CN110816000A

CN110816000A - Anticorrosive high-strength composite material and preparation method thereof

Info

Publication number: CN110816000A
Application number: CN201911117239.6A
Authority: CN
Inventors: 徐怀书
Original assignee: Hebei Fuente Electrical Equipment Group Co Ltd
Current assignee: Hebei Fuente Electrical Equipment Group Co Ltd
Priority date: 2019-11-15
Filing date: 2019-11-15
Publication date: 2020-02-21

Abstract

The invention relates to the field of metal anticorrosive coatings, in particular to an anticorrosive high-strength composite material and a preparation method thereof, wherein the anticorrosive high-strength composite material is of a seven-layer structure and sequentially comprises a first weather-resistant protective layer, a first rigid protective layer, a first flexible protective layer, a metal layer, a second flexible protective layer, a second rigid protective layer and a second weather-resistant protective layer from top to bottom; the thickness of the first weather-resistant protective layer and the second weather-resistant protective layer is 0.1-0.3 mm; the thickness of the first rigid protective layer and the second rigid protective layer is 0.5-3 mm; the thickness of the first flexible protection layer and the second flexible protection layer is 0.2-0.8 mm. The anticorrosive high-strength composite material disclosed by the invention has excellent compressive strength and tensile strength, has a very low heating size change rate, meets the relevant national or industrial standards, improves the mechanical properties of the anticorrosive high-strength composite material, and greatly saves the processing cost.

Description

Anticorrosive high-strength composite material and preparation method thereof

Technical Field

The invention relates to the field of metal anticorrosive coatings, in particular to an anticorrosive high-strength composite material and a preparation method thereof.

Background

In recent years, with the rapid development of the country and the high-speed construction of cities, a large amount of metal materials are applied to the fields of infrastructure, energy, chemical industry, buildings, traffic and the like, and the metal corrosion condition is more and more serious, so that a great deal of inconvenience is brought to the work and life of people, and huge loss is caused to the national economy. In order to prevent metal corrosion, an anticorrosive coating is usually applied on the metal surface to isolate the corrosive medium from contacting the metal surface, thereby achieving the anticorrosive effect. However, at present, most of the anticorrosive fillers are metals or metal compounds, which contain hexavalent heavy metals such as chromium and lead, and have the problems of high cost, short anticorrosive period, heavy metal pollution and the like, and the application of the anticorrosive fillers is strictly limited. The prior art is mostly surface spraying, the anticorrosive coating is extremely thin, and the anticorrosive effect and the mechanical strength are not very good. Such as: 1. when the composite layer is impacted by external force or thermally expanded, the composite layer is easy to deform and generate skin explosion because of no glue adhesion. 2. Under a long-time working environment, the anticorrosive layer is very thin, and the phenomenon of permeable corrosion is easy to occur, so that the protected material is damaged.

With the advent of advanced manufacturing, sustainable processes and materials will become increasingly important. Zinc-based alloys are the most common type of metal coating corrosion protection method in alloy steels to protect the bulk metal substrate at the expense of the reactive metal. This inevitably increases the production costs, since the degree of protection is proportional to the thickness of the coating, which requires long-term corrosion protection for sensitive parts. Chromium and various chromate coatings have been widely used for corrosion protection on carbon steel, zinc and aluminum substrates since the last century because of the ease of handling of electroplating and its excellent corrosion resistance, remarkable wear resistance, up to 1000kg/mm²The Vickers hardness value of the alloy, excellent surface smoothness and the like. However, the use of chromates for corrosion protection of metal coatings is severely limited due to the strong carcinogenicity of hexavalent chromium, environmental problems associated with the handling of electroplating baths, and the creation of hazardous materials during electroplating.

Currently, coating materials have been substituted for zinc and chromate, mainly including engineering polymers, conducting polymers, polysiloxanes, metal oxides, thermal sprayed cermets, self-assembled monolayer materials, active corrosion inhibitors, bioactive or biomimetic materials. The polymer coating has shown potential corrosion inhibition, but all are difficult to adhere to metal substrates, and the anticorrosive material has low compressive strength, low tensile strength, large heating dimension change rate and large processing cost.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides an anti-corrosion high-strength composite material, which has a seven-layer structure and sequentially comprises, from top to bottom, a first weather-resistant protective layer, a first rigid protective layer, a first flexible protective layer, a metal layer, a second flexible protective layer, a second rigid protective layer, and a second weather-resistant protective layer;

the thickness of the first weather-resistant protective layer and the second weather-resistant protective layer is 0.1-0.3 mm; the thickness of the first rigid protective layer and the second rigid protective layer is 0.5-3 mm; the thickness of the first flexible protection layer and the second flexible protection layer is 0.2-0.8 mm.

As an embodiment of the invention, the first weather-resistant protective layer and the second weather-resistant protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 40-70 parts of terpolymer, 20-30 parts of polyacrylate and 10-20 parts of polydibasic acid glycol ester.

In one embodiment of the present invention, the first rigid protective layer and the second rigid protective layer are made of the same raw materials, and the raw materials include, by weight, 30 to 50 parts of polyvinyl chloride resin, 10 to 30 parts of polyolefin resin, 10 to 30 parts of reinforcing agent, and 10 to 15 parts of auxiliary agent.

As an embodiment of the invention, the first flexible protection layer and the second flexible protection layer are prepared from the same raw materials, and the raw materials comprise 30-50 parts by weight of ethylene copolymer and 25-45 parts by weight of thermoplastic elastomer.

As an embodiment of the present invention, the reinforcing agent is selected from one or more of carbon black, zinc acrylate salt, calcium salt, glass fiber, basic magnesium sulfate, asbestos, carbon fiber, boron fiber, ceramic fiber, aramid fiber, stainless steel fiber, talc powder, mica powder, and silicon carbide.

As an embodiment of the present invention, the calcium salt is selected from one or more of calcium carbonate, calcium bicarbonate, calcium sulfate, calcium bisulfate, calcium sulfite, and calcium bisulfite.

As an embodiment of the present invention, the auxiliary is selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, diphenylguanidine and derivatives thereof, ethylenethiourea and derivatives thereof, N ' -diphenylpropylenediamine, N-cyclohexyl-p-anisidine, 2, 6-di-t-butyl-4-methylphenol, 2' -methylenebis- (4-methyl-6-t-butylphenol), 2' -thiobis- (4-methyl-6-t-butylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-dihydroquinoline, ceramic fiber, graphite powder, carbon black, and mixtures thereof, One or more of carbon fiber, ethylene propylene diene monomer, ethylene-octene copolymer, zinc oxide, stearic acid, zinc borate, lithium oxide and modified silicon dioxide.

In one embodiment of the present invention, the modified silica is a silica modified with a silane coupling agent.

As an embodiment of the present invention, the silane coupling agent is selected from one or more of an aminosilane coupling agent, an epoxy silane coupling agent, an acyloxy silane coupling agent, a vinyl silane coupling agent, a sulfur/mercapto silane coupling agent, an alkyl silane coupling agent, and a phenyl silane coupling agent.

The invention provides a preparation method of an anticorrosive high-strength composite material, which comprises the following steps:

(1) respectively melting preparation raw materials of a first weather-resistant protective layer, a second weather-resistant protective layer, a first rigid protective layer, a second rigid protective layer, a first flexible protective layer and a second flexible protective layer, extruding the raw materials from respective extruder heads, and then feeding the raw materials into different processing flow channels of a blow molding machine;

(2) respectively introducing air into different blow molding machines, expanding the mold blank into film bubbles, lifting the film bubbles upwards, and naturally cooling and forming the film bubbles in the lifting process to respectively obtain a first weather-resistant protective layer film, a second weather-resistant protective layer film, a first rigid protective layer film, a second rigid protective layer film, a first flexible protective layer film and a second flexible protective layer film;

(3) sequentially attaching a first flexible protective layer film, a first rigid protective layer film and a first weather-resistant protective layer film to the upper surface of the metal layer from bottom to top, and sequentially attaching a second flexible protective layer film, a second rigid protective layer film and a second weather-resistant protective layer film to the lower surface of the metal layer from top to bottom to obtain a pre-composite material;

(4) and (4) carrying out secondary heating on the pre-composite material in the step (3) by using an induction box to obtain the anticorrosive high-strength composite material.

Has the advantages that: the invention provides an anticorrosive high-strength composite material with a seven-layer structure, which has excellent compressive strength and tensile strength, has low heating size change rate, meets the relevant national or industrial standards, improves the mechanical property of the anticorrosive high-strength composite material, and saves the processing cost; the thickness of rigidity protective layer can be according to the thickness of operational environment adjustment rigidity protective layer, and the flexible protective layer in the middle of steel section bar and the rigidity protective layer plays the bonding effect, and the flexible protective layer has very high toughness, prevents rigidity protective layer and metal skeleton separation when receiving the impact. The service life of the product is effectively prolonged due to the increase of the thickness of the rigid protective layer.

Drawings

Fig. 1 is a schematic structural diagram of an anticorrosive high-strength composite material.

The interpretation of the numbered numerals in fig. 1 is in turn:

1. a first weatherable protective layer; 2. a first rigid protective layer; 3. a first flexible protective layer; 4. a metal layer; 5. a first flexible protective layer; 6. a second rigid protective layer; 7. a second weather-resistant protective layer.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing four or more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.

in a specific embodiment, the thickness of the first and second weather-resistant protective layers is 0.1 to 0.3 mm; the thickness of the first rigid protective layer and the second rigid protective layer is 0.5-3 mm; the thickness of the first flexible protection layer and the second flexible protection layer is 0.2-0.8 mm.

In a preferred embodiment, the first and second weather-resistant protective layers have a thickness of 0.2 mm; the thickness of the first rigid protective layer and the second rigid protective layer is 1.8 mm; the thickness of the first flexible protection layer and the second flexible protection layer is 0.5 mm.

In a specific embodiment, the first weather-resistant protective layer and the second weather-resistant protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 40-70 parts of a terpolymer, 20-30 parts of a polyacrylate and 10-20 parts of a polydiacid diol ester.

In a preferred embodiment, the weather-resistant protective layer is prepared from 55 parts by weight of terpolymer, 25 parts by weight of polyacrylate and 15 parts by weight of polydiacid glycol ester.

< first weather-resistant protective layer >

Terpolymer and process for preparing the same

In the present invention, the terpolymer refers to a terpolymer of diolefin containing styrene, acrylonitrile and no benzene ring.

In a specific embodiment, the terpolymer is selected from one or more of ethylene propylene rubber-styrene-acrylonitrile terpolymer, N-phenylmaleimide-styrene-acrylonitrile terpolymer, styrene-acrylonitrile-maleic anhydride terpolymer (SAM), acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile-acrylic rubber terpolymer (ASA), ethylene propylene rubber-styrene-acrylonitrile terpolymer, acrylonitrile-chlorinated polyethylene-styrene terpolymer.

In a preferred embodiment, the terpolymer is a mixture of acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile-acryl rubber terpolymer (ASA), and the mass ratio of the two is 1: (2.5-3).

Preferably, the mass ratio of acrylonitrile-butadiene-styrene terpolymer (ABS) to styrene-acrylonitrile-acryl rubber terpolymer (ASA) is 3: 8.

(ASA resin)

The ASA resin is an impact-resistant modified resin formed by copolymerizing terpolymers such as styrene, acrylonitrile, acrylic rubber and the like, has good mechanical and physical properties, is similar to ABS resin in structure and consists of acrylonitrile and butadiene rubber, and reserves the excellent mechanical and physical properties of the ABS resin as engineering plastic. The ASA resin has strong weather resistance and better high temperature resistance, and in addition, the ASA resin is an antistatic material and can ensure that dust is less accumulated on the surface.

The ASA resin was sold under the trademark PW-957 and purchased from Taiwan Qimei industries, Inc.

(ABS resin)

In the invention, the ABS resin is a graft copolymer of three monomers of Acrylonitrile (acrylonitile), 1, 3-Butadiene (Butadiene) and Styrene (Styrene). The molecular formula of the ABS resin can be written as (C)₈H₈)_x·(C₄H₆)_y·(C₃H₃N)_zBut in practice it is often a mixture of a butadiene-containing graft copolymer with an acrylonitrile-styrene copolymer, in which acrylonitrile is present in an amount of 15 to 35% by weight, butadiene is present in an amount of 5 to 30% by weight, and styrene is present in an amount of 5 to 30% by weightThe most common ratio is a: B: S ═ 20:30:50, at 40-60 wt%, where the ABS resin melting point is 175 ℃. The ABS resin is yellowish solid, has certain toughness and density of 1.04-1.06g/cm³. It has strong acid, alkali and salt corrosion resistance and can resist the dissolution of organic solvent to a certain extent. The ABS resin can normally perform at the temperature of between 25 ℃ below zero and 60 ℃, has good formability, and the processed product has smooth surface and is easy to dye and electroplate. Therefore, it can be used for daily necessities such as household appliance shells, toys and the like. The common le gao building blocks are ABS products. ABS resins can be compounded with a variety of resins to blends, such as PC/ABS, ABS/PVC, PA/ABS, PBT/ABS, etc., leading to new properties and new fields of application, such as: the transparent ABS resin can be produced by mixing ABS resin and PMMA.

The ABS resin is available under the trademark DP M305 from Enlish ABS.

Polyacrylate

In the invention, the polyacrylate is a homopolymer or a copolymer taking acrylate as a monomer.

In a specific embodiment, the polyacrylate is selected from one or more of polymethyl methacrylate, octyl polyacrylate, decyl polyacrylate, lauryl polyacrylate, and acrylic acid-acrylate copolymer.

Preferably, the polyacrylate is polymethyl methacrylate.

(polymethyl methacrylate)

In the invention, the polymethyl methacrylate (PMMA) is also called as acryl, Acrylic or plexiglass, Lucite (trade name), and is called as pressure application in taiwan, and is called as alhagi glue in hong kong, and has the advantages of high transparency, low price, easy machining, and the like, and is a glass substitute material frequently used in common. Because of its larger branched chain, polymethyl methacrylate has high viscosity, so when using the hot working method, the processing speed is relatively slow, and organic glass can be cut by a lathe and drilled by a drilling machine, can be bonded into various shapes by acetone, chloroform and the like, and can be processed into products with shapes and colors such as large airplane cabin covers, small false teeth, denture bases and the like by plastic molding methods such as blow molding, injection, extrusion and the like.

The polymethylmethacrylate is available under the trademark PMMA1100, available from Indian Chemical Resources.

Polyglycol esters of polydiacid

In the present invention, the polydiacid diol ester refers to a polycondensate of a dibasic acid and a diol.

In a specific embodiment, the polydiacid diol ester is selected from one or more of polybutylene dodecanedioate, polyethylene terephthalate, polybutylene succinate, polyacylohexanedioate diol ester, and polyacylohexanedioate l, 2-propanediol.

Preferably, the polyglycol ester is polyethylene terephthalate.

(polyethylene terephthalate)

In the invention, the polyethylene terephthalate has a chemical formula of (COC)₆H₄COOCH₂CH₂O)_n. (Polyethylene terephthalate, abbreviated as PET) is prepared by exchange of dimethyl terephthalate and ethylene glycol ester or esterification of terephthalic acid and ethylene glycol to synthesize dihydroxy ethyl terephthalate, and then polycondensation reaction. Alias: polyethylene terephthalate; polyethylene terephthalate; the quality is ensured; polyester fiber; polyethylene terephthalate; dacron, and the like. Polyethylene terephthalate is the most important variety of thermoplastic polyesters, commonly known as polyester resin. Belongs to crystalline saturated polyester, is milk white or light yellow and highly crystalline polymer, and has smooth and glossy surface. Is a common resin in life and can be divided into APET, RPET and PETG. The high-temperature-resistant and high-frequency-resistant composite material has excellent physical and mechanical properties in a wider temperature range, the long-term use temperature can reach 120 ℃, the electrical insulation property is excellent, even under high temperature and high frequency, the electrical property is still good, but the corona resistance is poor, and the creep resistance, the fatigue resistance, the friction resistance and the dimensional stability are good.

The polyethylene terephthalate is available under the trade designation PET-530, and is purchased from American MDI.

< second weather-resistant protective layer >

In the invention, the second weather-resistant protective layer is the same as the first weather-resistant protective layer.

The first weather-resistant protective layer and the second weather-resistant protective layer have good ultraviolet irradiation resistance and aging resistance, can effectively solve the problems of fading and aging of a product after being used for a period of time, and effectively protects the main structure of the bridge frame.

In a specific embodiment, the first rigid protective layer and the second rigid protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 30-50 parts of polyvinyl chloride resin, 10-30 parts of polyolefin resin, 10-30 parts of reinforcing agent and 10-15 parts of auxiliary agent.

In a preferred embodiment, the first rigid protective layer and the second rigid protective layer are made of the same raw materials, and the raw materials comprise, by weight, 25 parts of polyvinyl chloride resin, 20 parts of polyolefin resin, 20 parts of reinforcing agent and 13 parts of auxiliary agent.

< first rigid protective layer >

Polyvinyl chloride resin

In the present invention, the polyvinyl chloride resin refers to a polymer of vinyl containing chlorine.

In a specific embodiment, the polyvinyl chloride resin is selected from one or more of polyvinyl chloride resin, chlorinated polyvinyl chloride resin and chlorinated polyethylene resin.

In a preferred embodiment, the polyvinyl chloride resin is a mixture of polyvinyl chloride resin and chlorinated polyvinyl chloride resin, and the weight ratio of the polyvinyl chloride resin to the chlorinated polyvinyl chloride resin is (1.5-2): 1.

preferably, the polyvinyl chloride resin is polyvinyl chloride resin, and the weight ratio of the polyvinyl chloride resin to the chlorinated polyvinyl chloride resin is 5: 3.

(polyvinyl chloride resin)

In the present invention, the polyvinyl chloride resin, abbreviated as pvc (polyvinyl chloride), is a mixture of Vinyl Chloride Monomer (VCM) and peroxideAnd an initiator such as an azo compound, or a polymer obtained by polymerization by a radical polymerization mechanism under the action of light or heat. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively referred to as vinyl chloride resins. PVC is white powder with an amorphous structure, has small branching degree, relative density of about 1.4, glass transition temperature of 77-90 ℃, starts to decompose at about 170 ℃, has poor stability to light and heat, can decompose to generate hydrogen chloride at more than 100 ℃ or after long-time sunshine insolation, further automatically catalyzes and decomposes to cause color change, and the physical and mechanical properties are also rapidly reduced. The molecular weight of the PVC produced industrially is generally within the range of 5-11 ten thousand, and the PVC has larger polydispersity, and the molecular weight is increased along with the reduction of polymerization temperature; without a fixed melting point, softening begins at 80-85 ℃, the temperature of 130 ℃ becomes a viscoelastic state, and the temperature of 160-180 ℃ begins to be converted into a viscous state; has better mechanical property, tensile strength of about 60MPa and impact strength of 5-10kJ/m²(ii) a Has excellent dielectric properties. PVC has been the most widely used plastic in the world and is used in a very wide range of applications. The product has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like.

The polyvinyl chloride resin is R04-4, and is purchased from Shanghai chlor-alkali chemical Co.

(chlorinated polyvinyl chloride resin)

In the invention, the chlorinated polyvinyl chloride resin is prepared by chlorination modification of polyvinyl chloride resin, and is called chlorinated polyvinyl chloride (CPVC) for short. The product is white or light yellow, odorless, and nontoxic loose granule or powder. After the PVC resin is chlorinated, the irregularity of molecular bonds is increased, the polarity is increased, the solubility of the resin is increased, and the chemical stability is increased, so that the heat resistance, the acid resistance, the alkali resistance, the salt resistance, the oxidant resistance and the like of the material are improved. The mechanical property of the thermal deformation temperature of the resin is improved, the chlorine content is improved from 56.7 wt% to 63-69 wt%, the Vicat softening temperature is improved from 72-82 ℃ to 90-125 ℃, the maximum service temperature can reach 110 ℃, and the long-term service temperature is 95 ℃. The CPVC pipe has excellent corrosion resistance as a novel pipe, is widely applied to industries such as steel, metallurgy, petroleum, chemical industry, chemical fertilizer, dye, pharmacy, electric power, environmental protection, sewage treatment and the like in recent years, and is an ideal substitute of a metal anticorrosive material.

The chlorinated polyvinyl chloride resin was sold under the brand name 8067 and purchased from arkema, france.

Polyolefin resin

In the present invention, the polyolefin resin refers to a polymer of olefin.

In a specific embodiment, the polyolefin resin is a mixture of polypropylene resin and polyethylene resin, and the weight ratio of the two is 1: 1.

(Polypropylene resin)

In the invention, the polypropylene resin is a polymer formed by propylene addition polymerization, and is polypropylene for short. Polypropylene resin is a white wax-like material, transparent and light in appearance. The density is 0.89-0.91g/cm³It is inflammable, has a melting point of 165 ℃ and is softened at about 155 ℃, and the use temperature range is-30-140 ℃. Can resist corrosion of acid, alkali, salt solution and various organic solvents at the temperature of below 80 ℃, and can be decomposed at high temperature and under the action of oxidation. The polypropylene is widely applied to the production of fiber products such as clothes, blankets and the like, medical instruments, automobiles, bicycles, parts, conveying pipelines, chemical containers and the like, and is also used for packaging foods and medicines.

The polypropylene resin includes, for example: isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene. The terms "isotactic polypropylene" and "atactic polypropylene" in the present invention mean that polypropylene resins are classified into isotactic polypropylene, atactic polypropylene and syndiotactic polypropylene according to the difference in the methyl arrangement position. The methyl groups arranged on the same side of the main molecular chain are called isotactic polypropylene, if the methyl groups are arranged on both sides of the main molecular chain disorderly, the isotactic polypropylene is called, and when the methyl groups are arranged on both sides of the main molecular chain alternately, the syndiotactic polypropylene is called.

The polypropylene resin of the present invention is preferably a random polypropylene resin having a 5090T brand, which is available from Taibo polypropylene (Ningbo) Co., Ltd.

(polyethylene resin)

Polyethylene (PE) is a thermoplastic resin prepared by polymerizing ethylene, and also comprises a copolymer of ethylene and a small amount of α -olefin in industry, the polyethylene is odorless, non-toxic, feels like wax, has excellent low-temperature resistance (the lowest use temperature can reach-100 ℃), has good chemical stability, can resist corrosion of most acid and alkali (cannot resist acid with oxidation property), is insoluble in common solvents at normal temperature, has small water absorption and excellent electric insulation property, is a crystalline thermoplastic resin, and has a chemical structure, a molecular weight, a polymerization degree and other properties which are greatly dependent on a used polymerization method.

The polyethylene resins are classified into high density polyethylene, low density polyethylene and linear low density polyethylene according to the polymerization method, molecular weight and chain structure.

The LOW DENSITY POLYETHYLENE (LDPE) is commonly called high pressure POLYETHYLENE, and is mainly used for plastic bags, agricultural films and the like due to its LOW DENSITY and the softest material.

The high-density POLYETHYLENE (HIGH DENSITY POLYETHYLENE, HDPE) is commonly called low-pressure POLYETHYLENE, has higher temperature resistance, oil resistance, steam permeability resistance and environmental stress cracking resistance compared with LDPE and LLDPE, has good electrical insulation, impact resistance and cold resistance, and is mainly applied to the fields of blow molding, injection molding and the like.

The LLDPE has the appearance similar to that of LDPE, has poor transparency, but has good surface gloss, and has the advantages of LOW-temperature toughness, high modulus, bending resistance, stress cracking resistance, good impact strength at LOW temperature and the like.

The polyethylene resin of the present invention is preferably high density polyethylene, which is available from Russian Kashan organic synthetic Co., Ltd, under the trademark PE2NT 11-9.

Reinforcing agent

In the invention, the reinforcing agent is also called as a reinforcing material, and is a substance which can be added into resin to be tightly combined with the resin and obviously improve the mechanical property of the product.

In a specific embodiment, the reinforcing agent is selected from one or more of carbon black, zinc acrylate salts, calcium salts, glass fibers, basic magnesium sulfate, asbestos, carbon fibers, boron fibers, ceramic fibers, aramid fibers, stainless steel fibers, talc, mica powder, and silicon carbide.

In a preferred embodiment, the enhancer is a calcium salt.

In a preferred embodiment, the calcium salt is selected from one or more of calcium carbonate, calcium bicarbonate, calcium sulfate, calcium bisulfate, calcium sulfite, and calcium bisulfite.

Preferably, the calcium salt is a mixture of calcium carbonate and calcium bicarbonate, and the mass ratio of the calcium salt to the calcium carbonate is 1: 1.

in a preferred embodiment, the calcium carbonate is a modified calcium carbonate.

In a preferred embodiment, the modified calcium carbonate is a titanate coupling agent modified calcium carbonate.

In a preferred embodiment, the method for preparing the modified calcium carbonate comprises the following steps:

(1) weighing calcium carbonate, adding water, performing ultrasonic treatment to completely disperse the calcium carbonate, adjusting the pH value of a system to 9-10, and transferring the system into a constant-temperature oil bath pan;

(2) adding hydrazine hydrate and titanate coupling agent, reacting for 8h at 80 ℃, filtering while hot, repeatedly washing until the filtrate is neutral, and drying to obtain the final product;

the mass ratio of calcium carbonate to water in the step (1) is 1: 10; the molar ratio of hydrazine hydrate and titanate coupling agent in the step (2) to calcium carbonate in the step (1) is 2: 1.5: 1.

the titanate coupling agent has good coupling effect in filler systems such as thermoplastic plastics, thermosetting plastics, rubber and the like.

The titanate coupling agents can be broadly classified into four types according to their structures: monoalkoxy type, monoalkoxy pyrophosphate type, integral type, and ligand type.

The monoalkoxy titanate coupling agent produces a chemical bond at the interface of the inorganic powder and the matrix resin, and has the extremely unique property of forming a monomolecular film on the surface of the inorganic powder, while no polymolecular film is present at the interface. Because the chemical structure of titanate is still possessed, the surface energy is changed and the viscosity is greatly reduced in the presence of surplus coupling agent, and titanate molecules can be coupled in the matrix resin phase due to the trifunctional group and transesterification reaction of the coupling agent, so that the modification of titanate molecules and the selection of filled polymer systems are facilitated. The coupling agent (except the pyrophosphoric acid type) is particularly suitable for dry filler systems which do not contain free water and only contain chemically bonded water or physically bonded water, such as calcium carbonate, hydrated alumina and the like.

The monoalkoxy pyrophosphate titanate coupling agent is suitable for filler systems with high moisture content, such as argil, talcum powder and the like, in the systems, besides the reaction of monoalkoxy and hydroxyl on the surface of the filler to form coupling, pyrophosphate can also be decomposed to form phosphate ester, and part of water is combined.

The coordination type titanate coupling agent can avoid the side reaction of tetravalent titanate in some systems. Such as transesterification in polyesters, reaction with hydroxyl groups in epoxy resins, reaction with polyols or isocyanates in polyurethanes, and the like. The coupling agent is suitable for a plurality of filler systems, has good coupling effect, and has a coupling mechanism similar to that of a single alkoxy type.

The chelate type titanate coupling agent is suitable for high-humidity fillers and aqueous polymer systems, such as wet-process silica, argil, talcum powder, aluminum silicate, water-treated glass fiber, lamp black and the like, and in the high-humidity system, the general monoalkoxy type titanate has poor hydrolytic stability and low coupling effect, and has excellent hydrolytic stability, so that the chelating type titanate coupling agent shows good coupling effect.

In a preferred embodiment, the titanate coupling agent is selected from the group consisting of pyrophosphate titanate coupling agents, phosphite titanate coupling agents, and phosphate titanate coupling agents.

Preferably, the titanate coupling agent is a pyrophosphate titanate coupling agent.

In a preferred embodiment, the pyrophosphate-type titanate coupling agent is selected from one or more of isopropyl tris (dioctylpyrophosphate) titanate, bis (dioctyloxypyrophosphate) ethylene titanate and a solution of triethanolamine chelate.

Preferably, the pyrophosphoric acid type titanate coupling agent is isopropyl tris (dioctyl pyrophosphato acyloxy) titanate (brand No. UP-201, CAS No. 67691-13-8, available from Yokoku chemical Co., Ltd., Nanjing).

The titanium ester coupling agent modified calcium carbonate adopted in the invention not only improves the dispersibility of the calcium carbonate in a system and enables the calcium carbonate to be combined with components such as resin, modified silicon dioxide and the like more easily, but also has excellent properties and smaller heating size change rate when the UP-201 is adopted as the titanium ester coupling agent.

Auxiliary agent

In the invention, the auxiliary agent is used as a chemical additive used in a certain industry.

In a particular embodiment, the adjuvant is selected from one or more of a brightener, a plastic deodorant, a foaming agent, an antifogging agent, an antioxidant, a mold release agent, an anti-biting agent.

In a preferred embodiment, the auxiliaries are selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, diphenylguanidine and its derivatives, ethylenethiourea and its derivatives, N ' -diphenylpropylenediamine, N-cyclohexyl-p-anisidine, 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis- (4-methyl-6-tert-butylphenol), 2' -thiobis- (4-methyl-6-tert-butylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymers and 2-dihydroquinoline, ceramic fibers, graphite powder, carbon black, One or more of carbon fiber, ethylene propylene diene monomer, ethylene-octene copolymer, zinc oxide, stearic acid, zinc borate, lithium oxide and modified silicon dioxide.

In a preferred embodiment, the modified silica is a silica modified with a silane coupling agent.

In a preferred embodiment, the method for preparing the modified silica comprises the following steps:

(1) weighing a silane coupling agent, adding a solvent, adding silicon dioxide, and ultrasonically dispersing for 30-60min at normal temperature by using a JP-040/S type ultrasonic cleaner (200W) to obtain a uniform suspension;

(2) pouring the uniform suspension into a 150mL three-neck flask which is provided with a reflux condenser tube and is electrically stirred, stirring and reacting for 6-8h at the oil bath temperature, separating the reacted slurry at the normal temperature by a centrifuge at the centrifugal speed of 8000-10000r/min, and then placing the separated slurry into a vacuum drying box to dry for 6-12h at the temperature of 60-100 ℃ to obtain the prepared modified silicon dioxide.

The solvent is prepared from the following components in a volume ratio of 1: 2, a mixed solvent of ethanol and water; the mass ratio of the silane coupling agent to the solvent is 1: 30, of a nitrogen-containing gas; the mass ratio of the silane coupling agent to the silicon dioxide is 1: 5.

in a preferred embodiment, the silane coupling agent is selected from one or more of aminosilane coupling agents, epoxy silane coupling agents, acyloxy silane coupling agents, vinyl silane coupling agents, sulfur/mercapto silane coupling agents, alkyl silane coupling agents, and phenyl silane coupling agents.

Preferably, the silane coupling agent is an aminosilane coupling agent.

In a preferred embodiment, the aminosilane coupling agent is selected from one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- β (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-N-butyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, bis- [3- (triethoxysilyl) -propyl ] -amine, 3-anilinopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, bis- [3- (trimethoxysilyl) -propyl ] -amine.

Preferably, the aminosilane coupling agent is gamma-aminopropyltriethoxysilane (grade KH550, CAS 919-30-2).

In a preferred embodiment, the silane coupling agent-modified silica is present in an amount of 5 parts by weight or more.

Preferably, the weight part of the silicon dioxide modified by the silane coupling agent is 5-15 parts.

Preferably, the weight part of the silica modified by the silane coupling agent is 10 parts.

In a preferred embodiment, the mass ratio of the silane coupling agent-modified silica to the titanate coupling agent-modified calcium carbonate is 1: (1-2).

Preferably, the mass ratio of the silicon dioxide modified by the silane coupling agent to the calcium carbonate modified by the titanate coupling agent is 1: 1.3.

according to the invention, the coupling agent is adopted to modify the silicon dioxide and the calcium carbonate to improve the physical properties of the material, and the modified silicon dioxide and calcium carbonate have good compatibility in a system and can be uniformly dispersed. The inventors unexpectedly found that when the silica modified by using the aminosilane coupling agent is adopted and the coupling agent is KH550, the tensile property of the material is obviously improved, and the inventors speculate that when the aminosilane modified silica is added, a part of the aminosilane modified silica spontaneously migrates to a surface embedding system to be crosslinked and cured with resin under hot pressing, and the other part adsorbs the modified calcium carbonate with negative charges through the interaction of positive charges and negative charges to finally form a bicontinuous structure, so that the transfer of stress between the first rigid protective layer and the first flexible protective layer or the second rigid protective layer and the second flexible protective layer is easier, and the resin receives lone pair electrons of the silica to combine with the blending components to form a hybrid network to be efficiently compatibilized, and the viscoelasticity of the system is further improved. In order to ensure that the tensile property of the material is excellent, the mass ratio of the silicon dioxide modified by the silane coupling agent to the calcium carbonate modified by the titanate coupling agent is 1: (1-2) and the weight part of the silica modified by the silane coupling agent is more than 5.

< second rigid protective layer >

In the invention, the second rigid protective layer is the same as the first rigid protective layer.

The first rigid protective layer and the second rigid protective layer are formed by combining composite resin and high polymer material technologies, are extruded and molded by large-scale automatic equipment, have good corrosion resistance to acid, alkali, salt, ammonia and the like, have good flame retardant property besides good corrosion resistance, and have an oxygen index of over 32.

In an embodiment of the present invention, the first flexible protection layer and the second flexible protection layer are made of the same raw material, and the raw material is selected from one or more of ethylene copolymer, thermoplastic elastomer, and polymethyl methacrylate resin in parts by weight.

In a preferred embodiment, the first flexible protection layer and the second flexible protection layer are made of the same raw materials, and the raw materials comprise 30-50 parts by weight of ethylene copolymer and 25-45 parts by weight of thermoplastic elastomer.

In a preferred embodiment, the first flexible protection layer and the second flexible protection layer are made of the same raw materials, and the raw materials comprise 40 parts by weight of ethylene copolymer and 35 parts by weight of thermoplastic elastomer.

< first Flexible protective layer >

Ethylene copolymers

In the present invention, the ethylene copolymer is a copolymer containing ethylene and another monomer.

In a specific embodiment, the ethylene copolymer is selected from one or more of ethylene-acrylic acid copolymer, butyl acrylate-ethylene copolymer, and ethylene-vinyl acetate copolymer.

In a preferred embodiment, the ethylene copolymer is an ethylene-vinyl acetate copolymer.

(ethylene-vinyl acetate copolymer)

In the present invention, the ethylene-vinyl acetate copolymer is a general-purpose high molecular polymer, which is ethylene-vinyl acetate copolymer, abbreviated as EVA, and has a molecular formula of (C)₂H₄)_x(C₄H₆O₂)_yIt is flammable and has no irritation to combustion smell. When the content of vinyl acetate in the EVA is less than 20 wt%, the EVA can be used as plastic. EVA has good low temperature resistance, the thermal decomposition temperature is lower, about 230 ℃, the softening point of EVA is increased along with the increase of molecular weight, the processability and the surface gloss of plastic parts are reduced, but the strength is increased, the impact toughness and the environmental stress cracking resistance are improved, the chemical resistance and the oil resistance of EVA are slightly lower than those of PE (polyethylene) and PVC (polyvinyl chloride), and the change is more obvious along with the increase of the content of vinyl acetate. Ethylene and vinyl acetate copolymers are the most important products of ethylene copolymers, and are generally called EVA in foreign countries. However, in China, ethylene and vinyl acetate copolymers are classified into EVA resins, EVA rubbers and EVA emulsions according to the content of vinyl acetate therein. The product with the vinyl acetate content less than 40 wt% is EVA resin; the product with 40-70 wt% of vinyl acetate content is very flexible; the EVA resin with the content in the range is sometimes called EVA rubber due to the elastic characteristic; the vinyl acetate content is generally in the emulsion state in the range of 70 to 95% by weight, and is referred to as an EVA emulsion. The EVA emulsion is milky white or yellowish in appearance.

The EVA has improved performance compared with PE, mainly in the aspects of elasticity, flexibility, glossiness, air permeability and the like, in addition, the environmental stress cracking resistance of the EVA is improved, the compatibility to the filler is increased, and the reduction of the mechanical property of the EVA to the PE can be avoided or reduced by adopting a method of adding more reinforcing filler. EVA can also be used in new applications by modification, which can be mainly considered from two aspects: firstly, EVA is used as the stem of grafting of other monomers; secondly, performing partial alcoholysis on the EVA.

In a preferred embodiment, the ethylene-vinyl acetate copolymer is a modified ethylene-vinyl acetate copolymer.

In a preferred embodiment, the modified ethylene vinyl acetate copolymer is maleic anhydride grafted EVA, model VA1840, available from south-Beijing Huadu scientific and technical industries, Inc.

Thermoplastic elastomer

In the present invention, the thermoplastic elastomer refers to a polymer material having a glass transition temperature lower than a room temperature, an elongation at break of more than 50%, and a good restorability after removal of an external force, and broadly refers to a material that can be restored to its original shape after removal of an external force, but a material having elasticity is not necessarily a thermoplastic elastomer. The thermoplastic elastomer is a high polymer material which has obvious deformation only under weak stress and can be quickly recovered to be close to the original state and size after the stress is relaxed. Thermoplastic elastomers are an important class of elastomers. Thermoplastic elastomers are more important meaning a concept of physics and materials science, including a plurality of high molecular materials with different elastic deformation and diversified macromolecule chain crosslinking modes.

In a specific embodiment, the thermoplastic elastomer is selected from one or more of styrene-butadiene rubber, isoprene rubber, ethylene-propylene rubber, butyl rubber, chloroprene rubber, nitrile rubber, styrene-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer and thermoplastic elastomer TPE.

Preferably, the thermoplastic elastomer is a mixture of a polyurethane thermoplastic elastomer (TPU) and a thermoplastic elastomer TPE, and the weight ratio of the two is 1: (1.25-1.5).

Preferably, the weight ratio of the polyurethane thermoplastic elastomer (TPU) to the thermoplastic elastomer TPE is 3: 4.

(thermoplastic elastomer TPE)

In the present invention, the Thermoplastic elastomer TPE, also called elastomer, abbreviated as TPE or TPR, is an abbreviation of Thermoplastic rubber. The elastomer has the elasticity of rubber at normal temperature and can be plastically molded at high temperature. The thermoplastic elastomer has the structural characteristics that different resin segments and rubber segments are formed by chemical bonds, the resin segments form physical cross-linking points by virtue of inter-chain acting force, and the rubber segments are high-elasticity segments and contribute to elasticity. The physical cross-linking of the plastic segment changes reversibly with temperature, indicating the plastic processing characteristics of the thermoplastic elastomer. Therefore, thermoplastic elastomers have the physical and mechanical properties of vulcanized rubber and the processing properties of thermoplastics, are a novel polymer material between rubber and resin, and are often called third-generation rubber.

The thermoplastic elastomer TPE is available under the designation 500850 from the european VTC TPE group.

(thermoplastic polyurethane elastomer)

In the invention, the Thermoplastic polyurethane elastomer, called Thermoplastic polyurethanes for short TPU, is a high molecular material formed by the joint reaction and polymerization of diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), macromolecular polyols and low-molecular polyols (chain extenders). The halogen-free flame-retardant TPU can be widely applied to the fields of daily necessities, sports goods, toys, decorative materials and the like, and can also replace soft PVC to meet the environmental protection requirements of more and more fields.

The polyurethane elastomer is a special class of elastomers, and has a wide hardness range and a wide performance range, so that the polyurethane elastomer is a high polymer material between rubber and plastic. It is plasticized by heating, has no or little crosslinking in chemical structure, is essentially linear in its molecules, but has some physical crosslinking, and is referred to as a TPU.

The thermoplastic polyurethane elastomer is TPU modified SBS, and is prepared by the following steps: putting the TPU and the SBS into a kettle according to the mass ratio of 100:24, uniformly stirring, heating and stirring at 160 ℃ for 5 hours, and obtaining the TPU modified SBS.

Wherein the TPU is

R3000, purchased from basf, germany; SBS was DKX410 with a styrene content of 22 wt% and was purchased from Dingxin plastics materials Ltd, Dongguan.

In a preferred embodiment, the mass ratio of the maleic anhydride grafted EVA to the TPU modified SBS is (2.5-3): 1.

preferably, the mass ratio of the maleic anhydride grafted EVA to the TPU modified SBS is 8: 3.

according to the invention, maleic anhydride is adopted to graft EVA, TPU and TPE, so that the weather resistance and the heat aging resistance are improved, and meanwhile, the adhesive property is excellent. The inventors have found that with different thermoplastic elastomers, the adhesion is different, resulting in different tensile strengths of the material, especially when using TPU modified SBS, the properties of the material are superior. The inventor speculates that the styrene content of TPU modified SBS is 20-30 wt%, and the TPU modified SBS and the maleic anhydride grafted EVA can fix the elastic chain segment through the conjugation effect to play the role of internal plasticization; in addition, the inventor finds that when the mass ratio of the maleic anhydride grafted EVA to the TPU modified SBS is (2.5-3): 1, the tensile property and the compressive property of the composite material are both obviously improved, and the inventor speculates that the free maleic anhydride in the maleic anhydride grafted EVA is partially hydrolyzed during hot pressing to react with hydroxyl in the TPU modified SBS, and partially combines with N-H hydrogen bonds, further increases the crosslinking points of the resin to form a tighter three-dimensional network structure, and is firmly bonded on the metal surface.

< second Flexible protective layer >

In the invention, the second flexible protective layer is the same as the first flexible protective layer.

The first flexible protective layer/the second flexible protective layer acts between the metal layer and the first rigid protective layer/the second rigid protective layer, and has good toughness and adhesive force; the metal layer and the first flexible protective layer/the second flexible protective layer can be effectively prevented from being separated and boned due to different thermal expansion coefficients, and even if the first flexible protective layer/the second flexible protective layer cracks under the impact of external force locally, other parts of the first rigid protective layer/the second rigid protective layer can be effectively prevented from being separated.

< Metal layer >

In the present invention, the metal layer refers to a metal substrate.

The metal substrate is a metal circuit board material, belongs to electronic general elements, consists of a heat conduction insulating layer, a metal plate and a metal foil, and has the characteristics of special magnetic conductivity, excellent heat dissipation, high mechanical strength, good processing performance and the like.

The metal substrate is selected from one or more of steel profiles, steel special-shaped profiles, aluminum special-shaped profiles, copper profiles and copper special-shaped profiles.

In a specific embodiment of the invention, the metal plate is a low-carbon steel plate Q195, and the thickness is 2 mm.

In a preferred embodiment, the method for preparing the anticorrosive high-strength composite material comprises the following steps:

(4) carrying out secondary heating on the pre-composite material in the step (3) in an induction box to obtain the anticorrosive high-strength composite material;

the reaction conditions of the step (3) are as follows: the temperature is 200 ℃ and the pressure is 5000 kPa; the heating condition in the step (4) is as follows: the temperature is 300 ℃, and the heating time is 12 h.

The present invention will now be described specifically by way of examples, and the starting materials used are commercially available unless otherwise specified.

Examples

Example 1

Embodiment 1 provides an anticorrosive high-strength composite material, which has a seven-layer structure and sequentially comprises a first weather-resistant protective layer, a first rigid protective layer, a first flexible protective layer, a metal layer, a second flexible protective layer, a second rigid protective layer and a second weather-resistant protective layer from top to bottom;

the thickness of the first weather-resistant protective layer and the second weather-resistant protective layer is 0.2 mm; the thickness of the first rigid protective layer and the second rigid protective layer is 1.8 mm; the thickness of the first flexible protection layer and the second flexible protection layer is 0.5 mm.

The first weather-resistant protective layer and the second weather-resistant protective layer are prepared from the same raw materials, and the raw materials comprise 40 parts of terpolymer, 20 parts of polyacrylate and 10 parts of polydiacid dihydric alcohol ester in parts by weight;

the terpolymer is a mixture of acrylonitrile-butadiene-styrene terpolymer (ABS resin) and styrene-acrylonitrile-acryl rubber terpolymer (ASA resin), and the mass ratio of the acrylonitrile-butadiene-styrene terpolymer to the ASA resin is 3: 8; the ASA resin is PW-957, purchased from Qimei industries GmbH of Taiwan; the ABS resin is DP M305, purchased from Enlisha ABS company;

the polyacrylate is polymethylmethacrylate PMMA1100, purchased from Indian Chemical Resources, Inc.;

the polyglycol ester was polyethylene terephthalate PET-530, purchased from American MDI.

The first rigid protective layer and the second rigid protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 30 parts of polyvinyl chloride resin, 10 parts of polyolefin resin, 10 parts of reinforcing agent and 10 parts of auxiliary agent;

the polyvinyl chloride resin is a mixture of polyvinyl chloride resin and chlorinated polyvinyl chloride resin, and the weight ratio of the polyvinyl chloride resin to the chlorinated polyvinyl chloride resin is 5: 3; the polyvinyl chloride resin is R04-4 and is purchased from Shanghai chlor-alkali chemical industry Co., Ltd; the chlorinated polyvinyl chloride resin was 8067, purchased from arkema, france;

the polyolefin resin is a mixture of polypropylene resin and polyethylene resin, and the weight ratio of the polypropylene resin to the polyethylene resin is 1: 1; the polypropylene resin is a random polypropylene resin 5090T purchased from Taibo polypropylene (Ningbo) Co., Ltd; the polyethylene resin is high-density polyethylene, the trade name of the high-density polyethylene is PE2NT11-9, and the polyethylene resin is purchased from Russian Kanshan organic synthetic company;

the reinforcing agent is a mixture of calcium carbonate and calcium bicarbonate, and the mass ratio of the calcium carbonate to the calcium bicarbonate is 1: 1, the calcium carbonate is titanate coupling agent modified calcium carbonate;

the preparation method of the modified calcium carbonate comprises the following steps:

(1) weighing calcium carbonate, adding water, performing ultrasonic treatment to completely disperse the calcium carbonate, adjusting the pH value of a system to 9, and transferring the system into a constant-temperature oil bath pan;

(2) adding hydrazine hydrate and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, reacting for 8h at 80 ℃, filtering while hot, repeatedly washing until the filtrate is neutral, and drying to obtain the final product;

the mass ratio of calcium carbonate to water in the step (1) is 1: 10; the molar ratio of hydrazine hydrate, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in the step (2) to calcium carbonate in the step (1) is 2: 1.5: 1;

the auxiliary agent is modified silicon dioxide;

the preparation method of the modified silicon dioxide comprises the following steps:

(1) weighing gamma-aminopropyltriethoxysilane, adding a solvent, adding silicon dioxide, and ultrasonically dispersing for 45min at normal temperature by using a JP-040/S type ultrasonic cleaner (200W) to obtain a uniform suspension;

(2) pouring the uniform suspension into a 150mL three-neck flask provided with a reflux condenser tube and electrically stirred, stirring and reacting for 7h at the oil bath temperature, separating the reacted slurry at normal temperature by a centrifuge at a centrifugal speed of 9000r/min, then placing the separated slurry in a vacuum drying oven, and drying for 9h at 80 ℃ to obtain the prepared modified silicon dioxide;

the first flexible protective layer and the second flexible protective layer are prepared from the same raw materials, and the raw materials comprise 30 parts of ethylene copolymer and 25 parts of thermoplastic elastomer in parts by weight;

the ethylene copolymer is an ethylene-vinyl acetate copolymer which is maleic anhydride grafted EVA (ethylene-vinyl acetate copolymer) with the model of VA1840 and is purchased from Nanjing Huadu scientific and technical industry Co., Ltd;

the thermoplastic elastomer is a mixture of polyurethane thermoplastic elastomer (TPU) and thermoplastic elastomer (TPE), and the weight ratio of the TPU to the TPE is 3: 4; the TPE is 500850 and is purchased from the European VTCTPE group; the thermoplastic polyurethane elastomer is TPU modified SBS, and is prepared by the following steps: putting the TPU and the SBS into a kettle according to the mass ratio of 100:24, uniformly stirring, heating and stirring at 160 ℃ for 5 hours to obtain TPU modified SBS; wherein the TPU is

The metal layer is a Q195 low-carbon steel plate with the thickness of 2 mm.

A preparation method of an anticorrosive high-strength composite material comprises the following steps:

Example 2

Embodiment 2 provides an anticorrosive high-strength composite material, which is different from embodiment 1 in that the preparation raw materials of the first weather-resistant protective layer and the second weather-resistant protective layer comprise, by weight, 70 parts of a terpolymer, 30 parts of polyacrylate and 20 parts of polydibasic acid glycol ester; the preparation raw materials of the first rigid protective layer and the second rigid protective layer comprise 50 parts of polyvinyl chloride resin, 30 parts of polyolefin resin, 30 parts of reinforcing agent and 15 parts of auxiliary agent; the preparation raw materials of the first flexible protection layer and the second flexible protection layer comprise 50 parts of ethylene copolymer and 45 parts of thermoplastic elastomer.

Example 3

Embodiment 3 provides an anticorrosive high-strength composite material, which is different from embodiment 1 in that the preparation raw materials of the first weather-resistant protective layer and the second weather-resistant protective layer comprise, by weight, 55 parts of a terpolymer, 25 parts of polyacrylate and 15 parts of polydiacid dihydric alcohol ester; the preparation raw materials of the first rigid protective layer and the second rigid protective layer comprise 25 parts of polyvinyl chloride resin, 20 parts of polyolefin resin, 20 parts of reinforcing agent and 13 parts of auxiliary agent; the preparation raw materials of the first flexible protection layer and the second flexible protection layer comprise 40 parts of ethylene copolymer and 35 parts of thermoplastic elastomer.

Example 4

Example 4 provides an anticorrosive high-strength composite material, which is different from example 3 in that gamma-aminopropyltriethoxysilane in the preparation method of the modified silica is replaced by bis- [3- (trimethoxy silicon) -propyl ] -amine, the CAS number of which is 82985-35-1.

Example 5

Example 5 provides an anticorrosive high-strength composite material, which is different from example 3 in that gamma-aminopropyltriethoxysilane in the preparation method of modified silica is replaced by 1, 2-bis (triethoxysilyl) ethane, and the CAS number of the 1, 2-bis (triethoxysilyl) ethane is 16068-37-4.

Example 6

Example 6 provides an anticorrosive high-strength composite material, which is different from example 3 in that modified silica is replaced with silica.

Example 7

Example 7 provides an anticorrosive high-strength composite material, which is different from example 3 in that modified calcium carbonate is replaced with calcium carbonate.

Example 8

Example 8 provides an anticorrosive high-strength composite material, which is different from example 3 in that isopropyl tris (dioctyl pyrophosphato acyloxy) titanate in the preparation method of the modified calcium carbonate is replaced with isopropyl triisostearate having a CAS number of 61417-49-0.

Example 9

Example 9 provides an anticorrosive high-strength composite material, which is different from example 3 in that the reinforcing agent is 2 parts by weight.

Example 10

Example 10 provides an anticorrosive high-strength composite material, which is different from example 3 in that the auxiliary agent is 2 parts by weight.

Example 11

Example 11 provides a corrosion resistant high strength composite, differing from example 3 in that the maleic anhydride grafted EVA was replaced by EVA 1301, said EVA 1301 being purchased from Marco Polo International, USA.

Example 12

Example 12 provides an anticorrosive high strength composite, differing from example 3 in that the TPU modified SBS is replaced by 5712TPU, which 5712TPU is purchased from luobu run advanced materials company.

Example 13

Example 13 provides a corrosion resistant high strength composite, differing from example 3 in that the ethylene copolymer is present in 5 parts by weight.

Example 14

Example 14 provides an anticorrosive high-strength composite material, which is different from example 3 in that the thermoplastic elastomer is 5 parts by weight.

Example 15

Embodiment 15 provides an anticorrosive high-strength composite material, which is different from embodiment 3 in that the preparation step of the thermoplastic polyurethane elastomer modified by the TPU into the SBS comprises: putting TPU and SBS into a kettle according to the mass ratio of 10:24, stirring uniformly, and heating and stirring at 160 ℃ for 5 hours to obtain the TPU-SBS modified ABS resin.

Evaluation of Performance

1. Compressive strength: the compressive strength tests were performed on the corrosion-resistant high-strength composite materials of examples 1-15 using the GB/T8813-2008 standard.

2. Tensile strength: the tensile strength of the anticorrosive high-strength composite materials of examples 1 to 15 was measured according to the IPC-TM-650(2.4.19) method using a universal tensile machine as equipment, and it was judged that the tensile strength was higher than 100 MPa.

3. Heating size change rate: the corrosion resistant high strength composites of examples 1-15 were subjected to a heat dimensional change rate test according to ISO23999 standard.

Table 1 results of performance testing

From the test results in table 1, the anticorrosive high-strength composite material provided by the invention has excellent compressive strength and tensile strength, has a very low heating size change rate, meets the relevant national or industrial standards, improves the mechanical properties of the anticorrosive high-strength composite material, and saves the processing cost.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The anti-corrosion high-strength composite material is characterized by being of a seven-layer structure and sequentially comprising a first weather-resistant protective layer, a first rigid protective layer, a first flexible protective layer, a metal layer, a second flexible protective layer, a second rigid protective layer and a second weather-resistant protective layer from top to bottom;

2. The anticorrosive high-strength composite material according to claim 1, wherein the first weather-resistant protective layer and the second weather-resistant protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 40-70 parts of terpolymer, 20-30 parts of polyacrylate and 10-20 parts of polydiacid glycol ester.

3. The anticorrosive high-strength composite material as claimed in claim 1, wherein the first rigid protective layer and the second rigid protective layer are prepared from the same raw materials, and the raw materials comprise, by weight, 30-50 parts of polyvinyl chloride resin, 10-30 parts of polyolefin resin, 10-30 parts of reinforcing agent and 10-15 parts of auxiliary agent.

4. The anticorrosive high-strength composite material as claimed in claim 1, wherein the first flexible protective layer and the second flexible protective layer are prepared from the same raw materials, and the raw materials comprise 30-50 parts by weight of ethylene copolymer and 25-45 parts by weight of thermoplastic elastomer.

5. The corrosion-resistant high strength composite of claim 3 wherein the reinforcing agent is selected from one or more of carbon black, zinc acrylate salts, calcium salts, glass fibers, magnesium hydroxide sulfate, asbestos, carbon fibers, boron fibers, ceramic fibers, aramid fibers, stainless steel fibers, talc, mica powder, and silicon carbide.

6. The corrosion-resistant high strength composite of claim 5 wherein the calcium salt is selected from one or more of calcium carbonate, calcium bicarbonate, calcium sulfate, calcium bisulfate, calcium sulfite, and calcium bisulfite.

7. The corrosion-resistant high strength composite of any one of claims 4 to 5 wherein the coagent is selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, diphenylguanidine and its derivatives, ethylenethiourea and its derivatives, N ' -diphenylpropylenediamine, N-cyclohexyl-p-anisidine, 2, 6-di-t-butyl-4-methylphenol, 2' -methylenebis- (4-methyl-6-t-butylphenol), 2' -thiobis- (4-methyl-6-t-butylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-dihydroquinoline, bis (4-dihydroquinoline), bis (4-methyl-6-t-butylphenol), bis (4-methyl-6-t, Ceramic fiber, graphite powder, carbon black, carbon fiber, ethylene propylene diene monomer, ethylene-octene copolymer, zinc oxide, stearic acid, zinc borate, lithium oxide and modified silicon dioxide.

8. The corrosion-resistant high strength composite of claim 7 wherein the modified silica is a silane coupling agent modified silica.

9. The corrosion-resistant high strength composite of claim 8, wherein said silane coupling agent is selected from one or more of aminosilane coupling agents, epoxy silane coupling agents, acyloxy silane coupling agents, vinyl silane coupling agents, sulfur/mercapto silane coupling agents, alkyl silane coupling agents, and phenyl silane coupling agents.

10. The method of making a corrosion resistant high strength composite as claimed in any one of claims 1 to 9, comprising the steps of: