and polyester plasticizers;
the polyester plasticizer is a polyester plasticizer with the number average molecular weight of 1500-3000 g/mol;
the calcium soap is selected from one or more of calcium isooctanoate, calcium neodecanoate, calcium naphthenate, calcium stearate and calcium octadecanoxystearate;
the zinc soap is selected from one or more of zinc isooctanoate, zinc neodecanoate, zinc naphthenate, zinc stearate and zinc octohydroxystearate.
6. The modified polyvinyl chloride according to claim 1, wherein the epoxidized vegetable oil is epoxidized soybean oil and/or epoxidized linseed oil;
the phosphite ester is alkylphenol phosphite ester.
7. A method for preparing the modified polyvinyl chloride according to any one of claims 1 to 6, comprising:
and (2) carrying out melt extrusion granulation on polyvinyl chloride, a main plasticizer, epoxy vegetable oil, calcium soap, zinc soap, hindered amine, phosphite ester, amorphous calcium silicate and an auxiliary stabilizer to obtain modified polyvinyl chloride granules.
8. An irradiation-resistant venous indwelling needle connecting hose, which is prepared from the modified polyvinyl chloride of any one of claims 1 to 6 or the modified polyvinyl chloride prepared by the preparation method of claim 7.
9. An irradiation resistant venous indwelling needle, wherein the connecting hose in the indwelling needle is the connecting hose according to claim 8.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
US6288155B1 (en) * 1998-03-26 2001-09-11 Ajinomoto Co., Inc. Thermal stabilizer and thermally stabilized halogen-containing resin composition
CN102321316A (en) * 2011-08-25 2012-01-18 上海恒方大高分子材料科技有限公司 Medical polyvinyl chloride (PVC) material for gamma-ray irradiation disinfection and preparation method thereof
CN102827437A (en) * 2012-09-20 2012-12-19 山东威高集团医用高分子制品股份有限公司 Medical radiation-resistant polyvinyl chloride resin
CN102863720A (en) * 2012-10-29 2013-01-09 成都市新津事丰医疗器械有限公司 Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6288155B1 (en) * 1998-03-26 2001-09-11 Ajinomoto Co., Inc. Thermal stabilizer and thermally stabilized halogen-containing resin composition
CN102321316A (en) * 2011-08-25 2012-01-18 上海恒方大高分子材料科技有限公司 Medical polyvinyl chloride (PVC) material for gamma-ray irradiation disinfection and preparation method thereof
CN102827437A (en) * 2012-09-20 2012-12-19 山东威高集团医用高分子制品股份有限公司 Medical radiation-resistant polyvinyl chloride resin
CN102863720A (en) * 2012-10-29 2013-01-09 成都市新津事丰医疗器械有限公司 Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation

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