CN114133625A - Medical polypropylene irradiation-resistant premixing agent - Google Patents

Medical polypropylene irradiation-resistant premixing agent Download PDF

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Publication number
CN114133625A
CN114133625A CN202111392648.4A CN202111392648A CN114133625A CN 114133625 A CN114133625 A CN 114133625A CN 202111392648 A CN202111392648 A CN 202111392648A CN 114133625 A CN114133625 A CN 114133625A
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resistant
premix
medical polypropylene
medical
antioxidant
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Chinese (zh)
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王栋
朱军利
曹豫新
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Hefei Qianrun Steel Plastic Co ltd
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Hefei Qianrun Steel Plastic Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/132Phenols containing keto groups, e.g. benzophenones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/156Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575Six-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432Six-membered rings
    • C08K5/3435Piperidines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472Five-membered rings
    • C08K5/3475Five-membered rings condensed with carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34924Triazines containing cyanurate groups; Tautomers thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Abstract

The invention discloses a medical polypropylene irradiation-resistant premix which is non-toxic and tasteless white or light yellow particles, the volatile content of the medical polypropylene irradiation-resistant premix is less than or equal to 0.3wt%, the water content of the medical polypropylene irradiation-resistant premix is less than or equal to 0.1wt%, the medical polypropylene irradiation-resistant premix consists of an antioxidant, an ultraviolet absorbent, a light stabilizer, a nucleating agent and an acid absorbent, and the content (g) of each component in the formula is antioxidant 1000-. The invention can improve the crystallization rate of the material by adding the nucleating agent, achieves the characteristics of high gloss, low shrinkage, high heat resistance and the like, and simultaneously has good transparency without reducing the impact property.

Description

Medical polypropylene irradiation-resistant premixing agent
Technical Field
The invention belongs to the technical field of preparation of medical high polymer materials, and particularly relates to a medical polypropylene irradiation-resistant premix.
Background
At present, the sterilization mode adopted by domestic disposable medical instruments (such as disposable polypropylene syringes) is mainly ethylene oxide sterilization, and the method has the defects of environmental pollution, residual chemical substances harmful to human bodies, long period and the like. The high-energy electron beam is adopted to sterilize the medical instruments, and has the advantages of no pollution, no residue, short period and the like.
However, when polypropylene, which is one of the polymer materials for preparing disposable medical devices, is subjected to irradiation sterilization by high-energy electron beams, the polypropylene is prone to yellowing, the impact strength is reduced, the polypropylene becomes brittle, particularly, the mechanical property is reduced more obviously along with the passage of time, and in addition, the impact property, particularly, the low-temperature impact resistance of the product is reduced more obviously after irradiation, so that great difficulty is caused to the transportation of the disposable medical devices, particularly the transportation and the storage in winter, and the products are prone to cracking and damage. Polypropylene materials have a wide range of applications in medical devices, and their radiation resistance limits their use in radiation sterilization.
Therefore, it is necessary to invent a medical polypropylene radiation-resistant premix to solve the above problems.
Disclosure of Invention
Aiming at the problems, the invention provides a medical polypropylene radiation-resistant premix to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a medical polypropylene radiation-resistant premix is nontoxic and tasteless white or light yellow particles, the volatile content of the medical polypropylene radiation-resistant premix is less than or equal to 0.3wt%, the water content of the medical polypropylene radiation-resistant premix is less than or equal to 0.1wt%, the medical polypropylene radiation-resistant premix comprises an antioxidant, an ultraviolet absorbent, a light stabilizer, a nucleating agent and an acid absorbent, and the content (g) of each component in the formula comprises an antioxidant 1000-.
Further, the antioxidant is one or more of 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid or tris (2, 4-di-tert-butylphenyl) phosphite.
Further, the ultraviolet absorbent is one or more of 2- (5-chloro-2-phenyltriazolyl) -6-tert-butyl-4-methylphenol, 2-hydroxy-4-N-octoxybenzophenone or 2-hydroxy-4-N-octoxybenzophenone.
Further, the light stabilizer is bis-2, 2, 6, 6-tetramethylpiperidinol sebacate.
Further, the nucleating agent is one or more of 1, 3:2, 4-di (3, 4-dimethyl) benzylidene sorbitol acetal or 1, 3:2, 4-di-p-methyl benzylidene sorbitol.
Further, the acid absorbent is one or more of stearic acid amide or zinc stearate.
The invention has the technical effects and advantages that:
1. the polypropylene irradiation-resistant premix is suitable for medical-grade polypropylene products, can ensure that polypropylene particles after radiation sterilization have good processing performance and do not turn yellow and become crisp, can also be used for molded medical equipment such as syringes, test tubes, blood bottles and the like, can maintain the effect of not turning yellow and becoming crisp during irradiation sterilization of the equipment, and can increase the times of repeated sterilization and use.
2. The polypropylene product provided by the invention has no color change effect in the gamma ray disinfection process, provides excellent initial color of polypropylene in the polymerization and extrusion stages, can achieve the advantages of cost reduction, environmental protection and low VOC, and has good yellowing resistance and color stability in polypropylene.
3. The invention can improve the crystallization rate of the material by adding the nucleating agent, achieves the characteristics of high gloss, low shrinkage, high heat resistance and the like, and simultaneously has good transparency without reducing the impact property.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic diagram showing the comparison between the polypropylene sample with the irradiation-resistant premix added thereto and the polypropylene sample which does not change color and become brittle after being irradiated with gamma ray 30 KGY;
FIG. 2 shows a comparative schematic diagram of yellowing and brittleness of a polypropylene sample without adding the radiation-resistant premix after being irradiated by gamma ray 30 KGY.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a medical polypropylene radiation-resistant premix, as shown in figure 1-2, the medical polypropylene radiation-resistant premix is nontoxic and tasteless white or light yellow particles, the volatile component of the medical polypropylene radiation-resistant premix is less than or equal to 0.3wt%, the water content of the medical polypropylene radiation-resistant premix is less than or equal to 0.1wt%, the medical polypropylene radiation-resistant premix comprises an antioxidant, an ultraviolet absorbent, a light stabilizer, a nucleating agent and an acid absorbent, and the content (g) of each component in the formula comprises antioxidant 1000-.
The antioxidant is one or more of 1, 3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione (antioxidant 1790 for short, the content is 300-minus-inch-benzene 600), 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114 for short, the content is 500-minus-inch-benzene 800) or tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168 for short, the content is 1000-minus-inch-benzene 1500). The invention improves the anti-aging efficiency of the material and the stability of the product by adding the antioxidant; the ultraviolet absorbent is one or more of 2- (5-chloro-2-phenyltriazolyl) -6-tert-butyl-4-methylphenol (326 for short, the content is 1000-1800), 2-hydroxy-4-N-octoxy benzophenone or 2-hydroxy-4-N-octoxy benzophenone (531 for short, the content is 300-700). the invention achieves the absorption of ultraviolet rays by adding the ultraviolet absorbent, improves the stability of the product and prevents the product from aging; the light stabilizer is bis-2, 2, 6, 6-tetramethylpiperidinol sebacate (light stabilizer 770 for short, content 400-800), wherein the light stabilizer also has (light stabilizer 519, content 500-1000); the nucleating agent is one or more of 1, 3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal or 1, 3:2, 4-di-p-methyl benzylidene sorbitol, and the invention can improve the crystallization rate of the material by adding the nucleating agent, achieve the characteristics of high gloss, low shrinkage, high heat resistance and the like, and simultaneously has good transparency without reducing the impact property; the acid absorbent is one or more of stearic acid amide (with the content of 300-600) or zinc stearate (with the content of 500-1000);
the invention discloses a preparation method of a medical polypropylene irradiation-resistant premix, which comprises the following steps:
s1: adding the raw materials into a high-speed stirrer according to a proportion, premixing for 15 minutes, and uniformly premixing to obtain a premix;
s2: and adding the obtained premix into a double-screw extruder for melt blending, wherein the temperature of the double-screw extruder along the direction from a feeding port to a neck mold is 150-.
The polypropylene irradiation-resistant premix is suitable for medical-grade polypropylene products, can ensure that polypropylene particles after radiation sterilization have good processing performance and do not turn yellow and become crisp, can also be used for molded medical equipment such as syringes, test tubes, blood bottles and the like, can maintain the effect of not turning yellow and becoming crisp during irradiation sterilization of the equipment, and can increase the times of repeated sterilization;
the polypropylene product provided by the invention has no color change effect in the gamma ray disinfection process, provides excellent initial color of polypropylene in the polymerization and extrusion stages, can achieve the advantages of cost reduction, environmental protection and low VOC, and has good yellowing resistance and color stability in polypropylene.
Example 1: adding 1000g of antioxidant 168, 500g of antioxidant 3114, 300g of stearic acid amide, 500g of zinc stearate, 1000g of nucleating agent, 1000g of ultraviolet absorbent 326 and 400g of light stabilizer 770 into a high-speed stirrer for premixing for 15 minutes, uniformly premixing to obtain a premix, adding the premix into a double-screw extruder for melt blending, wherein the temperature of the double-screw extruder along the direction from a feeding port to a die is 150-250 ℃, the temperature of the die is 180-230 ℃, the rotating speed of a screw is 200 rpm, the residence time of the blend in the screw extruder is 3-5 minutes, and extruding particles to prepare the medical polypropylene irradiation resistant premix.
Example 2: adding 1000g of antioxidant 168, 500g of antioxidant 3114, 300g of antioxidant 1790, 600g of stearic acid amide, 800g of zinc stearate, 1500g of nucleating agent, 1000g of ultraviolet absorbent 326, 500g of ultraviolet absorbent 531, 400g of light stabilizer 770 and 500g of light stabilizer 519 into a high-speed stirrer for premixing for 15 minutes, uniformly premixing to obtain a premix, adding the premix into a double-screw extruder for melt blending, wherein the temperature of the double-screw extruder along the direction from a feeding port to a die is 150-.
Example 3: 1500g of antioxidant 168, 800g of antioxidant 3114, 600g of antioxidant 1790, 600g of stearic acid amide, 1000g of zinc stearate, 2000g of nucleating agent, 1800g of ultraviolet absorbent 326, 700g of ultraviolet absorbent 531, 800g of light stabilizer 770 and 700g of light stabilizer 519 are added into a high-speed stirrer for premixing for 15 minutes, the premix is obtained after uniform premixing, then the premix is added into a double-screw extruder for melt blending, the temperature of the double-screw extruder along the direction from a feed inlet to a die is 150-.
Example 4: adding the medical polypropylene irradiation-resistant premix prepared in the above examples 1-3 into a polypropylene material with a melt index of 20-40g/10min, uniformly stirring, granulating by using a 50-type double-screw extruder, wherein the rotating speed of a host is 300rpm, the feeding rotating speed is 500rpm, the temperature is 200-;
and finally, after the obtained polypropylene material sample and the polypropylene raw material are irradiated by the gamma ray of 30KGY, the melt flow rate, the tensile strength, the flexural modulus, the flexural strength and the notched izod impact strength of the polypropylene material sample are detected again, and the detection results are shown in the following table:
physical Properties (GB) Detection standard Polypropylene raw material Polypropylene raw material and radiation-resistant auxiliary agent After 30KGY experiment of polypropylene raw material After 30KGY experiment of polypropylene raw material and irradiation-resistant auxiliary agent
Melt flow rate g/10min GB/T3682 31 30.5 33 31.5
Tensile strength Mpa GB/T1040 36 38 35 37.8
Flexural modulus Mpa GB/T9341 1450 1600 1400 1610
Flexural strength Mpa GB/T9341 35.3 37.2 34.8 37.5
Cantilever beam gap impact strength KJ/square meter GB/T1843 1.85 1.9 1.1 1.88
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (6)

1. A medical polypropylene radiation-resistant premix is characterized in that: the medical polypropylene radiation-resistant premix is non-toxic and tasteless white or light yellow particles, the volatile content of the premix is less than or equal to 0.3wt%, the water content of the premix is less than or equal to 0.1wt%, the premix comprises an antioxidant, an ultraviolet absorbent, a light stabilizer, a nucleating agent and an acid absorbent, and the content (g) of each component in the formula comprises antioxidant 1000-.
2. The medical polypropylene radiation-resistant premix according to claim 1, characterized in that: the antioxidant is one or more of 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid or tris (2, 4-di-tert-butylphenyl) phosphite.
3. The medical polypropylene radiation-resistant premix according to claim 1, characterized in that: the ultraviolet absorbent is one or more of 2- (5-chloro-2-phenyltriazolyl) -6-tert-butyl-4-methylphenol, 2-hydroxy-4-N-octoxybenzophenone or 2-hydroxy-4-N-octoxybenzophenone.
4. The medical polypropylene radiation-resistant premix according to claim 1, characterized in that: the light stabilizer is bis-2, 2, 6, 6-tetramethyl piperidinol sebacate.
5. The medical polypropylene radiation-resistant premix according to claim 1, characterized in that: the nucleating agent is one or more of 1, 3:2, 4-di (3, 4-dimethyl) benzylidene sorbitol acetal or 1, 3:2, 4-di-p-methyl benzylidene sorbitol.
6. The medical polypropylene radiation-resistant premix according to claim 1, characterized in that: the acid absorbent is one or more of stearic acid amide or zinc stearate.
CN202111392648.4A 2021-11-23 2021-11-23 Medical polypropylene irradiation-resistant premixing agent Pending CN114133625A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114736454A (en) * 2022-03-24 2022-07-12 金发科技股份有限公司 Low-adsorption medical transparent polypropylene material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101828A (en) * 1984-03-13 1987-01-10 三井东压化学有限公司 The polypropylene resin composite of stable radiation
US20100233456A1 (en) * 2007-09-21 2010-09-16 Sumitomo Chemical Company, Limited Light-stabilized polypropylene
CN103834099A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Special radiation-resistant medical polypropylene material
CN104371197A (en) * 2014-11-13 2015-02-25 上海新上化高分子材料有限公司 High-efficiency electron beam irradiation-resistant composite polypropylene material
CN109320842A (en) * 2018-09-30 2019-02-12 杨战军 A kind of polypropylene for medical article thermoplastic elastomer (TPE) and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101828A (en) * 1984-03-13 1987-01-10 三井东压化学有限公司 The polypropylene resin composite of stable radiation
US20100233456A1 (en) * 2007-09-21 2010-09-16 Sumitomo Chemical Company, Limited Light-stabilized polypropylene
CN103834099A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Special radiation-resistant medical polypropylene material
CN104371197A (en) * 2014-11-13 2015-02-25 上海新上化高分子材料有限公司 High-efficiency electron beam irradiation-resistant composite polypropylene material
CN109320842A (en) * 2018-09-30 2019-02-12 杨战军 A kind of polypropylene for medical article thermoplastic elastomer (TPE) and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114736454A (en) * 2022-03-24 2022-07-12 金发科技股份有限公司 Low-adsorption medical transparent polypropylene material and preparation method and application thereof
CN114736454B (en) * 2022-03-24 2023-09-26 金发科技股份有限公司 Low-adsorption medical transparent polypropylene material and preparation method and application thereof

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Application publication date: 20220304