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CN115195243A - Radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy and preparation method thereof - Google Patents

Radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy and preparation method thereof Download PDF

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Publication number
CN115195243A
CN115195243A CN202210585601.8A CN202210585601A CN115195243A CN 115195243 A CN115195243 A CN 115195243A CN 202210585601 A CN202210585601 A CN 202210585601A CN 115195243 A CN115195243 A CN 115195243A
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parts
heat
polyethylene
shrinkable
density polyethylene
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CN115195243B (en
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张迟
智春丽
张建朋
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Qingdao Tianzhida Hi Tech Industrial Development Co ltd
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Qingdao Tianzhida Hi Tech Industrial Development Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D23/00—Producing tubular articles
    • B29D23/001—Pipes; Pipe joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • 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
    • C08L23/36—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 containing nitrogen, e.g. by nitration
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2207/066—LDPE (radical process)
    • 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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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a radiation cross-linked polyethylene full-surrounding outer sheath type floating pontoon and a preparation method thereof, relating to the technical field of floating pontoons, and the key point of the technical scheme is that the radiation cross-linked polyethylene full-surrounding outer sheath type floating pontoon comprises a barrel, wherein the outer surface of the barrel is coated with a heat-shrinkable belt layer, the heat-shrinkable belt layer comprises a heat-shrinkable belt substrate layer and a hot melt adhesive sheet layer, the barrel is made of Expanded Polystyrene (EPS), the heat-shrinkable belt layer is made of heat-shrinkable belts, the heat-shrinkable belt substrate layer is made of heat-shrinkable belt substrates, and the hot melt adhesive sheet layer is made of hot melt adhesive sheets; the polyethylene cylinder body is prepared from the following raw materials: high density polyethylene, low density polyethylene, novolac epoxy resin, butadiene rubber and maleic anhydride grafted high density polyethylene. The radiation cross-linked polyethylene fully-surrounded outer sheath type floating buoy has the advantages of excellent oxidation resistance, wear resistance and long service life.

Description

Radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy and preparation method thereof
Technical Field
The invention relates to the field of buoys, in particular to a radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy and a preparation method thereof.
Background
The mariculture net cage is generally composed of a net cage body, a net and a floating device, wherein the floating device comprises a plurality of cylindrical net cage buoys which are sequentially connected together and surround the circumferential surface of the net cage body, so that buoyancy is provided for the net cage body.
The prior patent application with the application publication number of CN110367164A which can be referred to in the prior art discloses a floating drum for an aquaculture net cage, which comprises a floating drum, connecting lugs, a culture water monitor and fixing components, wherein the left end and the right end of the floating drum are fixedly connected with the connecting lugs, the top surface of the floating drum is provided with a horizontal floating plate, the upper surface of the floating plate is provided with a plurality of supporting grooves, the fixing components are uniformly distributed on the inner sides of the supporting grooves, the middle parts of the floating plates are symmetrically provided with fixing holes, and warning lamps are arranged between the symmetrical fixing holes; wherein the material of the buoy is one of high molecular polyethylene, PE material or polyvinyl chloride.
However, since the buoy is soaked in the sea for a long time and is made of polyethylene, PE or polyvinyl chloride, when the buoy is exposed to the environment directly for a long time, the buoy is prone to aging phenomena such as brittleness, cracking, fading, color loss and the like due to wind erosion, seawater erosion, ultraviolet irradiation and microbial action, thereby affecting the service life of the buoy polyethylene cylinder.
Disclosure of Invention
In view of the defects in the prior art, a first object of the present invention is to provide a radiation crosslinked polyethylene all-around outer sheath type float buoy, which has the advantages of excellent oxidation resistance, wear resistance and long service life.
The second purpose of the invention is to provide a preparation method of the radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy, which has the advantages of simple preparation process and suitability for industrial production.
In order to achieve the first object, the invention provides the following technical scheme: a radiation cross-linked polyethylene fully-enclosed outer sheath type floating buoy comprises a cylinder body, wherein a heat-shrinkable belt layer is coated on the outer surface of the cylinder body and comprises a heat-shrinkable belt base material layer and a hot melt adhesive sheet layer, the hot melt adhesive sheet layer is positioned between the heat-shrinkable belt base material layer and one side, close to the cylinder body, of the cylinder body, the cylinder body is made of Expanded Polystyrene (EPS), the heat-shrinkable belt layer is made of a heat-shrinkable belt, the heat-shrinkable belt base material layer is made of a heat-shrinkable belt base material, and the hot melt adhesive sheet layer is made of a hot melt adhesive sheet;
the polyethylene cylinder is prepared from the following raw materials in parts by weight: 45-55 parts of high-density polyethylene, 15-20 parts of low-density polyethylene, 10-15 parts of phenolic epoxy resin, 15-25 parts of butadiene rubber and 10-15 parts of maleic anhydride grafted high-density polyethylene; the heat-shrinkable tape base material is prepared from the following raw materials in parts by weight: 50-60 parts of crosslinked polyethylene, 3-5 parts of an anti-ultraviolet agent, 3-5 parts of an antioxidant, 6-10 parts of dopamine, 15-20 parts of ethylene propylene rubber and 6-10 parts of maleic anhydride grafted low-density polyethylene; the hot melt adhesive sheet is prepared from the following raw materials in parts by weight: 60-70 parts of ethylene-vinyl acetate, 15-25 parts of tackifying resin, 1-3 parts of anti-ultraviolet agent and 1-3 parts of antioxidant.
By adopting the technical scheme, due to the thermal shrinkage performance of the cross-linked polyethylene in the thermal shrinkage band, the thermal shrinkage band can be tightly coated on the outer peripheral surface of the polyethylene cylinder body due to shrinkage when being heated, and the thermal shrinkage band is tightly attached to the outer surface of the polyethylene cylinder body after being cooled, so that the polyethylene cylinder body is protected, and the oxidation resistance and the ageing resistance of the polyethylene cylinder body are obviously improved. When the polyethylene cylinder and the heat-shrinkable belt are under a high-temperature condition, the polyethylene cylinder is easy to expand when being heated, the polyethylene cylinder is easy to crack in a long-time expansion process, and at the moment, the crosslinked polyethylene in the heat-shrinkable belt has good heat shrinkability, so that the polyethylene cylinder is effectively prevented from expanding and cracking, and the overall structure of the polyethylene cylinder is more stable.
The novolac epoxy resin and the butadiene rubber enable the polyethylene cylinder to have good mechanical strength, high temperature resistance and good toughness and elasticity, and when the polyethylene cylinder is subjected to external temperature change, acid-base change and ultraviolet irradiation, the polyethylene cylinder is not easy to deform and crack, so that the wear resistance of the polyethylene cylinder is improved. Meanwhile, a plurality of maleic anhydride molecules are grafted on the polyethylene molecular chains by maleic anhydride grafted high-density polyethylene through a chemical reaction means, so that the product has the good processability of the high-density polyethylene, the re-reactivity and strong polarity of the maleic anhydride polar molecules, and the compatibility of the high-density polyethylene and other materials can be improved, thereby being beneficial to connecting the materials into a compact three-dimensional network structure, further enabling the polyethylene cylinder to have good ultraviolet resistance, acid and alkali resistance, toughness and oxidation resistance, and prolonging the service life of the polyethylene cylinder.
The antioxidant and the ultraviolet resistant agent in the heat-shrinkable tape base material can improve the tolerance of the crosslinked polyethylene to active oxygen and ultraviolet in the environment and delay the oxidation and aging of the crosslinked polyethylene; meanwhile, dopamine is introduced into the formula to serve as an active oxygen scavenger, and-OH groups in molecules of the dopamine are easy to oxidize and can preferentially react with active oxygen in the environment, so that other materials in the formula are protected from being oxidized, the oxidation resistance and ageing resistance of the heat-shrinkable tape base material are further improved, the service cycle of the hot ocean floating buoy is prolonged, and the cost is saved. In addition, the aging degree of the heat-shrinkable belt base material can be visually monitored through color change in the dopamine oxidation process, and the aged ocean floating buoy can be replaced in time. The ethylene propylene rubber in the formula enhances the flexibility of the heat-shrinkable belt substrate, so that the heat-shrinkable belt substrate can play a good material memory role and processing performance; in addition, the ethylene propylene rubber can also improve the performances of weather resistance, acid and alkali resistance, corrosion resistance and the like of the heat-shrinkable belt, but because the molecular structure of the ethylene propylene rubber and the molecular structure of the polyethylene do not have polar groups, the maleic anhydride grafted low-density polyethylene is introduced to improve the compatibility between the ethylene propylene rubber and the polyethylene, so that the materials are favorably connected to form a compact three-dimensional network structure, the base material of the heat-shrinkable belt has good ultraviolet resistance, acid and alkali resistance, toughness and oxidation resistance, and the service life of the polyethylene cylinder is prolonged.
The ethylene-vinyl acetate in the hot melt adhesive sheet has a crisscross net structure, so that the adhesive strength of the hot melt adhesive sheet is enhanced, and the adhesive strength between the polyethylene cylinder and the heat shrinkable belt of the hot melt adhesive sheet is enhanced; meanwhile, the ethylene-vinyl acetate improves the water resistance and toughness of the hot-melt adhesive sheet in the using process, so that the hot-melt adhesive sheet is not easy to crack in the using process. In order to improve the bonding strength and weather resistance of the hot-melt adhesive sheet, tackifying resin, an anti-ultraviolet agent and an antioxidant are added in the formula, so that the effect of firmer bonding between the heat-shrinkable belt and the polyethylene cylinder is achieved, and the service life of the floating buoy is further prolonged.
Further, the thickness of the base material of the thermal shrinkage belt is 1.2mm, the thickness of the hot-melt film layer is 1.3mm, and the total thickness of the thermal shrinkage belt is 2.5mm.
Through adopting above-mentioned technical scheme, pyrocondensation area base material thickness is 1.2mm, the thickness of hot melt film layer is 1.3mm and the total thickness of pyrocondensation area is 2.5mm and is favorable to the pyrocondensation area to adhere to the polyethylene barrel outer peripheral face to protect the polyethylene barrel.
Further, the preparation method of the heat-shrinkable tape base material comprises the following steps:
(1) Weighing 50-60 parts of crosslinked polyethylene, 3-5 parts of an anti-ultraviolet agent, 3-5 parts of an antioxidant, 6-10 parts of dopamine, 15-20 parts of ethylene propylene rubber and 6-10 parts of maleic anhydride grafted low-density polyethylene;
(2) Uniformly mixing the materials weighed in the step (1) at normal temperature to obtain a mixed material;
(3) Melting and extruding the blend obtained in the step (2) through a double-screw extruder to obtain molten liquid;
(4) And (4) rolling and cooling the molten liquid obtained in the step (3) to obtain the sheet-shaped heat-shrinkable tape base material.
By adopting the technical scheme, because the heat-shrinkable belt substrate is in a sheet shape, all materials are melted after being mixed and then pressed into a sheet, thereby being beneficial to coating the polyethylene cylinder.
Further, the crosslinked polyethylene is prepared by radiation crosslinking of triallyl isocyanurate and high-density polyethylene in a mass ratio of 1.
By adopting the technical scheme, compared with chemical crosslinking, the radiation crosslinking has high processing efficiency, and other chemical agents are not required to be added in the crosslinking process, so that other byproducts are not generated, and the product is pure and easy to process; triallyl isocyanurate is more sensitive to high-energy radiation as a sensitizer with three functional groups, so active oxygen generated after radiation can prolong the dynamic length of active oxygen crosslinking reaction, the crosslinking degree can be obviously improved under the same radiation dose, and the crosslinking process is promoted to be carried out.
Further, the preparation method of the crosslinked polyethylene comprises the following steps:
(1) weighing a certain amount of triallyl isocyanurate and high-density polyethylene according to the mass ratio of 1;
(2) uniformly mixing the triallyl isocyanurate weighed in the step (1) and the high-density polyethylene at normal temperature to obtain a premix;
(3) melting, extruding, cooling and granulating the premix obtained in the step (2) in a double-screw extruder to obtain mixed particles;
(4) and (4) crosslinking the mixed particles obtained in the step (3) by electron beam radiation to obtain crosslinked polyethylene.
By adopting the technical scheme, the triallyl isocyanurate and the high-density polyethylene are mixed, melted and extruded for granulation, and then the radiation crosslinking is carried out, so that the crosslinking process can be promoted, and the property of the crosslinked polyethylene can be improved.
Further, the preparation method of the polyethylene cylinder comprises the following steps:
1) Weighing 45-55 parts of high-density polyethylene, 15-20 parts of low-density polyethylene, 10-15 parts of novolac epoxy resin, 15-25 parts of butadiene rubber and 10-15 parts of maleic anhydride grafted high-density polyethylene;
2) Mixing the materials weighed in the step 1) at normal temperature to obtain a mixture;
3) Melting and extruding the mixture obtained in the step 2) in a double-screw extruder to obtain a blank body;
4) And carrying out injection molding on the blank obtained in the step 3) by using an injection molding machine, and cooling to obtain the polyethylene cylinder.
By adopting the technical scheme, the materials are mixed and melted and then subjected to injection molding, so that the polyethylene cylinder with fixed shape and good hardness performance is obtained.
Further, the ultraviolet screening agent was prepared from 2- (2 ' -hydroxy-3 ',5' -di-t-phenyl) -5-chlorobenzotriazole, 4-benzoyloxy-2, 6-tetramethylpiperidine and AM-101 in a weight ratio of 3.
By adopting the technical scheme, the 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorinated benzotriazole can play a role together with the absorption effect of ultraviolet rays and the quenching effect of AM-101 on excited polymer molecules, so that photochemical reaction is avoided, and the generation of active oxygen around the polyethylene cylinder is reduced; meanwhile, the 4-benzoyloxy-2, 6-tetramethylpiperidine can assist dopamine in capturing active oxygen in the environment, so that the active oxygen removal effect of the dopamine is enhanced, and further the damage of the active oxygen around the polyethylene cylinder to the polyethylene cylinder is reduced.
Further, the antioxidant is prepared from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of 1.
By adopting the technical scheme, the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is used as a high molecular weight hindered phenol antioxidant to capture active oxygen generated in oxidative degradation, so that chain degradation reaction is interrupted, and when the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is used together with dilauryl thiodipropionate, the polyethylene antioxidant has a good synergistic effect, so that the decomposition rate of polyethylene due to oxidation can be delayed, and high-activity hydroperoxide can be decomposed into low-activity molecules, so that the heat resistance and the oxygen resistance of polyethylene are changed.
In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy comprises the following steps:
s1, preparing a hot-melt film:
s11, weighing 60-70 parts of ethylene-vinyl acetate, 15-25 parts of tackifying resin, 1-3 parts of anti-ultraviolet agent and 1-3 parts of antioxidant;
s12, uniformly mixing the materials weighed in the S11 at normal temperature to obtain a mixed material;
s13, melting and extruding the mixed material obtained in the step S12 through a double-screw extruder to obtain molten slurry;
s14, calendering and cooling the molten slurry obtained in the S13 to obtain a flaky hot-melt adhesive sheet;
s15, placing the hot-melt adhesive sheet on a heat-shrinkable tape base material, and heating to combine the hot-melt adhesive sheet and the heat-shrinkable tape base material to obtain a heat-shrinkable tape;
and S2, heating and hot-melting the heat-shrinkable belt prepared in the step S15 to the outer surface of the polyethylene cylinder body, so as to obtain the floating buoy.
Through adopting above-mentioned technical scheme, earlier with the polyethylene barrel, hot melt film and pyrocondensation area substrate prepare the back respectively, then form the pyrocondensation area on with hot melt film hot melt pyrocondensation area substrate, at last to the surface of polyethylene barrel of pyrocondensation area hot melt, because the pyrocondensation performance of crosslinked polyethylene in the pyrocondensation area, can make the pyrocondensation area tightly wrap in polyethylene barrel outer peripheral face because of the shrink when heating, closely laminate in polyethylene barrel surface after the cooling, thereby protect the polyethylene barrel, thereby the oxidation resistance and the ageing resistance of polyethylene barrel have been showing and have been improved. The preparation process is simple and suitable for industrial production.
In conclusion, the invention has the following beneficial effects:
according to the invention, after the thermal shrinkage belt is heated and then is hot-melted on the outer surface of the polyethylene cylinder, the thermal shrinkage belt can be tightly attached to the outer surface of the polyethylene cylinder after being cooled, so that the polyethylene cylinder is protected, and the oxidation resistance and the ageing resistance of the polyethylene cylinder are obviously improved. When the polyethylene cylinder and the heat-shrinkable tape are under a high-temperature condition, the polyethylene cylinder is easy to expand when being heated, the polyethylene cylinder is easy to crack in a long-time expansion process, and at the moment, the crosslinked polyethylene in the heat-shrinkable tape has good heat-shrinkable performance, so that the polyethylene cylinder is effectively prevented from expanding and cracking, and the integral structure of the polyethylene cylinder is more stable.
Firstly, dopamine is preferably introduced to be used as an active oxygen scavenger, and-OH groups in molecules of the dopamine are easy to oxidize and can preferentially react with active oxygen in the environment, so that other materials in the formula are protected from being oxidized, the oxidation resistance and ageing resistance of the heat-shrinkable tape base material are further improved, the service cycle of the hot ocean floating buoy is prolonged, and the cost is saved. In addition, the aging degree of the heat-shrinkable belt base material can be visually monitored through color change in the dopamine oxidation process, and the aged ocean floating buoy can be replaced in time.
Secondly, the radiation crosslinking is preferentially adopted in the invention, the processing efficiency of the radiation crosslinking is high compared with that of the chemical crosslinking, and other chemical agents are not required to be added in the crosslinking process, so that other byproducts are not generated, and the product is pure and easy to process; triallyl isocyanurate is more sensitive to high-energy radiation as a sensitizer with three functional groups, so active oxygen generated after radiation can prolong the dynamic length of active oxygen crosslinking reaction, the crosslinking degree can be obviously improved under the same radiation dose, and the crosslinking process is promoted to be carried out.
Thirdly, after respectively preparing the polyethylene cylinder, the hot-melt adhesive sheet and the thermal shrinkage tape substrate, then forming the thermal shrinkage tape by hot-melting the hot-melt adhesive sheet on the thermal shrinkage tape substrate, and finally hot-melting the thermal shrinkage tape on the outer surface of the polyethylene cylinder. Simple preparation process and suitability for industrial production
Drawings
FIG. 1 is a schematic view of the overall structure of the marine flotation tank in examples 1-5;
FIG. 2 is a schematic longitudinal sectional view of the marine flotation tank of examples 1 to 5;
in the figure, 1, a cylinder; 2. a heat-shrinkable tape layer; 21. a heat-shrinkable tape substrate layer; 22. and a hot melt adhesive sheet layer.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples.
Preparation of crosslinked polyethylene
The triallyl isocyanurate in the preparation example of the crosslinked polyethylene is triallyl isocyanurate provided by Dongjia chemical raw material Co., ltd, dongguan city, the content of which is 99 percent, and the type of which is TAIC; the high density polyethylene is high density polyethylene supplied by Dow, USA under the trade name DGDK-3364.
(1) Weighing a certain amount of triallyl isocyanurate and high-density polyethylene according to the mass ratio of 1;
(2) uniformly mixing the triallyl isocyanurate weighed in the step (1) and the high-density polyethylene at normal temperature to obtain a premix;
(3) melting, extruding, cooling and granulating the premix obtained in the step (2) in a double-screw extruder to obtain mixed particles; (the temperatures of the first zone to the fourth zone of the double-screw extruder are respectively controlled at 160 ℃, 170 ℃ and 185 ℃, the head temperature is 200 ℃, and the screw rotating speed is 30 r/min);
(4) and (4) carrying out radiation crosslinking treatment on the mixed particles obtained in the step (3) by using electron beams, wherein the radiation dose is 100KGy, and obtaining the crosslinked polyethylene.
Preparation example of Heat-shrinkable tape base Material
The crosslinked polyethylene in each preparation example of the heat-shrinkable tape base material was prepared from a preparation example of crosslinked polyethylene; the dopamine is dopamine powder provided by Sian Baichuan biotechnology limited, the content of the dopamine powder is 98 percent, and the product number of the dopamine powder is A-03688; the ultraviolet inhibitor is prepared from 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 4-benzoyloxy-2, 6-tetramethylpiperidine and AM-101 in a weight ratio of 3; the antioxidant is prepared from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with the weight ratio of 1]Pentaerythritol ester and dilauryl thiodipropionate; the ethylene-propylene rubber is ethylene-propylene-diene monomer provided by Dow, and the grade is Nordel4770; the maleic anhydride grafted low-density polyethylene is maleic anhydride grafted low-density polyethylene provided by Shanghai Plastic materials Co., ltd, dongguan, and has a melt index (190 ℃,2.16 Kg) of 6g/10min, a grafting rate of 12 percent and a density of 0.914g/cm 3 。
Preparation example 1 of Heat-shrinkable tape base Material
(1) Weighing 50kg of crosslinked polyethylene, 3kg of an anti-ultraviolet agent, 3kg of an antioxidant, 6kg of dopamine, 15kg of ethylene propylene rubber and 6kg of maleic anhydride grafted low-density polyethylene;
(2) Uniformly mixing the materials weighed in the step (1) at normal temperature to obtain a mixed material;
(3) Melting and extruding the blend obtained in the step (2) by a double-screw extruder (the temperature of each section of the double-screw extruder is 180 ℃ in a first area, 180 ℃ in a second area, 185 ℃ in a third area, 190 ℃ in a fourth area, 180 ℃ in a fifth area, 180 ℃ in a sixth area, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 45 r/min) to obtain molten liquid;
(4) And (4) calendering the molten liquid obtained in the step (3) into a sheet with the thickness of 1.2mm by a three-roll calender, and cooling at 0 ℃ to obtain the heat shrinkable tape base material.
Preparation example 2 of Heat-shrinkable tape base Material
(1) Weighing 55kg of crosslinked polyethylene, 4kg of an anti-ultraviolet agent, 4kg of an antioxidant, 8kg of dopamine, 17.5kg of ethylene propylene rubber and 8kg of maleic anhydride grafted low-density polyethylene;
(2) Uniformly mixing the materials weighed in the step (1) at normal temperature to obtain a mixed material;
(3) Melting and extruding the blend obtained in the step (2) by a double-screw extruder (the temperature of each section of the double-screw extruder is 180 ℃ in a first area, 180 ℃ in a second area, 185 ℃ in a third area, 190 ℃ in a fourth area, 180 ℃ in a fifth area, 180 ℃ in a sixth area, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 45 r/min) to obtain molten liquid;
(4) And (4) calendering the molten liquid obtained in the step (3) into a sheet with the thickness of 1.2mm by a three-roll calender, and cooling at 0 ℃ to obtain the heat shrinkable tape base material.
Preparation example 3 of Heat-shrinkable tape base Material
(1) Weighing 60kg of crosslinked polyethylene, 5kg of an anti-ultraviolet agent, 5kg of an antioxidant, 10kg of dopamine, 20kg of ethylene propylene rubber and 10kg of maleic anhydride grafted low-density polyethylene;
(2) Uniformly mixing the materials weighed in the step (1) at normal temperature to obtain a mixed material;
(3) Melting and extruding the blend obtained in the step (2) by a double-screw extruder (the temperature of each section of the double-screw extruder is 180 ℃ in a first area, 180 ℃ in a second area, 185 ℃ in a third area, 190 ℃ in a fourth area, 180 ℃ in a fifth area, 180 ℃ in a sixth area, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 45 r/min) to obtain molten liquid;
(4) And (4) calendering the molten liquid obtained in the step (3) into a sheet with the thickness of 1.2mm by a three-roll calender, and cooling at 0 ℃ to obtain the heat shrinkable tape base material.
Preparation example 4 of Heat-shrinkable tape base Material
The difference between the preparation example and the preparation example 1 is that the step (1) in the preparation example is as follows: weighing 50kg of crosslinked polyethylene, 3kg of ultraviolet resistant agent, 3kg of antioxidant, 15kg of ethylene propylene rubber and 6kg of maleic anhydride grafted low density polyethylene.
Preparation example 5 of Heat-shrinkable tape base Material
The difference between the preparation example and the preparation example 1 is that the step (1) in the preparation example is as follows: weighing 50kg of crosslinked polyethylene, 3kg of antioxidant, 6kg of dopamine, 15kg of ethylene propylene rubber and 6kg of maleic anhydride grafted low-density polyethylene.
Preparation example of polyethylene tube
The high density polyethylene in each preparation example of the polyethylene cylinder was high density polyethylene supplied by Dow, USA, having a designation DGDK-3364, density of 0.947g/cm 3 Melt flow rate (190 ℃/2.16 kg) 0.75g/10min; low-density polyethylene available from Tianshi plastics chemical Co., ltd, dongguan, brand LL7420D, density 0.918g/cm 3 The melt flow rate is 2.0g/10min; the novolac epoxy resin is novolac epoxy resin F-51 provided by the chemistry of China and Guangdong, and the softening point is 25 ℃; the butadiene rubber is butadiene rubber provided by Yanshan petrochemical company, and is of the type BR9000; the maleic anhydride grafted high-density polyethylene is maleic anhydride grafted high-density polyethylene provided by Acacia albiflora chemical Co., ltd, dongguan, and has a melt index of 1.25g/10min and a density of 0.875g/cm 3 Graft MAH content 1%.
Preparation example 1 of polyethylene Cartridge
1) Weighing 45kg of high-density polyethylene, 15kg of low-density polyethylene, 10kg of phenolic epoxy resin, 15kg of butadiene rubber and 10kg of maleic anhydride grafted high-density polyethylene;
2) Mixing the materials weighed in the step 1) at normal temperature to obtain a mixture;
3) Melting and extruding the mixture obtained in the step 2) in a double-screw extruder (the temperature of each section of the double-screw extruder is 190 ℃ in a first area, 200 ℃ in a second area, 210 ℃ in a third area, 220 ℃ in a fourth area, 230 ℃ in a fifth area, 240 ℃ in a sixth area, the temperature of a machine head is 250 ℃, and the rotating speed of screws is 45 r/min) to obtain a blank body;
4) And (4) subjecting the green body obtained in the step (3) to injection molding by an injection molding machine (the temperature of a charging barrel of the injection molding machine is 150 ℃, the temperature of a nozzle of the injection molding machine is 180 ℃, the temperature of a mold is 30 ℃, the injection molding speed is 160mm/s, the injection molding pressure is 4MPa, the pressure maintaining pressure is 4MPa, and the injection time is 40 s), and performing injection molding and cooling to obtain the polyethylene cylinder.
Preparation example 2 of polyethylene Cartridge
1) Weighing 50kg of high-density polyethylene, 17.5kg of low-density polyethylene, 12.5kg of phenolic epoxy resin, 17.5kg of butadiene rubber and 12.5kg of maleic anhydride grafted high-density polyethylene;
2) Mixing the materials weighed in the step 1) at normal temperature to obtain a mixture;
3) Melting and extruding the mixture obtained in the step 2) in a double-screw extruder (the temperature of each section of the double-screw extruder is 190 ℃ in the first zone, 200 ℃ in the second zone, 210 ℃ in the third zone, 220 ℃ in the fourth zone, 230 ℃ in the fifth zone, 240 ℃ in the sixth zone, the temperature of a machine head is 250 ℃, and the rotating speed of screws is 45 r/min) to obtain a blank;
4) And (3) subjecting the blank obtained in the step (3) to injection molding by an injection molding machine (the temperature of a charging barrel of the injection molding machine is 150 ℃, the temperature of a nozzle of the injection molding machine is 180 ℃, the temperature of a mold is 30 ℃, the injection molding speed is 160mm/s, the injection molding pressure is 4MPa, the pressure maintaining pressure is 4MPa, and the injection time is 40 s), and performing injection molding and cooling to obtain the polyethylene cylinder.
Preparation example 3 of polyethylene Cartridge
1) 55kg of high-density polyethylene, 20kg of low-density polyethylene, 15kg of phenolic epoxy resin, 25kg of butadiene rubber and 15kg of maleic anhydride grafted high-density polyethylene are weighed;
2) Mixing the materials weighed in the step 1) at normal temperature to obtain a mixture;
3) Melting and extruding the mixture obtained in the step 2) in a double-screw extruder (the temperature of each section of the double-screw extruder is 190 ℃ in the first zone, 200 ℃ in the second zone, 210 ℃ in the third zone, 220 ℃ in the fourth zone, 230 ℃ in the fifth zone, 240 ℃ in the sixth zone, the temperature of a machine head is 250 ℃, and the rotating speed of screws is 45 r/min) to obtain a blank;
4) And (3) subjecting the blank obtained in the step (3) to injection molding by an injection molding machine (the temperature of a charging barrel of the injection molding machine is 150 ℃, the temperature of a nozzle of the injection molding machine is 180 ℃, the temperature of a mold is 30 ℃, the injection molding speed is 160mm/s, the injection molding pressure is 4MPa, the pressure maintaining pressure is 4MPa, and the injection time is 40 s), and performing injection molding and cooling to obtain the polyethylene cylinder.
Examples
The ethylene-vinyl acetate copolymer in each example was an ethylene-vinyl acetate copolymer available from tsu, geon & plastification, inc, under the designation FL00226CC; the tackifying resin is hydrogenated rosin glyceride which is provided by Henan sea Rui chemical products GmbH; the ultraviolet resistant agent is prepared from 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 4-benzoyloxy-2, 6-tetramethylpiperidine and AM-101 in a weight ratio of 3; the antioxidant is prepared from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of 1.
Example 1
A radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy refers to fig. 1 and fig. 2 and comprises a cylindrical cylinder body 1, wherein a heat-shrinkable belt layer 2 is coated on the outer surface of the cylinder body 1. The heat-shrinkable tape layer 2 comprises a heat-shrinkable tape base material layer 21 and a hot melt adhesive sheet layer 22, and the hot melt adhesive sheet layer 22 is positioned between the heat-shrinkable tape base material layer 21 and one side of the cylinder body 1, which are close to each other. The cylinder body 1 is made of Expanded Polystyrene (EPS), the heat-shrinkable belt layer 2 is made of a heat-shrinkable belt, the heat-shrinkable belt substrate layer 21 is made of a heat-shrinkable belt substrate, and the hot melt adhesive sheet layer 22 is made of a hot melt adhesive sheet. The preparation method of the ocean floating buoy comprises the following steps:
s1, preparing a hot-melt film:
s11, weighing 60kg of ethylene-vinyl acetate, 15kg of tackifying resin, 1kg of anti-ultraviolet agent and 1kg of antioxidant;
s12, uniformly mixing the materials weighed in the S11 at normal temperature to obtain a mixed material;
s13, melting and extruding the mixed material obtained in the S12 by a double-screw extruder (the temperature of each section of the double-screw extruder is 190 ℃ in a first area, 200 ℃ in a second area, 210 ℃ in a third area, 220 ℃ in a fourth area, 230 ℃ in a fifth area, 240 ℃ in a sixth area, the temperature of a machine head is 250 ℃, and the rotating speed of a screw is 45 r/min) to obtain molten slurry;
s14, calendering the molten pulp obtained in the step S13 by a three-roll calender and cooling to room temperature to obtain a flaky hot-melt film with the thickness of 1.3 mm;
s15, placing the hot-melt adhesive sheet on a heat-shrinkable tape base material, and heating at 60 ℃ to combine the hot-melt adhesive sheet and the heat-shrinkable tape base material to obtain a heat-shrinkable tape with the total thickness of 2.5 mm;
and S2, heating the thermal shrinkage band prepared in the step S15 to 120 ℃, stretching, and then thermally melting the thermal shrinkage band to the outer surface of the polyethylene cylinder body to obtain the ocean floating buoy.
The heat-shrinkable tape base material used in the present example was prepared by the preparation example of the heat-shrinkable tape base material; the polyethylene cylinder is prepared by the preparation 1 of the polyethylene cylinder.
Example 2
The present embodiment is different from embodiment 1 in that step S11 of the present embodiment is: 65kg of ethylene-vinyl acetate, 20kg of tackifying resin, 2kg of ultraviolet resistant agent and 2kg of antioxidant are weighed.
The heat-shrinkable tape base material used in this example was prepared by preparation example 1 of a heat-shrinkable tape base material; the polyethylene cylinder is prepared by the preparation 1 of the polyethylene cylinder.
Example 3
The present embodiment is different from embodiment 1 in that step S11 of the present embodiment is: 70kg of ethylene-vinyl acetate, 25kg of tackifying resin, 3kg of anti-ultraviolet agent and 3kg of antioxidant are weighed.
The heat-shrinkable tape base material used in this example was prepared in preparation example 1 of a heat-shrinkable tape base material; the polyethylene cylinder is prepared by the preparation 1 of the polyethylene cylinder.
Example 4
The difference between this example and example 1 is that the heat-shrinkable tape base material used in this example is the heat-shrinkable tape base material provided in preparation example 2 of the heat-shrinkable tape base material, and the polyethylene cylinder body used in this example is the polyethylene cylinder body provided in preparation example 2 of the polyethylene cylinder body.
Example 5
The difference between this example and example 1 is that the heat-shrinkable tape base material used in this example is the heat-shrinkable tape base material provided in preparation example 3 of the heat-shrinkable tape base material, and the polyethylene cylinder body used in this example is the polyethylene cylinder body provided in preparation example 3 of the polyethylene cylinder body.
Comparative example
Comparative example 1
The comparative example is different from example 1 in that the outer peripheral surface of the polyethylene cylinder of the comparative example is not coated with the heat-shrinkable tape.
Comparative example 2
This comparative example is different from example 1 in that the heat-shrinkable tape substrate used in this comparative example was the heat-shrinkable tape substrate provided in heat-shrinkable tape substrate preparation example 4.
Comparative example 3
This comparative example is different from example 1 in that the heat-shrinkable tape base material used in this comparative example was the heat-shrinkable tape base material provided in heat-shrinkable tape base material production example 5.
Performance test
1. And (3) detecting mechanical properties:
the floating cartridges prepared in examples 1 to 5 and comparative examples 1 to 3 were tested, and the criteria used in the test items were as follows: tensile strength GB/T1040-2006 determination of tensile Properties of plastics; elongation at break GB/T1040-2006 determination of tensile Properties of plastics; flexural modulus GB/T9341-2008 & lt & ltdetermination of Plastic flexural Property & gt; environmental stress cracking time GB/T1842-2008 polyethylene environmental stress cracking test method; low temperature embrittlement temperature GB/T5470-2008 test method of plastic impact embrittlement temperature; the test results are shown in table 1:
TABLE 1 test results of mechanical Properties of examples 1 to 5 and comparative examples 1 to 3
Figure BDA0003665819350000111
As can be seen from table 1, the floating barrels prepared in examples 1 to 5 are superior to the conventional floating barrels in tensile strength, elongation at break, flexural modulus, environmental stress cracking resistance time, and embrittlement temperature, which indicates that the present invention can improve the mechanical properties and weather resistance of the polyethylene barrel by wrapping the polyethylene barrel with the heat-shrinkable tape. Compared with the comparative example 1, the embodiment 1 shows that the tensile strength, the tensile elongation, the flexural modulus, the environmental stress cracking resistance time and the brittle temperature of the floating cylinder prepared by the invention are obviously superior to those of the traditional floating cylinder, and the heat-shrinkable belt prepared by the invention is coated on the outer peripheral surface of the polyethylene cylinder body, so that the floating cylinder has good mechanical property and weather resistance. By comparing the embodiment 1 with the comparative examples 2 to 3, the introduction of the dopamine is shown to be capable of obviously improving the flexural modulus, the environmental stress cracking resistance time and the embrittlement temperature of the floating barrel, and meanwhile, the dopamine is introduced into the formula to be used as an active oxygen scavenger, and-OH groups in molecules of the dopamine are easy to oxidize and preferentially react with active oxygen in the environment, so that other materials in the formula are protected from being oxidized, the oxidation resistance and the aging resistance of the heat-shrinkable tape base material are improved, and the floating barrel is enabled to obtain good mechanical properties, particularly excellent performances of the flexural modulus, the environmental stress cracking resistance time and the embrittlement temperature.
2. And (3) detecting the oxidation resistance of the thermal shrinkage band:
plates of the same size were cut from the floating cylinders prepared in examples 1-5 and comparative examples 1-3 from the outside inwards, and the plates were irradiated under sealed conditions with UV lamps (model UVB-313NM, power 40w, lamp wavelength range 280-315 NM, supplied by Shenzhen Guanyu electro-optical technology Co., ltd.) separately, the irradiation was stopped at intervals of 10d and the color of the plates was recorded for times of 0d, 10d and 20d, respectively, and the results are shown in Table 2.
TABLE 2 test results of color change of examples 1 to 5 and comparative examples 1 to 3
Test items Irradiation time 0d Irradiation time 10d Irradiation time 20d
Example 1 White colour Light red Red colour
Example 2 White colour Pink colour Light red
Example 3 White colour Light pink colour Pink colour
Example 4 White colour White colour White colour
Example 5 White colour White colour White colour
Comparative example 1 White colour Brown colour Black color (black)
Comparative example 2 White colour Deep red color Brown colour
Comparative example 3 White colour Red colour Deep red color
As can be seen from Table 2, the colors of the flotation cartridges prepared in examples 1-5 are between white and red, indicating that the flotation cartridges prepared by the present invention have good oxidation and aging resistance and the performance thereof increases with the addition of each material. The comparison between the example 1 and the comparative example 1 shows that the color change of the comparative example 1 is more obvious than that of the example 1, and the heat-shrinkable tape outside the polyethylene cylinder can prevent the polyethylene cylinder from being damaged by external factors such as ultraviolet rays and the like, so that the polyethylene cylinder is protected, the integral mechanical property of the polyethylene cylinder is improved, and the service life of the polyethylene cylinder is prolonged. By comparing the example 1 with the comparative example 2, the dopamine in the invention has a remarkable scavenging effect on active oxygen in the surrounding environment, so that other materials in the heat-shrinkable belt are protected from being oxidized by the active oxygen, the polyethylene cylinder body is effectively protected, and the integral oxidation resistance and aging resistance of the ocean floating cylinder are improved. By comparing example 1 with comparative example 3, it is demonstrated that 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole of the present invention acts together with the absorption of ultraviolet light and the quenching of the excited polymer molecules by AM-101, thereby avoiding photochemical reactions and reducing the generation of active oxygen around the polyethylene cylinder; meanwhile, the 4-benzoyloxy-2, 6-tetramethylpiperidine can assist dopamine in capturing active oxygen in the environment, so that the active oxygen removal effect of the dopamine is enhanced, and further the damage of the active oxygen around the polyethylene cylinder to the polyethylene cylinder is reduced.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as required after reading the present specification, but all of them are protected by patent law within the scope of the present invention.

Claims (9)

1. A radiation crosslinked polyethylene full-surrounding outer sheath type floating buoy is characterized by comprising a cylinder body, wherein the outer surface of the cylinder body is coated with a heat-shrinkable belt layer, the heat-shrinkable belt layer comprises a heat-shrinkable belt base material layer and a hot melt adhesive sheet layer, the hot melt adhesive sheet layer is positioned between the heat-shrinkable belt base material layer and one side, close to each other, of the cylinder body, the cylinder body is made of Expanded Polystyrene (EPS), the heat-shrinkable belt layer is made of heat-shrinkable belts, the heat-shrinkable belt base material layer is made of heat-shrinkable belt base materials, and the hot melt adhesive sheet layer is made of hot melt adhesive sheets;
the polyethylene cylinder is prepared from the following raw materials in parts by weight: 45-55 parts of high-density polyethylene, 15-20 parts of low-density polyethylene, 10-15 parts of novolac epoxy resin, 15-25 parts of butadiene rubber and 10-15 parts of maleic anhydride grafted high-density polyethylene;
the heat-shrinkable tape base material is prepared from the following raw materials in parts by weight: 50-60 parts of crosslinked polyethylene, 3-5 parts of an anti-ultraviolet agent, 3-5 parts of an antioxidant, 6-10 parts of dopamine, 15-20 parts of ethylene propylene rubber and 6-10 parts of maleic anhydride grafted low-density polyethylene;
the hot melt adhesive sheet is prepared from the following raw materials in parts by weight: 60-70 parts of ethylene-vinyl acetate, 15-25 parts of tackifying resin, 1-3 parts of anti-ultraviolet agent and 1-3 parts of antioxidant.
2. The fully-enclosed, externally-sheathed, float bowl of radiation crosslinked polyethylene as claimed in claim 1, wherein the thickness of the heat-shrinkable tape substrate is 1.2mm, the thickness of the heat-fusible film layer is 1.3mm, and the total thickness of the heat-shrinkable tape is 2.5mm.
3. The radiation crosslinked polyethylene all-around sheath float bowl of claim 1,
the preparation method of the heat-shrinkable tape base material comprises the following steps:
(1) Weighing 50-60 parts of crosslinked polyethylene, 3-5 parts of an anti-ultraviolet agent, 3-5 parts of an antioxidant, 6-10 parts of dopamine, 15-20 parts of ethylene propylene rubber and 6-10 parts of maleic anhydride grafted low-density polyethylene;
(2) Uniformly mixing the materials weighed in the step (1) at normal temperature to obtain a mixed material;
(3) Melting and extruding the blend obtained in the step (2) through a double-screw extruder to obtain molten liquid;
(4) And (4) rolling and cooling the molten liquid obtained in the step (3) to obtain the sheet-shaped heat-shrinkable tape base material.
4. The radiation crosslinked polyethylene all-around outer sheath float bowl according to claim 1, wherein the crosslinked polyethylene is prepared by radiation crosslinking of triallyl isocyanurate and high density polyethylene in a mass ratio of 1.
5. The radiation crosslinked polyethylene all-around outer sheath type floating pontoon according to claim 4, wherein the preparation method of the crosslinked polyethylene comprises the following steps:
(1) weighing triallyl isocyanurate and high-density polyethylene according to the mass ratio of 1;
(2) uniformly mixing the triallyl isocyanurate weighed in the step (1) and the high-density polyethylene at normal temperature to obtain a premix;
(3) melting, extruding, cooling and granulating the premix obtained in the step (2) by a double-screw extruder to obtain mixed particles;
(4) and (4) crosslinking the mixed particles obtained in the step (3) by electron beam radiation to obtain crosslinked polyethylene.
6. The radiation crosslinked polyethylene full-surrounding outer sheath type floating buoy as claimed in claim 1, wherein the preparation method of the polyethylene cylinder comprises the following steps:
1) Weighing 45-55 parts of high-density polyethylene, 15-20 parts of low-density polyethylene, 10-15 parts of novolac epoxy resin, 15-25 parts of butadiene rubber and 10-15 parts of maleic anhydride grafted high-density polyethylene;
2) Mixing the materials weighed in the step 1) at normal temperature to obtain a mixture;
3) Melting and extruding the mixture obtained in the step 2) in a double-screw extruder to obtain a blank body;
4) And injection molding the blank obtained in the step 3) by an injection molding machine and cooling to obtain the polyethylene cylinder.
7. The fully-enclosed, externally-sheathed, float bowl of radiation-crosslinked polyethylene according to claim 1, wherein the anti-uv agent is made from 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 4-benzoyloxy-2, 6-tetramethylpiperidine and AM-101 in a weight ratio of 3.
8. The radiation crosslinked polyethylene full-surrounding sheath float bowl according to claim 1, wherein the antioxidant is made of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate in a weight ratio of 1.
9. A preparation method of a radiation cross-linked polyethylene full-surrounding outer sheath type floating buoy is characterized by comprising the following steps:
s1, preparing a hot-melt film:
s11, weighing 60-70 parts of ethylene-vinyl acetate, 15-25 parts of tackifying resin, 1-3 parts of anti-ultraviolet agent and 1-3 parts of antioxidant;
s12, uniformly mixing the materials weighed in the S11 at normal temperature to obtain a mixed material;
s13, melting and extruding the mixed material obtained in the step S12 through a double-screw extruder to obtain molten slurry;
s14, rolling and cooling the molten slurry obtained in the step S13 to obtain a flaky hot melt adhesive sheet;
s15, placing the hot-melt adhesive sheet on a heat-shrinkable tape base material, and heating to combine the hot-melt adhesive sheet and the heat-shrinkable tape base material to obtain a heat-shrinkable tape;
and S2, heating and hot-melting the heat-shrinkable belt prepared in the step S15 to the outer surface of the polyethylene cylinder body, so as to obtain the floating buoy.
CN202210585601.8A 2022-05-27 2022-05-27 Radiation crosslinked polyethylene full-surrounding outer sheath type floating barrel and preparation method thereof Active CN115195243B (en)

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