CN117511039B - Water antibacterial and antioxidant modified composite plastic and preparation method and application thereof - Google Patents

Water antibacterial and antioxidant modified composite plastic and preparation method and application thereof Download PDF

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CN117511039B
CN117511039B CN202311590181.3A CN202311590181A CN117511039B CN 117511039 B CN117511039 B CN 117511039B CN 202311590181 A CN202311590181 A CN 202311590181A CN 117511039 B CN117511039 B CN 117511039B
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antioxidant
antibacterial
polyethylene
composite plastic
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CN117511039A (en
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孙树利
孙毅
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China Huangshan Yao Lee Water Facilities Co ltd
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China Huangshan Yao Lee Water Facilities Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L2023/40—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds changing molecular weight
    • C08L2023/44—Coupling; Molecular weight increase
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish

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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The application relates to an aquatic antibacterial and antioxidant modified composite plastic, and a preparation method and application thereof, and relates to the technical field of plastics, wherein the aquatic antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight: 55-70 parts of a first polyethylene material, 20-35 parts of a second polyethylene material, 2-6 parts of modified polyethylene wax, 0.5-1 part of hydrotalcite, 1-2 parts of sepiolite, 1-5 parts of an antioxidant and 1-5 parts of an antibacterial agent. The application provides an aquatic antibacterial and antioxidant modified composite plastic suitable for long-term water surface contact, which has excellent mechanical property and antibacterial and antioxidant properties in water, can meet the use requirements of polyethylene plastics under different water area characteristics of rivers, lakes and seas, is applied to the preparation of aquatic key component facilities such as aquatic floating paradises, aquatic floating bridges, aquatic floating wharfs, aquatic floating platforms and the like, and has wide practical application values.

Description

Water antibacterial and antioxidant modified composite plastic and preparation method and application thereof
Technical Field
The application relates to the technical field of plastics, in particular to an overwater antibacterial and antioxidant modified composite plastic, and a preparation method and application thereof.
Background
As the demand for water play by people increases, so does the places of water sports and water play. Meanwhile, various large amusement equipment manufacturers are continuously developing new water amusement equipment so as to meet the demands of people. The plastic floating body equipment is water amusement equipment with wider application range, is light in material, economical and durable, and is suitable for places such as yacht wharfs, fishing platforms, holiday villages and the like on various water bodies.
Polyethylene plastic is easy to age, and the technology for aging resistance of polyethylene plastic is mature at present, but the existing polyethylene plastic aging resistance technical scheme is based on land insolation. However, the plastic floating body equipment is used for outdoor water surface for a long time, is easy to age in water after being soaked for a long time, and is easy to attach microorganisms and parasites, so that the disease spread and infection of the crowd are caused. Therefore, the oxidation resistance and weather resistance of the polyethylene plastic in common fresh water areas, acid-base high water areas, oxygen-enriched water areas and water areas with large temperature difference change are necessarily improved, and the service life is prolonged, so that the polyethylene plastic is suitable for the comprehensive green healthy development direction and policy of the aquatic traveling body and meets the use requirements of the polyethylene plastic under the characteristics of different water areas of rivers, lakes and seas.
Disclosure of Invention
In order to solve the problems, the application provides an overwater antibacterial and antioxidant modified composite plastic, and a preparation method and application thereof.
In a first aspect, the application provides an aquatic antibacterial and antioxidant modified composite plastic, which comprises the following components in parts by weight:
55-70 parts of a first polyethylene material, 20-35 parts of a second polyethylene material, 2-6 parts of modified polyethylene wax, 0.5-1 part of hydrotalcite, 1-2 parts of sepiolite, 1-5 parts of an antioxidant and 1-5 parts of an antibacterial agent;
Wherein the first polyethylene material is ultra-high molecular weight polyethylene with weight average molecular weight of 500-700 ten thousand;
The second polyethylene material is high-density polyethylene with the density of 0.941-0.960 g/cm 3;
The modified polyethylene wax is obtained by crosslinking and modifying polyethylene wax and tung oil.
Further, the weight ratio of the first polyethylene material to the second polyethylene material is (2-3): 1.
Further, the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight:
65 parts of a first polyethylene material, 26 parts of a second polyethylene material, 5 parts of modified polyethylene wax, 0.8 part of hydrotalcite, 1.6 parts of sepiolite, 3 parts of an antioxidant and 2 parts of an antibacterial agent.
Further, the preparation method of the modified polyethylene wax comprises the following steps:
heating and stirring polyethylene wax and tung oil to obtain a liquid mixture;
And (3) placing the liquid mixture, the crosslinking agent and the photoinitiator in an ultraviolet crosslinking reactor, reacting for 2-3 hours in inert gas, filtering after the reaction is finished, taking a filter cake, extracting for 30-60 minutes by using xylene in a reflux way, filtering and drying to obtain the modified polyethylene wax.
Further, the weight ratio of the polyethylene wax to the tung oil to the cross-linking agent to the photoinitiator is (10-15): 6-9): 2-5): 0.5-1.5; the ultraviolet light wavelength in the ultraviolet crosslinking reactor is 360-420 nm, and the irradiation distance is 12-18 cm.
Further, the crosslinking agent comprises at least one of methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate; the photoinitiator includes at least one of fluorinated diphenyl titanocene and bis (pentafluorophenyl) titanocene.
Further, the particle sizes of the hydrotalcite and the sepiolite are 300-500 meshes; the antioxidant consists of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of (4-7) to (1-3); the antibacterial agent is a metal ion antibacterial agent.
In a second aspect, the present application provides a method for preparing the waterborne antibacterial antioxidant modified composite plastic according to any one of the first aspect, the method comprising the following steps:
mixing the first polyethylene material and the second polyethylene material, performing microwave heating treatment, and cooling to room temperature to obtain a premix;
And (3) carrying out melt extrusion and granulating on the premix, the modified polyethylene wax, the hydrotalcite, the sepiolite, the antioxidant and the antibacterial agent to obtain the waterborne antibacterial and antioxidant modified composite plastic.
Further, the working parameters of the microwave heating treatment include: the microwave power is 1100-1200W, the heating temperature is 100-115 ℃ and the time is 5-10 minutes.
In a third aspect, the application provides the waterborne antibacterial and antioxidant modified composite plastic prepared by the preparation method in any one of the first aspects and/or the application of the waterborne antibacterial and antioxidant modified composite plastic prepared by the preparation method in any one of the second aspects in the preparation of waterborne facilities.
Compared with the prior art, the technical scheme provided by the embodiment of the application has at least the following advantages:
The embodiment of the application provides an antibacterial and antioxidant modified composite plastic on water, which effectively overcomes the defect that polyethylene plastic is easy to age by using ultrahigh molecular weight polyethylene with specific molecular weight and high density polyethylene with specific density as a novel polyethylene base material system in a matching way; meanwhile, the modified polyethylene wax obtained by crosslinking modification of the polyethylene wax and the tung oil is added, so that the compatibility of a polyethylene base material system with hydrotalcite, sepiolite, an antioxidant, an antibacterial agent and other components is improved, and the melt extrusion molding property of the ultra-high molecular weight polyethylene is improved, so that the water antibacterial and antioxidant modified composite plastic suitable for long-term water surface contact is prepared, has excellent mechanical property and antibacterial and antioxidant property in water, can meet the use requirements of the polyethylene plastic under different water area characteristics of rivers, lakes and seas, is applied to the preparation of water key component facilities such as water floating paradises, water floating bridges, water floating wharfs, water floating platforms and the like, and has wide practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a preparation method of an antibacterial and antioxidant modified composite plastic on water, which is provided by the embodiment of the application;
FIG. 2 is a schematic flow chart of a method for preparing a modified polyethylene wax according to an embodiment of the application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
In a first aspect, the application provides an aquatic antibacterial and antioxidant modified composite plastic, which comprises the following components in parts by weight:
55-70 parts of a first polyethylene material, 20-35 parts of a second polyethylene material, 2-6 parts of modified polyethylene wax, 0.5-1 part of hydrotalcite, 1-2 parts of sepiolite, 1-5 parts of an antioxidant and 1-5 parts of an antibacterial agent;
Wherein the first polyethylene material is ultra-high molecular weight polyethylene with weight average molecular weight of 500-700 ten thousand;
The second polyethylene material is high-density polyethylene with the density of 0.941-0.960 g/cm 3;
The modified polyethylene wax is obtained by crosslinking and modifying polyethylene wax and tung oil.
The embodiment of the application provides an antibacterial and antioxidant modified composite plastic on water, which effectively overcomes the defect that polyethylene plastic is easy to age by using ultrahigh molecular weight polyethylene with specific molecular weight and high density polyethylene with specific density as a novel polyethylene base material system in a matching way; meanwhile, the modified polyethylene wax obtained by crosslinking modification of the polyethylene wax and the tung oil is added, so that the compatibility of a polyethylene base material system with hydrotalcite, sepiolite, an antioxidant, an antibacterial agent and other components is improved, and the melt extrusion molding property of the ultra-high molecular weight polyethylene is improved, so that the water antibacterial and antioxidant modified composite plastic suitable for long-term water surface contact is prepared, has excellent mechanical property and antibacterial and antioxidant property in water, can meet the use requirements of the polyethylene plastic under different water area characteristics of rivers, lakes and seas, is applied to the preparation of water key component facilities such as water floating paradises, water floating bridges, water floating wharfs, water floating platforms and the like, and has wide practical application value.
In the application, the ultra-high molecular weight polyethylene (UHMW-PE) is a high molecular compound, has ultra-strong wear resistance and self-lubricity, high strength, stable chemical property and strong ageing resistance, but has poor molding processability, thereby limiting the wide application. In some embodiments, the ultra-high molecular weight polyethylene having a weight average molecular weight of 500 to 700 tens of thousands may be commercially available products such as korean oil company, trade mark a-500, etc., and may be specifically selected from products such as product model UHMWPEU050 (weight average molecular weight 500 tens of thousands), product model UHMWPEU 050F (weight average molecular weight 550 tens of thousands), product model UHMWPEU070 (weight average molecular weight 700 tens of thousands), etc. The first polyethylene material may be 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, etc.
In the application, the high-density polyethylene is a nonpolar thermoplastic polymer material with high crystallinity, and has better wear resistance, electrical insulation, toughness and cold resistance, but has poorer high-temperature resistance, mechanical property and chemical resistance which can not meet the requirements of practical use at times, thus restricting the wide application of the high-density polyethylene. In some embodiments, a high density polyethylene powder having a density of 0.951g/cm 3 provided by Toguan Wenyu plastic materials limited may be selected; the second polyethylene material may be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, etc.
In some embodiments, the modified polyethylene wax may be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, etc. by weight.
In some embodiments, the parts by weight of hydrotalcite may be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc.
In some embodiments, the parts by weight of sepiolite may be 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, and the like.
In some embodiments, the parts by weight of the antioxidant may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.
In some embodiments, the weight fraction of antimicrobial agent may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.
Preferably, the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight:
65 parts of a first polyethylene material, 26 parts of a second polyethylene material, 5 parts of modified polyethylene wax, 0.8 part of hydrotalcite, 1.6 parts of sepiolite, 3 parts of an antioxidant and 2 parts of an antibacterial agent.
Preferably, the weight ratio of the first polyethylene material to the second polyethylene material is (2-3): 1.
In some embodiments, as shown in fig. 2, the preparation method of the modified polyethylene wax comprises the following steps:
heating and stirring polyethylene wax and tung oil to obtain a liquid mixture;
And (3) placing the liquid mixture, the crosslinking agent and the photoinitiator in an ultraviolet crosslinking reactor, reacting for 2-3 hours in inert gas, filtering after the reaction is finished, taking a filter cake, extracting for 30-60 minutes by using xylene in a reflux way, filtering and drying to obtain the modified polyethylene wax.
In some specific embodiments, the weight ratio of the polyethylene wax, the tung oil, the cross-linking agent and the photoinitiator is (10-15): (6-9): (2-5): (0.5-1.5); the ultraviolet light wavelength in the ultraviolet crosslinking reactor is 360-420 nm, and the irradiation distance is 12-18 cm.
In some embodiments, the crosslinking agent comprises at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; the photoinitiator includes at least one of fluorinated diphenyl titanocene and bis (pentafluorophenyl) titanocene.
In some embodiments, the particle size of the hydrotalcite and the sepiolite are both 300 to 500 mesh; the antioxidant consists of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of (4-7) to (1-3); the antibacterial agent is a metal ion antibacterial agent, and can be specifically selected from nano zinc oxide.
The components involved in the waterborne antibacterial antioxidant modified composite plastic provided by the embodiment of the application can be directly commercially available products if the components are not limited or described in particular.
In a second aspect, based on a general inventive concept, the present application provides a method for preparing the waterborne antibacterial and antioxidant modified composite plastic according to any one of the first aspect, as shown in fig. 1, the method comprising the steps of:
mixing the first polyethylene material and the second polyethylene material, performing microwave heating treatment, and cooling to room temperature to obtain a premix;
And (3) carrying out melt extrusion and granulating on the premix, the modified polyethylene wax, the hydrotalcite, the sepiolite, the antioxidant and the antibacterial agent to obtain the waterborne antibacterial and antioxidant modified composite plastic.
The preparation method of the waterborne antibacterial antioxidant modified composite plastic provided by the application is simple to operate, does not need additional specific equipment, has excellent dispersibility and compatibility in the whole batching system, can be processed and molded by adopting a conventional plastic processing technology, and is suitable for industrial production. Meanwhile, the preparation method of the waterborne antibacterial and antioxidant modified composite plastic is realized based on the waterborne antibacterial and antioxidant modified composite plastic in any one of the first aspect, so that the waterborne antibacterial and antioxidant modified composite plastic at least has all the beneficial effects brought by the technical scheme of the embodiment, and the description is omitted herein.
In some embodiments, the operating parameters of the microwave heating process include: the microwave power is 1100-1200W, the heating temperature is 100-115 ℃ and the time is 5-10 minutes.
In some specific embodiments, the step of melt extruding and granulating the premix, modified polyethylene wax, hydrotalcite, sepiolite, antioxidant and antimicrobial agent to obtain the waterborne antimicrobial and antioxidant modified composite plastic comprises the following steps:
Adding the premix, the modified polyethylene wax, the hydrotalcite, the sepiolite, the antioxidant and the antibacterial agent according to a proportion, putting the mixture into a high-speed mixer, and mixing the mixture for 10 to 15 minutes at the temperature of between 50 and 60 ℃ to obtain a mixed material;
Extruding and granulating the obtained mixture in double-screw equipment, wherein the temperature of a machine body of double-screw extrusion is 190-220 ℃, the temperature of an extruder head is 190-210 ℃, and the rotating speed of a screw is 120-180 r/min, so that the waterborne antibacterial and antioxidant modified composite plastic is obtained.
It should be noted that the operation steps and parameters involved in the preparation process of the waterborne antibacterial and antioxidant modified composite plastic provided by the embodiment of the application can be carried out according to the existing preparation process or by adopting the existing equipment if no special limitation or specific description exists.
In a third aspect, based on a general inventive concept, the present application provides the above-mentioned antibacterial and antioxidant modified composite plastic in any one of the first aspects, and/or the above-mentioned antibacterial and antioxidant modified composite plastic prepared by the preparation method in any one of the second aspects, for use in preparing an above-water facility.
The waterborne antibacterial and antioxidant modified composite plastic provided by the embodiment of the application has excellent mechanical property and antibacterial and antioxidant properties in water, can meet the use requirements of polyethylene plastics under different water area characteristics of rivers, lakes and seas, is applied to the preparation of waterborne key component facilities such as a waterborne floating paradise, a waterborne floating bridge, a waterborne floating wharf, a waterborne floating platform and the like, and has wide practical application value.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
The embodiment provides a waterborne antibacterial and antioxidant modified composite plastic, which comprises the following components in parts by weight: 65 parts of a first polyethylene material, 26 parts of a second polyethylene material, 5 parts of modified polyethylene wax, 0.8 part of hydrotalcite (with the particle size of 300-500 meshes), 1.6 parts of sepiolite (with the particle size of 300-500 meshes), 3 parts of an antioxidant (specifically consisting of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and dilauryl thiodipropionate with the weight ratio of 5:2) and 2 parts of an antibacterial agent (specifically nano zinc oxide); wherein the first polyethylene material is ultra-high molecular weight polyethylene with weight average molecular weight of 500-700 ten thousand (specifically UHMWPEU 050F, weight average molecular weight of 550 ten thousand); the second polyethylene material is high-density polyethylene with the density of 0.941-0.960 g/cm 3 (specifically high-density polyethylene powder with the density of 0.951g/cm 3); the modified polyethylene wax is obtained by crosslinking and modifying polyethylene wax and tung oil.
The preparation method of the waterborne antibacterial and antioxidant modified composite plastic comprises the following steps:
step (1), preparing modified polyethylene wax: heating and stirring polyethylene wax and tung oil to obtain a liquid mixture;
Placing the liquid mixture, the cross-linking agent and the photoinitiator in an ultraviolet crosslinking reactor, reacting for 2.5 hours in inert gas, filtering to obtain a filter cake after the reaction is finished, extracting with xylene under reflux for 40min, filtering and drying to obtain modified polyethylene wax; wherein the weight ratio of the polyethylene wax, the tung oil, the cross-linking agent (particularly ethyl acrylate) and the photoinitiator (particularly fluorinated diphenyl titanocene) is 13:7:3:0.8; the ultraviolet light wavelength in the ultraviolet crosslinking reactor is 360-420 nm, and the irradiation distance is 12-18 cm;
step (2), preparing the waterborne antibacterial and antioxidant modified composite plastic:
(2.1): mixing the first polyethylene material and the second polyethylene material, performing microwave heating treatment, and cooling to room temperature to obtain a premix; wherein, the working parameters of the microwave heating treatment comprise: the microwave power is 1150W, the heating temperature is 110 ℃, and the time is 8 minutes;
(2.2): adding the premix obtained in the step (2.1), the modified polyethylene wax obtained in the step (1), hydrotalcite, sepiolite, an antioxidant and an antibacterial agent in proportion, putting into a high-speed mixer, and mixing for 12min at 55 ℃ to obtain a mixed material; extruding and granulating the obtained mixture in double-screw equipment, wherein the temperature of a machine body extruded by the double screws is 200 ℃, the temperature of an extruder head is 200 ℃, and the rotating speed of a screw is 150r/min, so that the waterborne antibacterial and antioxidant modified composite plastic is obtained.
Example 2
The present example provides an antibacterial and antioxidant modified composite plastic on water and a preparation method thereof, which are different from example 1 only in that: the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight: 55 parts of a first polyethylene material, 20 parts of a second polyethylene material, 2 parts of modified polyethylene wax, 0.5 part of hydrotalcite, 1 part of sepiolite, 1 part of an antioxidant and 1 part of an antibacterial agent; the rest steps and parameters are the same.
Example 3
The present example provides an antibacterial and antioxidant modified composite plastic on water and a preparation method thereof, which are different from example 1 only in that: the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight: 70 parts of a first polyethylene material, 35 parts of a second polyethylene material, 6 parts of modified polyethylene wax, 1 part of hydrotalcite, 2 parts of sepiolite, 5 parts of an antioxidant and 5 parts of an antibacterial agent; the rest steps and parameters are the same.
Example 4
The present example provides an antibacterial and antioxidant modified composite plastic on water and a preparation method thereof, which are different from example 1 only in that: the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight: 70 parts of a first polyethylene material, 20 parts of a second polyethylene material, 5 parts of modified polyethylene wax, 0.8 part of hydrotalcite, 1.6 parts of sepiolite, 3 parts of an antioxidant and 2 parts of an antibacterial agent; the rest steps and parameters are the same.
Comparative example 1
This example provides a modified composite plastic and a method for preparing the same, which differ from example 1 only in that: the first polyethylene material is ultra-high molecular weight polyethylene with the weight average molecular weight of 370 ten thousand (purchased from Tarultam plastic raw materials Co., dongguan, product model UHMWPEU H); the rest steps and parameters are the same.
Comparative example 2
This example provides a modified composite plastic and a method for preparing the same, which differ from example 1 only in that: the modified polyethylene wax is adjusted to polyethylene wax (meanwhile, the preparation step of the modified polyethylene wax is omitted); the rest steps and parameters are the same.
Comparative example 3
This example provides a modified composite plastic and a method for preparing the same, which differ from example 1 only in that: the step (2) in the preparation method of the antibacterial and antioxidant modified composite plastic is adjusted as follows: adding the first polyethylene material, the second polyethylene material, the modified polyethylene wax obtained in the step (1), hydrotalcite, sepiolite, an antioxidant and an antibacterial agent in proportion, and putting into a high-speed mixer to mix for 12min at 55 ℃ to obtain a mixed material; extruding and granulating the obtained mixture in double-screw equipment, wherein the temperature of a machine body of double-screw extrusion is 200 ℃, the temperature of an extruder head is 200 ℃, and the rotating speed of a screw is 150r/min to obtain the waterborne antibacterial and antioxidant modified composite plastic (namely, the step (2.1) is omitted); the rest steps and parameters are the same.
Comparative example 4
This example provides a modified composite plastic and a method for preparing the same, which differ from example 1 only in that: adjusting the dosage of hydrotalcite to 0 part and the dosage of sepiolite to 2.4 parts; the rest steps and parameters are the same.
Comparative example 5
This example provides a modified composite plastic and a method for preparing the same, which differ from example 1 only in that: adjusting the consumption of sepiolite to 0 part and hydrotalcite to 2.4 parts; the rest steps and parameters are the same.
Test case
In this example, the modified composite plastics obtained in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance test.
1. Antioxidant and anti-aging test: the polyethylene plastic samples obtained in each of the above examples and comparative examples were respectively immersed in water at 100 ℃ for 5000 minutes and then tested for OIT (oxidation induction period, minutes), and the OIT (oxidation induction period, minutes) test results are shown in table 1; the polyethylene plastic samples obtained after soaking in water at 100 ℃ for 5000 minutes were then air-dried and subjected to uv aging tests using standard ASTM G155, radiant energy: the results of the tensile strength retention of 0.35W/m2 at 340nm, cycle 102 minutes, dry, 18 minutes wet, UV calculation are shown in Table 2.
2. Acid and base resistance retention test: detection solution: hydrochloric acid solution with the concentration of 6.5kmol/m 3 and sodium hydroxide solution with the concentration of 6.5kmol/m 3; the testing steps are as follows: (1) Respectively weighing the polyethylene plastic sample before soaking in air and measuring the tensile strength; (2) The polyethylene plastic samples obtained in examples 1 to 4 were respectively put into the above two detection solutions at a detection temperature of 23 ℃. Taking out the polyethylene plastic sample after 70 hours, flushing with running water, wiping the sample with filter paper, adjusting for 30 minutes at room temperature, and respectively weighing the soaked polyethylene plastic sample; (3) Respectively measuring the tensile strength of the soaked polyethylene plastic sample within 30 minutes; (4) The weight change rate and the tensile strength change rate were calculated, and the test results are shown in table 3 (test results for immersed hydrochloric acid solution) and table 4 (test results for immersed sodium hydroxide solution); reference before soaking solution: the mass change rate before soaking is 0%; tensile strength: example 1 was 72.4/MPa, example 2 was 58.6/MPa, example 3 was 60.1/MPa, example 4 was 48.9/MPa, comparative example 1 was 59.8/MPa, comparative example 2 was 38.6/MPa, comparative example 3 was 52.0/MPa, comparative example 4 was 53.7/MPa, and comparative example 5 was 49.8/MPa.
TABLE 1
Test sample Oxidation induction period (minutes)
Example 1 289
Example 2 259
Example 3 265
Example 4 243
Comparative example 1 228
Comparative example 2 219
Comparative example 3 230
Comparative example 4 235
Comparative example 5 238
TABLE 2
TABLE 3 Table 3
Test sample Weight change Rate (%) Tensile Strength Change Rate (%)
Example 1 0.21 0.38
Example 2 0.48 0.65
Example 3 0.52 0.71
Example 4 0.76 0.97
TABLE 4 Table 4
Test sample Weight change Rate (%) Tensile Strength Change Rate (%)
Example 1 0.18 0.33
Example 2 0.51 0.69
Example 3 0.55 0.81
Example 4 0.82 1.05
In addition, the antibacterial properties of the plastic samples obtained in examples 1 to 4 are tested according to QB/T2591-2003A antibacterial Plastic antibacterial Performance test method and antibacterial Effect, and the test results show that: the antibacterial properties of the plastic samples obtained in examples 1 to 4 were greater than 99% for both E.coli and Staphylococcus aureus, and had excellent antibacterial properties.
In summary, the embodiment of the application provides the waterborne antibacterial and antioxidant modified composite plastic, which has excellent mechanical property and antibacterial and antioxidant properties in water, can meet the use requirements of polyethylene plastic under different water area characteristics of rivers, lakes and seas, is applied to the preparation of waterborne key component facilities such as a waterborne floating paradise, a waterborne floating bridge, a waterborne floating wharf, a waterborne floating platform and the like, and has wide practical application value.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. 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 application. Thus, the present application 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 (8)

1. The waterborne antibacterial and antioxidant modified composite plastic is characterized by comprising the following components in parts by weight:
55-70 parts of a first polyethylene material, 20-35 parts of a second polyethylene material, 2-6 parts of modified polyethylene wax, 0.5-1 part of hydrotalcite, 1-2 parts of sepiolite, 1-5 parts of an antioxidant and 1-5 parts of an antibacterial agent;
wherein the first polyethylene material is ultra-high molecular weight polyethylene with weight average molecular weight of 500-700 ten thousand;
The second polyethylene material is high-density polyethylene with density of 0.941-0.960 g/cm;
the modified polyethylene wax is obtained by crosslinking modification of polyethylene wax and tung oil;
The preparation method of the modified polyethylene wax comprises the following steps:
heating and stirring polyethylene wax and tung oil to obtain a liquid mixture;
placing the liquid mixture, the cross-linking agent and the photoinitiator in an ultraviolet crosslinking reactor, reacting for 2-3 hours in inert gas, filtering after the reaction is finished to obtain a filter cake, extracting for 30-60 minutes by using xylene in a reflux way, filtering and drying to obtain modified polyethylene wax; the cross-linking agent comprises at least one of methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate;
The preparation method of the waterborne antibacterial and antioxidant modified composite plastic comprises the following steps:
mixing the first polyethylene material and the second polyethylene material, performing microwave heating treatment, and cooling to room temperature to obtain a premix;
And (3) carrying out melt extrusion and granulating on the premix, the modified polyethylene wax, the hydrotalcite, the sepiolite, the antioxidant and the antibacterial agent to obtain the waterborne antibacterial and antioxidant modified composite plastic.
2. The waterborne antibacterial and antioxidant modified composite plastic according to claim 1, wherein the weight ratio of the first polyethylene material to the second polyethylene material is (2-3): 1.
3. The waterborne antibacterial and antioxidant modified composite plastic according to claim 1, wherein the waterborne antibacterial and antioxidant modified composite plastic comprises the following components in parts by weight:
65 parts of a first polyethylene material, 26 parts of a second polyethylene material, 5 parts of modified polyethylene wax, 0.8 part of hydrotalcite, 1.6 parts of sepiolite, 3 parts of an antioxidant and 2 parts of an antibacterial agent.
4. The waterborne antibacterial antioxidant modified composite plastic according to claim 1, wherein the weight ratio of the polyethylene wax to the tung oil to the cross-linking agent to the photoinitiator is (10-15): (6-9): (2-5): (0.5-1.5); the ultraviolet light wavelength in the ultraviolet crosslinking reactor is 360-420 nm, and the irradiation distance is 12-18 cm.
5. The waterborne antimicrobial antioxidant modified composite plastic of claim 4, wherein the photoinitiator comprises at least one of fluorinated diphenyl titanocene and bis (pentafluorophenyl) titanocene.
6. The waterborne antibacterial and antioxidant modified composite plastic according to claim 1, wherein the particle sizes of the hydrotalcite and the sepiolite are 300-500 meshes; the antioxidant consists of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of (4-7) to (1-3); the antibacterial agent is a metal ion antibacterial agent.
7. The waterborne antibacterial antioxidant modified composite plastic according to claim 1, wherein the operating parameters of the microwave heating treatment comprise: the microwave power is 1100-1200W, the heating temperature is 100-115 ℃ and the time is 5-10 minutes.
8. The use of the waterborne antibacterial antioxidant modified composite plastic according to any one of claims 1-7 in the preparation of waterborne facilities.
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Denomination of invention: A waterborne antibacterial and antioxidant modified composite plastic and its preparation method and application

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