Transparent radiation-resistant toughened PP (polypropylene) composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of medical instruments, and relates to a transparent radiation-resistant toughened PP composite material and a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing 100 parts of a PP material, 5-10 parts of a composite elastomer and 0.1-0.5 part of a beta crystal form nucleating agent in a high-speed mixer, and carrying out melt extrusion granulation to obtain a cold-resistant toughening modified master batch; and uniformly mixing 100 parts of PP material, 10-20 parts of cold-resistant toughening modified master batch, 0.1-0.5 part of composite antioxidant and 0.1-0.5 part of composite light stabilizer, and carrying out melt blending extrusion to obtain the cold-resistant toughening modified PP material. The material not only has excellent transparency and radiation resistance, but also has excellent cold resistance, toughness and impact resistance; the material can be widely applied to the hemodialyzer, and especially can endow the hemodialyzer with excellent performance as a shell material of the hemodialyzer.

Description

Technical Field

[0001] This invention belongs to the field of medical device technology, and relates to a transparent radiation-resistant toughened PP composite material, its preparation method and application. Background Technology

[0002] Polypropylene (PP) is a type of general-purpose plastic with abundant raw material sources. As a high-performance thermoplastic polymer, it is generally a colorless, semi-transparent, lightweight thermoplastic plastic that is inexpensive, has a low relative density, excellent processing performance, high yield strength, tensile strength and elastic modulus, good electrical insulation, and good resistance to stress cracking and chemicals. Its products are non-toxic, odorless and have good gloss, so it is widely used in automobiles, machinery, home appliances, packaging, medical and other fields.

[0003] In the field of medical consumables, materials are generally sterilized using three methods: high-temperature steam sterilization, ethylene oxide sterilization, and irradiation sterilization. However, steam sterilization has very high requirements for materials, so it is difficult to popularize. Currently, the most common sterilization method for medical polymer materials in China is ethylene oxide sterilization. While it offers good sterilization and causes minimal physical damage to the sterilized products, it is a toxic gas, leaving residues of the gas and byproducts on the surface of the sterilized materials, posing a significant safety hazard. Furthermore, ethylene oxide sterilization requires an additional environmental residue test, greatly increasing manufacturing time and costs. Therefore, electron beam irradiation sterilization is the optimal choice for medical devices. Irradiation sterilization offers advantages such as strong penetration, rapid sterilization, high efficiency, and room-temperature sterilization. However, polypropylene primarily forms alkyl radicals under high-energy radiation. These radicals react with oxygen in the air to form peroxide radicals, triggering oxidative degradation, leading to main chain breakage and an increase in low-molecular-weight products. This results in poor radiation resistance for polypropylene, and irradiated polyolefin products become brittle with reduced notched impact strength, especially at low temperatures. With prolonged storage, polypropylene degradation continues until it becomes unusable. With the increasing demand for polypropylene in various industries and the development of science and technology, people have higher and higher requirements for the comprehensive performance of polypropylene materials, which has led to an urgent need to improve many of its properties.

[0004] Patent document CN 111499988 B discloses a modified polyvinyl chloride (PVC) and its preparation method. Using PVC as a matrix, a hindered amine stabilizer is used as a functional additive to modify PVC for radiation resistance, thereby improving the polymer's light stability. However, the PVC substrate is not environmentally friendly, and its processing method is too time-consuming. Patent document CN 112063043 A discloses a radiation-resistant meltblown grade polypropylene composite material and its preparation method. Using polypropylene as a matrix, triallyl isocyanurate is used as a photosensitizer to improve the polymer's light stability. However, it poses significant risks to human health and has a potential impact on the environment, and is only applicable to polypropylene meltblown grade nonwoven fabrics sterilized by radiation. Patent document CN118063655A discloses a hindered amine stabilizer polypropylene resin composition and its preparation. Using polypropylene as a matrix, long-chain alkyl groups are introduced into the hindered amine stabilizer to enhance the compatibility between the hindered amine and the polypropylene matrix, making it easy for large-scale industrial production. However, in the field of medical consumables, this preparation method has stringent conditions and complex processes, increasing manufacturing costs. In the medical field, such as infusion containers, medical catheters, and packaging materials, medical-grade PP materials not only require dimensional stability but also must maintain the colorless and semi-transparent nature of PP itself. However, the performance and appearance of traditional PP are significantly affected after exposure to high-energy radiation. Therefore, radiation-resistant modification of PP materials has become a research hotspot for scholars both domestically and internationally. At the same time, improving the cold resistance of PP materials will also broaden its application range in the field of medical materials.

[0005] Existing research on technologies that maintain dimensional stability and high toughness of PP materials while resisting radiation primarily focuses on applications in cosmetic containers, consumer electronics, and automotive injection molded parts. Furthermore, PP composites used in these fields are generally opaque, compromising the translucency of PP. Reports on the application of PP materials in medical injection molding are scarce, especially research on modifications that maintain PP transparency while ensuring radiation resistance and low-temperature toughness. Summary of the Invention

[0006] Therefore, the purpose of this invention is to provide a transparent, radiation-resistant, toughened PP composite material. This material not only possesses excellent transparency and radiation resistance, but also excellent cold resistance, toughness, and impact resistance. This invention also provides a method for preparing this material, which is simple in process, uses readily available raw materials, and is easily mass-produced.

[0007] This invention also provides the application of the material in a hemodialysis machine and a hemodialysis machine containing the material.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a transparent radiation-resistant toughened PP composite material, comprising 100 parts PP material, 10-20 parts cold-resistant toughening modified masterbatch, 0.1-0.5 parts composite antioxidant, and 0.1-0.5 parts composite light stabilizer; the cold-resistant toughening modified masterbatch comprises 100 parts PP material, 5-10 parts composite elastomer, and 0.1-0.5 parts β-crystal nucleating agent; the raw materials are in parts by weight.

[0009] Furthermore, after being irradiated with a 40 kgy electron beam, the transparent radiation-resistant toughened PP composite material exhibits a melt flow index above 3.5 g / 10 min, a yellowing index below 2.8, a light transmittance above 80%, and a haze below 35%; its tensile strength is above 22 MPa, and its notched impact strength at 23°C remains at 18 kJ / m. 2 Above, the notched impact strength at -20℃ remains at 2.0 KJ / m. 2 above.

[0010] Further, the composite antioxidant is composed of any two of the following: 2,6-di-tert-butyl-4-methylphenol (antioxidant 264), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168); preferably, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076) and tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) are compounded in a ratio of 2-5:1-3, preferably 2:1.

[0011] Further, the composite light stabilizer is composed of any three of the following: light stabilizer 944, light stabilizer 116, light stabilizer 5050H, light stabilizer 326, and light stabilizer 622; preferably, light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 are compounded in a ratio of 2-3:0.5-1:1-2, preferably 2:1:1; wherein light stabilizer 944 is poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-bis[(2,2,6,6,-tetramethyl-piperidinyl)imine] [1,6-dihexylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, light stabilizer 116 is N-alkoxy hindered amine (NOR-HALS), light stabilizer 5050H is the reaction product of maleic anhydride α-olefin (C20-24) polymer and 2266-tetramethyl-4-piperidinylamine, light stabilizer 326 is 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and light stabilizer 622 is poly(1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate).

[0012] Furthermore, the melt index of the PP material is 3-5 g / 10 min, and the β-crystal nucleating agent is an amide-based β-crystal nucleating agent, including 1,5-diazabicyclo[4.3.0]non-5-ene (DCHT), sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate (TMB-5), or N,N'-dicyclohexyl-2,6-naphthalenediamide (NAB-100).

[0013] Furthermore, the composite elastomer is composed of any two of ethylene / α-olefin copolymer (POE), polyolefin plastisol (POP), and linear low-density polyethylene (LLDPE); preferably, ethylene / α-olefin copolymer (POE) and polyolefin plastisol (POP) are compounded, or ethylene / α-olefin copolymer (POE) and linear low-density polyethylene (LLDPE) are compounded; the compounding ratio is 1-1.5:1, preferably 1:1.

[0014] This invention further provides a method for preparing the above-mentioned transparent radiation-resistant toughened PP composite material, comprising the following steps: S1, the PP material, composite elastomer and β-crystal nucleating agent are mixed in a high-speed mixer in proportion, and then melt-extruded and granulated to obtain the cold-resistant and toughened modified masterbatch. S2, the PP material, cold-resistant toughening modified masterbatch, composite antioxidant and composite light stabilizer are mixed in proportion and then melt-blended and extruded to obtain the final product.

[0015] Furthermore, the mixing conditions of the high-speed mixer in S1 are: rotation speed 150~200 rpm, time 5~10 min; the granulation conditions are: main machine rotation speed 120~150 rpm, feeding speed 10~25 rpm, pelletizing speed 12~25 rpm, and extruder temperature in each zone 185~210℃.

[0016] Furthermore, the mixing conditions of the high-speed mixer in S2 are: rotation speed 100~200 rpm, time 5~10 min; the granulation conditions are: main machine rotation speed 110~130 rpm, feeding speed 10~25 rpm, pelletizing speed 8~25 rpm, and extruder temperature in each zone 205~225℃.

[0017] The present invention further provides an application of the above-mentioned transparent radiation-resistant toughened PP composite material in a hemodialysis machine.

[0018] The present invention further provides a hemodialysis machine containing the above-mentioned transparent radiation-resistant toughened PP composite material.

[0019] The beneficial effects of this invention are: 1. The transparent radiation-resistant toughened PP composite material provided by the present invention not only has excellent transparency and radiation resistance, but also excellent cold resistance, toughness and impact resistance. Compared with the base material PP, the flowability is also improved.

[0020] 2. The transparent, radiation-resistant, toughened PP composite material provided by this invention, after being irradiated with a 40 kgy electron beam, exhibits a melt flow index above 3.5 g / 10 min, a yellowing index below 2.8, a light transmittance above 80%, and a haze below 35%; its tensile strength is above 22 MPa, and its notched impact strength at 23°C remains at 18 kJ / m. 2 Above, the notched impact strength at -20℃ remains at 2.0 KJ / m. 2 above.

[0021] 3. The method for preparing transparent radiation-resistant toughened PP composite material provided by this invention is simple, uses readily available raw materials, and is easy to mass-produce. The preparation of the cold-resistant toughening modified masterbatch helps to achieve more uniform mixing of the transparent radiation-resistant toughened PP composite material during processing, avoiding uneven dispersion of additives due to deposition, and further contributing to better performance consistency of the finished product.

[0022] 4. The transparent, radiation-resistant, toughened PP composite material provided by this invention can be widely used in hemodialysis machines, especially as the outer shell material of hemodialysis machines, which can endow them with excellent performance. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below through embodiments. All mentioned embodiments are implemented based on the technical solutions of the present invention, and detailed implementation processes are given. However, it should be stated that the scope of protection of the present invention is not limited to the following embodiments.

[0024] This invention provides a transparent radiation-resistant toughened PP composite material, comprising 100 parts PP material, 10-20 parts cold-resistant toughening modified masterbatch, 0.1-0.5 parts composite antioxidant, and 0.1-0.5 parts composite light stabilizer; the cold-resistant toughening modified masterbatch comprises 100 parts PP material, 5-10 parts composite elastomer, and 0.1-0.5 parts β-crystal nucleating agent; the raw materials are in parts by weight.

[0025] This invention further provides a method for preparing the above-mentioned transparent radiation-resistant toughened PP composite material, comprising the following steps: S1, the PP material, composite elastomer, low-density polyethylene and β-crystal nucleating agent are mixed in a high-speed mixer in proportion, and then melt-extruded and granulated to obtain the cold-resistant toughening modified masterbatch. S2, the PP material, cold-resistant toughening modified masterbatch, composite antioxidant and composite light stabilizer are mixed in a high-speed mixer in proportion, and then melt-blended and extruded to granulate, thus obtaining the final product.

[0026] By using the preparation method of this invention and controlling the preparation process parameters, under the synergistic effect of various raw materials, the resulting transparent radiation-resistant toughened PP composite material not only has excellent transparency and radiation resistance, but also excellent cold resistance, toughness, and impact resistance. The flowability of the base PP is also improved.

[0027] The composite antioxidant in this composite material can effectively prevent the polymer from losing strength and toughness due to thermal degradation and oxidative degradation during the extrusion and injection molding process. It can maintain the original mechanical properties and aging resistance of the polymer. It can reduce the chemical bond breakage and free radical generation of polypropylene under high-energy irradiation, thereby reducing the risk of further damage caused by the chain reaction of oxygen-generated peroxy free radicals.

[0028] Composite light stabilizers have a good inhibitory effect on the photo-oxidative degradation reaction of polymers. They inhibit the photo-oxidative degradation reaction through multiple pathways, such as capturing free radicals, decomposing hydrogen peroxides, and transferring the energy of excited state components.

[0029] This invention first prepares a cold-resistant and toughening modified masterbatch, which helps to make the transparent radiation-resistant toughened PP composite material more uniformly mixed during processing, avoids uneven dispersion of additives caused by deposition, and further contributes to better performance consistency of the product.

[0030] The β-crystal nucleating agent in the cold-resistant and toughening modified masterbatch can induce the transformation of the crystal form from α-crystal to β-crystal in PP, thereby significantly increasing the load deformation temperature. The β-crystal also has better toughness, and can maintain good impact resistance, especially at low temperatures.

[0031] The nucleating agent modified in this invention has superior nucleation ability. Its molecular structure matches the lattice parameters of β-crystalline PP. By adsorbing PP molecular chains on the surface, it induces them to arrange themselves in a β-crystalline manner, exhibiting outstanding characteristics such as superior impact resistance, high heat distortion temperature, long-term creep resistance, and strong ductility. The ability to induce polypropylene (PP) to form β-crystalline form is usually quantified by the proportion of β crystals in the total crystal, such as conversion rate (β conversion rate = 100% × (β crystal content + α crystal content) / β crystal content × 100%). The high conversion rate of the β nucleating agent is related to the crystal characteristics of the nucleating agent. The nucleation spacing (c) of the nucleating agent is close to the repeating distance of the PP helical axis, which is conducive to the epitaxial growth of β~PP wafers, transforming PP from homogeneous crystallization to heterogeneous crystallization, making PP grains uniformly finer, thereby improving the transparency, surface gloss, and mechanical strength of PP, which is beneficial to the high performance of PP.

[0032] The excellent performance of elastomer POE is closely related to its structural characteristics: (1) The soft chain coil structure of α-olefins and the crystalline ethylene segments serve as physical crosslinking points, giving it both excellent toughness and good processability; (2) The narrow molecular weight distribution obtained through metallocene active polymerization results in good compatibility with polyolefins and better flowability; (3) POE molecules do not contain unsaturated double bonds, making its weather resistance superior to other elastomers; (4) Strong shear sensitivity and melt strength enable high extrusion and increased production; (5) Good flowability improves filler dispersion and enhances the weld strength of the product. Elastomer POP is mainly composed of propylene, with the introduction of comonomers such as ethylene or butene to form random copolymer chains. Propylene segments tend to form locally regular structures (microcrystals), while ethylene / α-olefin segments break down crystals to form soft segments. Although the controllability of comonomer distribution is slightly lower than that of POE, propylene microcrystals, as a physical crosslinking network, provide higher dimensional stability and better transparency. Low-density polyethylene (LDPE) can be cross-linked with POE / POP in experiments, which can further reduce the overall hardness and improve toughness. The long branches of LDPE may inhibit the growth of α crystals in PP, thereby improving the toughening properties, transparency and processing performance of PP.

[0033] The following embodiments provide detailed implementation procedures for the technical solutions of the present invention. Unless otherwise specified, the experimental methods used in the following experimental examples are conventional methods; unless otherwise specified, the materials and reagents used are commercially available.

[0034] Example 1 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 5 parts by weight of composite elastomer (POE8450 (Dow) and LLDPE7402 (Sinopec), with a composite ratio of 1:1), and 0.1 parts by weight of NAB~100~β crystal nucleating agent (Shanxi Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 150 rpm for 5 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 120 rpm, feeding speed of 10 rpm, pelletizing speed of 12 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0035] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 10 parts by weight of cold-resistant toughening modified masterbatch, 0.1 parts by weight of composite antioxidant (antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.1 parts by weight of composite light stabilizer (light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 100 rpm for 5 minutes. The granulation conditions are: extruder speed of 110 rpm, feed rate of 10 rpm, pelletizing rate of 10 rpm, and extruder temperature of 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0036] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0037] Example 2 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 8 parts by weight of composite elastomer (POE8450 (Dow) and LLDPE7402 (Sinopec), with a composite ratio of 1:1), and 0.1 parts by weight of DCHT~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute). The mixture is added to a high-speed mixer and mixed evenly at a speed of 155 rpm for 6 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 135 rpm, feeding speed of 15 rpm, pelletizing speed of 12 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0038] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 13 parts by weight of cold-resistant toughening modified masterbatch, 0.2 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.2 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 125 rpm for 6 minutes. The granulation conditions are: extruder speed 115 rpm, feed rate 15 rpm, pelletizing rate 12 rpm, and extruder temperature 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0039] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0040] Example 3 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 10 parts by weight of composite elastomer (POE8450 (Dow) and LLDPE7402 (Sinopec), with a composite ratio of 1:1), and 0.1 parts by weight of TMB~5~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 150 rpm for 7 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 120 rpm, feeding speed of 14 rpm, pelletizing speed of 14 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0041] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 15 parts by weight of cold-resistant toughening modified masterbatch, 0.3 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.3 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 150 rpm for 7 minutes. The granulation conditions are: extruder speed 120 rpm, feed rate 14 rpm, pelletizing rate 14 rpm, and extruder temperature 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0042] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0043] Example 4 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 8 parts by weight of composite elastomer (POE8450 (Dow) and LLDPE7402 (Sinopec), with a composite ratio of 1.5:1), and 0.5 parts by weight of NAB~100~β crystal nucleating agent (Shanxi Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 185 rpm for 8 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 135 rpm, feeding speed of 16 rpm, pelletizing speed of 18 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0044] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 18 parts by weight of cold-resistant toughening modified masterbatch, 0.4 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.4 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 175 rpm for 8 minutes. The granulation conditions are: extruder speed 125 rpm, feed rate 16 rpm, pelletizing rate 16 rpm, and extruder temperature 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0045] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0046] Example 5 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 10 parts by weight of composite elastomer (POE8450 (Dow) and LLDPE7402 (Sinopec), with a composite ratio of 1.5:1), and 0.5 parts by weight of TMB~5~β crystal nucleating agent (Shanxi Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 200 rpm for 10 min. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 150 rpm, feeding speed of 18 rpm, pelletizing speed of 20 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0047] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 20 parts by weight of cold-resistant toughening modified masterbatch, 0.5 parts by weight of composite antioxidant (antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.5 parts by weight of composite light stabilizer (light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 200 rpm for 10 minutes. The granulation conditions are: extruder speed 130 rpm, feed rate 18 rpm, pelletizing rate 18 rpm, and extruder temperature 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0048] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0049] Example 6 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 10 parts by weight of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1.5:1), and 0.5 parts by weight of DCHT~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 185 rpm for 9 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 140 rpm, feeding speed of 20 rpm, pelletizing speed of 22 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0050] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 20 parts by weight of cold-resistant toughening modified masterbatch, 0.5 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.5 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 175 rpm for 8 minutes. The granulation conditions are: extruder speed of 125 rpm, feed rate of 20 rpm, pelletizing rate of 20 rpm, and extruder temperature of 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0051] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0052] Example 7 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 8 parts by weight of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1.5:1), and 0.3 parts by weight of NAB~100~β crystal nucleating agent (Shanxi Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 180 rpm for 7 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 135 rpm, feeding speed of 22 rpm, pelletizing speed of 25 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0053] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 18 parts by weight of cold-resistant toughening modified masterbatch, 0.4 parts by weight of composite antioxidant (antioxidant 1076 and antioxidant 168 in a 2:1 ratio), 0.4 parts by weight of composite light stabilizer (light stabilizer 944 and light stabilizer 5050H) and light stabilizer 326 in a 2:1:1 ratio, at a speed of 150 rpm for 6 minutes. The uniformly mixed material is then extruded and granulated under the following conditions: extruder speed of 120 rpm, feeding speed of 22 rpm, pelletizing speed of 22 rpm, and extruder temperature of 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0054] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0055] Example 8 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 10 parts by weight of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1:1), and 0.3 parts by weight of TMB~5~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 185 rpm for 5 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 130 rpm, feeding speed of 24 rpm, pelletizing speed of 25 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0056] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 15 parts by weight of cold-resistant toughening modified masterbatch, 0.3 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.3 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 125 rpm for 5 minutes. The granulation conditions are: extruder speed 125 rpm, feed rate 23 rpm, pelletizing rate 24 rpm, and extruder temperature 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0057] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0058] Example 9 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 8 parts by weight of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1:1), and 0.3 parts by weight of DCHT~β crystal nucleating agent (Shanxi Chemical Research Institute). The mixture is added to a high-speed mixer and mixed evenly at a speed of 150 rpm for 6 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 150 rpm, feeding speed of 25 rpm, pelletizing speed of 25 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0059] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 13 parts by weight of cold-resistant toughening modified masterbatch, 0.2 parts by weight of composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.2 parts by weight of composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 100 rpm for 6 minutes. The granulation conditions are: extruder speed of 130 rpm, feed rate of 25 rpm, pelletizing rate of 25 rpm, and extruder temperature of 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0060] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0061] Example 10 The preparation of a cold-resistant and toughening modified masterbatch involves weighing 100 parts by weight of PP5015 material (Sinopec), 5 parts by weight of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1:1), and 0.3 parts by weight of NAB~100~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 150 rpm for 8 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 140 rpm, feeding speed of 20 rpm, pelletizing speed of 22 rpm, and extruder temperature of 185~210℃ to obtain the cold-resistant and toughening modified masterbatch.

[0062] The preparation of a transparent radiation-resistant toughened PP composite material involves mixing 100 parts by weight of PP material, 10 parts by weight of cold-resistant toughening modified masterbatch, 0.1 parts by weight of composite antioxidant (antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.1 parts by weight of composite light stabilizer (light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 100 rpm for 8 minutes. The granulation conditions are: extruder speed of 125 rpm, feed rate of 20 rpm, pelletizing rate of 20 rpm, and extruder temperature of 205~225℃ to obtain the transparent radiation-resistant toughened PP composite material.

[0063] A dialyzer shell was obtained by injection molding of a transparent, radiation-resistant, toughened PP composite material, which was then applied to medical consumables products, thus solving the problems of radiation resistance and breakage during transportation.

[0064] Comparative Example 1 The dialyzer shell is obtained by injection molding of pure PP5015 material (Sinopec).

[0065] Comparative Example 2 The preparation of a PP composite material involves weighing 100 parts by mass of PP5015 material (Sinopec), 10 parts by mass of composite elastomer (POE8450 (Dow) and POP6202 (ExxonMobil), with a composite ratio of 1.5:1), and 0.5 parts by mass of DCHT~β crystal nucleating agent (Shanxi Provincial Chemical Research Institute), adding them to a high-speed mixer and mixing them evenly at a speed of 100 rpm for 8 minutes. The evenly mixed material is then extruded and granulated under the following conditions: main extruder speed of 125 rpm, feeding speed of 20 rpm, pelletizing speed of 20 rpm, and extruder temperature of 205~225℃, to obtain a PP composite material.

[0066] Comparative Example 3 The preparation of a PP composite material involves mixing 100 parts by weight of PP5015 material (Sinopec), 0.5 parts by weight of a composite antioxidant (a mixture of antioxidant 1076 and antioxidant 168 in a 2:1 ratio), and 0.5 parts by weight of a composite light stabilizer (a mixture of light stabilizer 944, light stabilizer 5050H, and light stabilizer 326 in a 2:1:1 ratio). The mixture is extruded and granulated at a speed of 100 rpm for 8 minutes. The granulation conditions are: extruder speed of 125 rpm, feed rate of 20 rpm, pelletizing rate of 20 rpm, and extruder temperature of 205~225℃ to obtain a PP composite material.

[0067] For the composite materials prepared in the above examples and comparative examples, the melt flow rate (MFR) was determined before irradiation using the method specified in GB / T 3682.1-2018 Plastics - Determination of melt mass flow rate (MFR) and melt volumetric flow rate (MVR) - Part 1: Standard methods. After the granules were irradiated with a 40 kgy electron beam, samples were taken and pressed into sheets for testing, and the following performance characteristics were characterized: (1) Yellowing index test: The yellowing index was determined using a spectrophotometer. The sample size was a square piece of 60 mm × 60 mm with a thickness of 1 mm. The yellowing index and the radiation resistance of the material were inversely proportional. (2) Tensile property test according to standard GB / T 1040.2-2006. The sample is made by injection molding. The size is 1A type sample. The tensile speed is 50mm / min. Five standard samples are tested for each group of samples. Finally, the average value is calculated. (3) Impact strength test according to standard GB / T 1843-2008. The sample is made by injection molding, with a cut depth of 1 mm, a pendulum weight of 5.5 J, a sample width of 9 mm, and a sample thickness of 4 mm. Five standard samples are tested for each group of samples, and the average value is calculated. (4) Transparency test shall be conducted in accordance with GBT2410-2008-Transparent Plastics Transmittance and Haze Test Method.

[0068] The test results are shown in the table below: As shown in the table, the transparent radiation-resistant toughened PP composite material prepared using the method provided in this invention exhibits the following characteristics after irradiation with a 40 kgy electron beam: melt flow index above 3.5 g / 10 min, yellowing index below 2.8, light transmittance above 80%, haze below 35%, tensile strength above 22 MPa, and notched impact strength at 23°C maintained at 18 kJ / m. 2 Above, the notched impact strength at -20℃ remains at 2.0 KJ / m. 2 above.

[0069] Specifically, the composite materials prepared in Examples 1-10 of this invention exhibit excellent performance in multiple indicators such as yellowing, melt index, impact resistance, transparency, and cold resistance. Taking Example 6 as an example, the lowest yellowing index ∆Yi is 0.2, the melt index is 5.52 g / 10 min, and the highest impact strength is 22.8 KJ / m. 2 The best transparency values ​​were 93.4% and 19.4%. Impact performance testing at -20℃ showed a maximum impact strength of 6.4 KJ / m. 2 Compared to the comparative example, the material properties in the embodiments are significantly improved. Therefore, the transparent, radiation-resistant, toughened PP composite material obtained in the embodiments of the present invention can be widely used in hemodialysis machines, especially as the shell material of hemodialysis machines, which can endow them with excellent properties.

[0070] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not 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

1. A transparent radiation resistant toughened PP composite material, characterized in that, The raw material comprises 100 parts of PP material, 10-20 parts of cold-resistant toughening modified master batch, 0.1-0.5 parts of composite antioxidant and 0.1-0.5 parts of composite light stabilizer; the cold-resistant toughening modified master batch comprises 100 parts of PP material, 5-10 parts of composite elastomer and 0.1-0.5 parts of β crystal nucleating agent; the raw material is by weight.

2. The transparent radiation resistant toughened PP composite of claim 1, wherein, The composite antioxidant is composed of any two of 2,6-di-tert-butyl-4-methylphenol, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and tris(2,4-di-tert-butylphenyl) phosphite.

3. The transparent radiation resistant toughened PP composite of claim 1, wherein, The composite light stabilizer is composed of any three of light stabilizer 944, light stabilizer 116, light stabilizer 5050H, light stabilizer 326 and light stabilizer 622.

4. The transparent radiation resistant toughened PP composite of claim 1, wherein, The PP material has a melt index of 3-5 g / 10 min, the β crystal nucleating agent is an amide β crystal nucleating agent, and comprises 1,5-diazabicyclo[4.3.0]non-5-ene, 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate sodium or N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide.

5. The transparent radiation resistant, toughened PP composite of claim 1, wherein, The composite elastomer is composed of any two of ethylene / α-olefin copolymer, polyolefin plastomer and linear low density polyethylene.

6. A method for preparing the transparent radiation resistant toughened PP composite material according to any one of claims 1 to 5, characterized in that, The method comprises the following steps: S1, uniformly mixing the PP material, composite elastomer and β crystal nucleating agent in a high-speed mixer, and then melt-extruding and granulating to obtain the cold-resistant toughening modified master batch; S2, uniformly mixing the PP material, cold-resistant toughening modified master batch, composite antioxidant and composite light stabilizer, and then melt-blending and extruding and granulating to obtain the product.

7. The production method according to claim 6, wherein The mixing condition of the high-speed mixer in S1 is that the rotating speed is 150-200 rpm and the time is 5-10 min; and the granulating condition is that the rotating speed of the main machine is 120-150 rpm, the feeding speed is 10-25 rpm, the cutting speed is 12-25 rpm, and the temperature of each zone of the extruder is 185-210 ℃.

8. The production method according to claim 6, wherein The mixing condition of the high-speed mixer in S2 is that the rotating speed is 100-200 rpm and the time is 5-10 min; and the granulating condition is that the rotating speed of the main machine is 110-130 rpm, the feeding speed is 10-25 rpm, the cutting speed is 8-25 rpm, and the temperature of each zone of the extruder is 205-225 ℃.

9. Application of the transparent radiation-resistant toughened PP composite material in any one of claims 1-5 to a hemodialyzer.

10. Hemodialyzer containing the transparent radiation-resistant toughened PP composite material in any one of claims 1-5.

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