CN113913053A - Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof - Google Patents
Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof Download PDFInfo
- Publication number
- CN113913053A CN113913053A CN202010661450.0A CN202010661450A CN113913053A CN 113913053 A CN113913053 A CN 113913053A CN 202010661450 A CN202010661450 A CN 202010661450A CN 113913053 A CN113913053 A CN 113913053A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- weight
- filler
- parts
- crosslinkable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/06—Polyethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of polyethylene compositions, and in particular relates to a crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and a preparation method and application thereof, and a crosslinked polyethylene product and a preparation method and application thereof. The crosslinkable polyethylene composition comprises: polyethylene matrix resin, compatibility promoter, peroxide crosslinking agent and filler; relative to 100 parts by weight of polyethylene matrix resin, the using amount of the compatilizer is 1-15 parts by weight, the using amount of the peroxide crosslinking agent is 0.5-3 parts by weight, and the using amount of the filler is 1-12 parts by weight; the filler comprises platy filler or/and phosphate; the D90 of the flaky filler is less than or equal to 100 mu m, and the diameter-thickness ratio is more than or equal to 8. The crosslinked polyethylene composition has excellent adhesion with a metal matrix, and the cathode stripping resistance of the product can be remarkably improved by coating the crosslinked polyethylene composition on the surface of the metal matrix.
Description
Technical Field
The invention relates to the field of polyethylene compositions, and in particular relates to a crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and a preparation method and application thereof, and a crosslinked polyethylene product and a preparation method and application thereof.
Background
The combination of organic coating and cathodic protection is the main measure of metal corrosion prevention at the present stage. The most significant forms of coating failure are organic coating degradation and metal corrosion under the coating, resulting in a weakening of the coating's bond to the metal causing the coating to peel away from the metal surface. There are mainly 3 forms of organic coating peeling off from the metal surface: osmotic bubbling, cathodic disbanding, and anodic destruction. Among these, cathodic disbonding is the predominant form of failure of the protective properties of the coating/metal system.
Several organic coating materials are currently in common use on the market: the sintered epoxy resin FBE is brittle, has high requirements on construction quality and is easy to cause mechanical damage; the common PE has no high temperature resistance and poor adhesive force; polyolefin has poor high temperature resistance and ESCR; polytetrafluoroethylene is difficult to process and expensive; and the high-cohesiveness XLPE has excellent comprehensive performance. However, the highly adhesive XLPE resin performed very poorly in the cathodic disbondment test. The high-cohesiveness XLPE is popularized and applied in metal corrosion prevention, and the problem of poor cathode stripping performance of the high-cohesiveness XLPE resin must be solved.
CN102363689A discloses a heavy-duty anticorrosive powder coating composition with high cathodic disbonding resistance, which comprises epoxy resin, anticorrosive filler and curing agent, as well as a small amount of flatting agent, antifoaming agent, coupling agent and accelerator, and is uniformly mixed, then the mixture is added into a screw extruder, melted and extruded at the temperature of 100 ℃ and 125 ℃, and then the mixture is subjected to double-roller cooling and tabletting, the powder is ground into powder and added with fumed silica, and the powder collected after passing through a 120-160-mesh rotary screen is the powder coating. Wherein the anticorrosive filler is one or more of wollastonite, zinc phosphate, aluminum tripolyphosphate, zinc powder, aluminum powder mica powder, montmorillonite and fumed silica. However, the matrix resin of the coating composition is mainly epoxy resin and has more components, the construction process is complex, and the obtained coating film is brittle and has limited temperature resistance.
CN103374293A discloses a solvent-free polyurethane joint coating anticorrosive paint for pipelines, and relates to the technical field of general corrosion prevention of metal materials and pipeline systems. The epoxy resin composition comprises a component A and a component B, wherein the component A comprises a hydroxyl component with the average molecular weight of 200-2000-adulterant, the hydroxyl component is a polyethylene oxide addition compound with a specific molecular structure and takes bisphenol A as an initiator, and the component B is isocyanate. The coating has the advantages of small water absorption, high reaction activity and excellent cathode stripping resistance and hot water adhesion resistance of a film forming material. The component A also comprises a dispersant, a defoaming agent, a water removing agent, an anti-settling agent, a coupling agent, a curing accelerator, an antirust pigment, titanium dioxide, mica powder and barium sulfate. Wherein the rust-proof pigment is zinc phosphate. However, the matrix resin of the coating composition is polyurethane, the components are more, the requirement on the construction environment is higher, the construction process is complex, and the temperature resistance of the obtained coating film is limited.
CN109796849A discloses a high-temperature-resistant powder coating and a high-temperature-resistant anticorrosive steel pipe fitting using the same. The coating comprises 50-60 parts of a first compound, 10-20 parts of a second compound, 10-30 parts of a graphene pre-dispersion body and 10-20 parts of a nano filler. The graphene pre-dispersion is added into the coating, so that the glass transition temperature Tg of the powder coating can be effectively improved, and the cathode stripping resistance of the powder coating can be improved. The first compound is a compound of phenolic aldehyde modified epoxy resin and bisphenol A epoxy resin, and the second compound is a compound of dicyandiamide curing agent and phenolic curing agent. The graphene pre-dispersion is prepared by mixing 2-5 parts of graphene, 10-25 parts of a dispersing agent, 2-5 parts of a coupling agent and 86-65 parts of nano barium sulfate in proportion. However, the matrix resin of the coating composition is a two-component cured epoxy resin, the component for improving cathode stripping is a graphene pre-dispersion, the components are more, and the process is complex.
CN109486359A discloses a long-acting heavy-duty anticorrosive coating containing graphene-zinc powder and a preparation method thereof, wherein the component A comprises the following components in percentage by mass: 15-25 wt% of epoxy resin, 1-3.5 wt% of graphene, 15-45 wt% of zinc powder, 20-35 wt% of filler, 1-5 wt% of anti-settling agent and 10-24 wt% of organic solvent; the sum of the mass percentages of the raw materials of the component A is 100 percent; the component B comprises the following components in percentage by mass: 40-70 wt% of polyamide, 2-7 wt% of accelerator, 5-10 wt% of silane coupling agent and 15-50 wt% of organic solvent; the sum of the mass percentages of the raw materials of the component B is 100 percent. The graphene is added into the anticorrosive paint, and by utilizing the overlarge specific surface area, excellent conductivity and anticorrosive performance of the graphene, the content of zinc powder is greatly reduced, zinc mist during welding and cutting is reduced, and the environment-friendly effect is achieved. The coating has excellent adhesion and long-term cathodic disbonding resistance. However, the coating composition is a two-component cured epoxy matrix resin, the components for improving the cathode stripping performance are graphene and zinc particles, the content of the zinc particles is high, the environment-friendly degree needs to be improved, and the obtained coating film is brittle and has limited temperature resistance.
In summary, the formula of the prior art has many components, complex components, large filler addition amount, and most of matrix resins are epoxy resins, so that the application is limited.
Disclosure of Invention
The invention aims to overcome the problem of poor cathodic disbonding resistance of a crosslinked polyethylene coating film in the prior art, and provides a crosslinkable polyethylene composition, crosslinked polyethylene and a preparation method thereof, a crosslinked polyethylene product and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a crosslinkable polyethylene composition resistant to cathodic disbondment, wherein the composition comprises: polyethylene matrix resin, compatibility promoter, peroxide crosslinking agent and filler;
relative to 100 parts by weight of polyethylene matrix resin, the using amount of the compatilizer is 1-15 parts by weight, the using amount of the peroxide crosslinking agent is 0.5-3 parts by weight, and the using amount of the filler is 1-12 parts by weight; the filler comprises platy filler or/and phosphate; the particle size D90 of the flaky filler is not more than 100 mu m, and the diameter-thickness ratio is not less than 8.
In a second aspect, the present invention provides a crosslinked polyethylene, wherein the crosslinked polyethylene is prepared from the crosslinkable polyethylene composition.
The third aspect of the present invention provides a method for preparing the above crosslinked polyethylene, wherein the method comprises: in a double-screw extruder, carrying out melt blending, granulation or extrusion/tape casting on the crosslinkable polyethylene composition to form a film; the crosslinkable polyethylene composition is the crosslinkable polyethylene composition described above.
The invention provides in a fourth aspect a crosslinked polyethylene article, wherein the crosslinked polyethylene article comprises at least one metal substrate and a crosslinked polyethylene coating;
the crosslinked polyethylene coating is made from the crosslinkable polyethylene composition described above.
The fifth aspect of the present invention provides a method for preparing a crosslinked polyethylene product, wherein the method comprises applying the crosslinkable polyethylene composition onto a surface of a metal substrate, and crosslinking to obtain the crosslinked polyethylene product.
In a sixth aspect, the present invention provides a use of the crosslinkable polyethylene composition, the crosslinked polyethylene or the crosslinked polyethylene article in an oil and gas transportation pipeline.
Through the technical scheme, the crosslinkable polyethylene composition, the crosslinked polyethylene and the preparation method thereof, the crosslinked polyethylene product and the preparation method and application thereof provided by the invention have the following beneficial effects:
in the crosslinkable polyethylene composition provided by the invention, the polyethylene resin is used as the matrix resin, the dosage of the filler is obviously reduced, and the compatibility accelerator, the peroxide crosslinking agent and the specific filler are matched with each other, so that the adhesion between the crosslinkable polyethylene composition and a metal matrix can be obviously improved.
Further, the crosslinked polyethylene product obtained by coating the crosslinkable polyethylene composition provided by the invention on the surface of a metal matrix shows excellent cathodic disbonding resistance, and can meet the requirements of oil and gas transmission pipelines.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a crosslinkable polyethylene composition resistant to cathodic disbondment, wherein said composition comprises: polyethylene matrix resin, compatibility promoter, peroxide crosslinking agent and filler;
relative to 100 parts by weight of polyethylene matrix resin, the using amount of the compatilizer is 1-15 parts by weight, the using amount of the peroxide crosslinking agent is 0.5-3 parts by weight, and the using amount of the filler is 1-12 parts by weight; the filler comprises platy filler or/and phosphate; the particle size D90 of the flaky filler is not more than 100 mu m, and the diameter-thickness ratio is not less than 8.
In the crosslinkable polyethylene composition provided by the invention, the polyethylene resin is used as the matrix resin, the dosage of the filler is obviously reduced, and the compatibility accelerator, the peroxide crosslinking agent and the specific filler are matched with each other, so that the adhesion between the crosslinkable polyethylene composition and a metal matrix can be obviously improved. And the inventors have conducted extensive studies to find that the overall properties of the crosslinkable polyethylene composition are more excellent when the amounts of the components of the composition satisfy the above-mentioned limits.
In the invention, the diameter-thickness ratio of the sheet material refers to the ratio of the diameter to the thickness of the sheet material.
Further, the cross-linkable polyethylene composition has more excellent properties when the compatibilizer is used in an amount of 1 to 10 parts by weight, the peroxide cross-linking agent is used in an amount of 0.5 to 2 parts by weight, and the filler is used in an amount of 1 to 10 parts by weight, relative to 100 parts by weight of the polyethylene base resin.
According to the invention, the flaky filler and/or phosphate with the D90 of not more than 100 mu m and the aspect ratio of not less than 8 is/are selected as the filler and added into the crosslinkable polyethylene matrix resin, so that the flaky filler and/or phosphate can be dispersed, uniformly leveled and formed into a film, and the cathode stripping resistance of the product can be remarkably improved by coating the film on the surface of a metal matrix.
Furthermore, when the D90 of the flaky filler is less than or equal to 50 μm and the aspect ratio is more than or equal to 10, the crosslinkable polyethylene composition has more excellent effect.
According to the present invention, the plate-like filler is selected from at least one of mica powder, glass flake, graphene and graphene oxide.
According to the invention, the phosphate is selected from at least one of zinc phosphate hydrate, aluminium triphosphate hydrate, modified zinc phosphate and ultra-phosphorous zinc white powder.
In the present invention, when the filler is a plate-like filler, preferably, the filler further comprises reducing metal particles, wherein the electrode potential of the reducing metal particles is less than-0.409V, and the reducing metal particles do not react with water at 20 to 30 ℃.
In the present invention, when the flake filler is used in combination with the specific reducing metal particles as a filler, the coating thereof on the surface of the metal substrate can further improve the cathode peeling property of the product.
According to the present invention, the reducing metal particles are selected from at least one of zinc powder, aluminum powder and magnesium powder.
According to the invention, the ratio of the amount of the platy filler to the amount of the reducing metal particles is 0.1-6:0.5-10, preferably 0.5-5:1: 8.
According to the invention, the polyethylene matrix resin is selected from ethylene homopolymers and/or ethylene-C4-8Olefin copolymer. Specifically, the polyethylene matrix resin may be at least one of polyethylene, high density polyethylene, low density polyethylene, and linear low density polyethylene.
According to the invention, the polyethylene matrix resin has a density of 0.850 to 0.965g/cm3And a melt index at 190 ℃ under a load of 2.16kg of 0.5 to 50g/10 min.
According to the invention, the polyethylene matrix resin has a density of 0.920 to 0.965g/cm3And a melt index at 190 ℃ under a load of 2.16kg of 2 to 30g/10 min.
In the invention, the inventor researches and discovers that the addition of the compatibility promoter can obviously improve the adhesion between the crosslinkable polyethylene and the metal matrix and simultaneously contribute to improving the cathode stripping resistance of the crosslinked polyethylene product.
In particular, the use of modifier-grafted polyolefins and/or coupling agents as compatibility promoters allows more excellent technical results to be obtained.
According to the present invention, preferably, the compatibility promoter is the modified grafted polyolefin and the coupling agent, and when the modified grafted polyolefin and the coupling agent are used in an amount ratio of 3 to 15:0.3 to 3, preferably 4 to 12:0.6 to 3, the crosslinkable polyethylene composition thus obtained has more excellent effects.
According to the invention, the modifier is selected from at least one of unsaturated carboxylic acids and/or anhydrides.
According to the present invention, the modifier is at least one selected from the group consisting of (meth) acrylate monomers, (meth) acrylic monomers, and maleic anhydride.
According to the invention, the grafting yield of the modifier is greater than 0.1% by weight, preferably between 0.5 and 1.8% by weight.
According to the invention, the coupling agent is a silane coupling agent; preferably, the silane coupling agent is selected from at least one of an alkyl silane coupling agent, a vinyl silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, and a methacryloxy silane coupling agent.
According to the invention, the peroxide crosslinking agent is selected from at least one of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, bis (2, 4-dichlorobenzoyl) peroxide, bis (4-methylbenzoyl) peroxide, bis (tert-butylperoxyisopropyl) benzene, dibenzoyl peroxide, dodecyl peroxide, tert-butylcumyl peroxide and dodecyl peroxide.
According to the invention, the composition also comprises a crosslinking accelerator and an antioxidant.
According to the present invention, the crosslinking accelerator is used in an amount of 0.1 to 3 parts by weight and the antioxidant is used in an amount of 0.1 to 2 parts by weight, relative to 100 parts by weight of the polyethylene base resin.
According to the present invention, the crosslinking accelerator is used in an amount of 0.1 to 2 parts by weight and the antioxidant is used in an amount of 0.1 to 1 part by weight, relative to 100 parts by weight of the polyethylene base resin.
According to the present invention, the crosslinking accelerator is selected from at least one of 1,2 polybutadiene, diallyl terephthalate, divinylbenzene, triallyl cyanurate, and triallyl isocyanate.
According to the invention, the antioxidant is selected from 2, 4-diphenyl-4-methyl-1-pentene, 4,4' -thiobis (6-tert-butyl-3-methyl-phenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 2' -thiobis (2-tert-butyl-p-cresol), 2' -thiobis (4-chloro-6-isopropyl-3-methylphenol), 4' -thiobis (6-tert-butyl-m-cresol), 4' -thiobis (2-methyl-6-tert-butylphenol) and 4,4' -thiobis (2-tert-butyl-5-methylphenol).
In a second aspect, the present invention provides a crosslinked polyethylene, wherein the crosslinked polyethylene is prepared from the crosslinkable polyethylene composition.
According to the invention, the crosslinked polyethylene has a degree of crosslinking of greater than or equal to 20%, preferably between 25 and 85%.
The third aspect of the present invention provides a method for preparing the above crosslinked polyethylene, wherein the method comprises: in a twin-screw extruder, the crosslinkable polyethylene composition is melt blended, pelletized or extruded/cast into a film.
The crosslinkable polyethylene composition is the crosslinkable polyethylene composition described above.
According to the invention, the temperature of the melt blending is 130-150 ℃.
The invention provides in a fourth aspect a crosslinked polyethylene article, wherein the crosslinked polyethylene article comprises at least one metal substrate and a crosslinked polyethylene coating;
the crosslinked polyethylene coating is made from the crosslinkable polyethylene composition described above.
According to the invention, the metal in the metal matrix is selected from at least one of aluminium, steel and copper.
The fifth aspect of the present invention provides a method for preparing a crosslinked polyethylene product, wherein the method comprises applying the crosslinkable polyethylene composition onto a surface of a metal substrate, and crosslinking to obtain the crosslinked polyethylene product.
According to the invention, the coating mode is at least one selected from rolling coating, spraying coating and coating;
according to the invention, the conditions of crosslinking include: the crosslinking temperature is 180 ℃ and 240 ℃, and the crosslinking time is 3-300 min.
In a sixth aspect, the present invention provides a use of the crosslinkable polyethylene composition, the crosslinked polyethylene or the crosslinked polyethylene article in an oil and gas transportation pipeline.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
HDPE 8920 (melt index 20g/10min, density 0.960 g/cm)3) Supplied by the well-petrochemical monster corporation;
LLDPE 7042 (melt index of 2g/10min, density of 0.924 g/cm)3) Supplied by Shenhua corporation;
the modifier grafted polyolefin was PE grafted maleic anhydride (FB16E5, graft 0.8 wt%), available from QIYI corporation;
silane coupling agent a was gamma-aminopropyltriethoxysilane (KH550), available from santong cheng guang corporation;
silane coupling agent B was vinyltriethoxysilane (A171), available from Shandong Chenguang company;
the antioxidant is antioxidant 300, purchased from Guangzhou silver well refinement science and technology Limited;
the cross-linking agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane;
the crosslinking accelerator is industrial grade triacrylate isocyanurate (TAIC);
the types of fillers and their respective physicochemical parameters are shown in table 1;
the other raw materials used in the examples and comparative examples are all commercial products.
And (3) testing the crosslinking degree:
the degree of crosslinking of the crosslinked polyethylene product was determined according to ASTM D2765. The test method is as follows: a plastic block having a mass of W1 (about 0.300. + -. 0.015g) was cut from the cross-linked polyethylene product, cut up and placed into a 100ml stainless steel mesh bag (specification for mesh bags refer to ASTM D2765). After the sample was extracted in xylene solution at 170 ℃ for 20 hours, the sample was taken out and dried in a vacuum oven at 90 ℃ for 6 hours, and the mass was designated as W2. The degree of crosslinking was (W2/W1) × 100%.
And (3) testing the peel strength:
the peel strength was determined according to GBT23257-2009, test method as follows: a cross-linked polyethylene product is scribed into a strip with the width of about 1cm, the length of the strip is more than 20cm, and the depth of the scratch is equal to that of a steel plate. Stripping one end of a cross-linked polyethylene strip by at least 2cm from a steel plate, pulling the stripped cross-linked polyethylene by using a tensile machine, fixing the steel plate by using the other end of the cross-linked polyethylene strip, pulling the cross-linked polyethylene at the speed of 10mm/min, reading the stress value of the tensile machine, and taking the average value after the tension is stable as the peeling strength in the unit of N/cm.
And (3) testing the cathodic disbonding resistance:
testing the cathodic disbonding resistance according to the test standard of GBT23257-2009
Placing a sample piece with the coating thickness of (300-. The corrosion protection layer was inserted with a knife through the test hole and the coating was pried along the scribe line with a horizontal force until the coating exhibited significant resistance to prying. And (4) measuring the stripping distance of each scribing line from the edge of the test hole, and calculating the average value of the stripping distances, namely the cathode stripping distance of the test piece. Expressed as the arithmetic mean of the cathodic disbondment of two parallel test pieces to the nearest 0.1 mm.
TABLE 1 examples and comparative fillers
| Serial number | Name of Material | Physical and chemical parameters |
| Filler 1 | Graphene | D90 is 35 μm, and the ratio of diameter to thickness is more than 3000 |
| Filler 2 | Zinc particles | Electrode potential-0.763V, D90 ═ 4.5 μm |
| Filler 3 | Dihydrate of zinc phosphate | Particle size D90 ═ 9.6 μm |
| Filler 4 | Glass flakes | D90 is 50 μm, and the ratio of diameter to thickness is more than or equal to 30 |
| Filler 5 | White carbon black | D90 is 30 μm, and the ratio of diameter to thickness is 1 |
| Filler 6 | Iron powder | Electrode potential-0.409V, D90 ═ 6 μm |
| Filler 7 | Graphite | D90 is 800 μm, and the ratio of diameter to thickness is less than or equal to 3 |
Examples 1 to 6 and comparative examples 1 to 9
The crosslinkable polyethylene compositions of examples 1-6 and comparative examples 1-9 were prepared by extrusion at 140 c and 120rpm using a twin-screw extruder according to the formulations listed in tables 2, 3, and then cut to pellets and ground into powder using a plastic mill. And coating the crosslinkable polyethylene powder on a steel plate, and crosslinking for 30min at 210 ℃ to obtain a crosslinked polyethylene coating product. And tested for performance. The formulations and test results are shown in tables 2 and 3.
TABLE 2
TABLE 3
It is apparent from tables 2 and 3 that the examples containing the cross-linking agent, the compatibilizer and the filler in the formulation have better comprehensive performance, are obviously superior to comparative example 1 without the filler, are obviously superior to comparative example 2 without the cross-linking agent, are obviously superior to comparative example 3 without the compatibilizer, are obviously superior to comparative example 4 with higher addition of the cross-linking agent, and are obviously superior to comparative example 5 with less addition of the filler. Meanwhile, as can be seen from examples 2,5 and 6, the compounding of the silane coupling agent and the polyolefin graft type compatibilizer has a certain synergistic effect on improving the peel strength and the cathodic disbonding resistance of the XLPE coating. Example 2 is significantly better than comparative example 6, and when the flake filler is graphene, the peel strength of the coating film is affected by the addition of higher zinc particles. Example 2 is significantly superior to comparative example 9, and it can be seen that when the lamellar filler is graphene, the effect of improving the cathode peel strength of the coating film by compounding with iron powder is not good. In comparative examples 7 and 9, the aspect ratio of the filler was small, and there was almost no effect of improving the cathode peeling property of the coating film.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A crosslinkable polyethylene composition, wherein the composition comprises: polyethylene matrix resin, compatibility promoter, peroxide crosslinking agent and filler;
relative to 100 parts by weight of polyethylene matrix resin, the using amount of the compatilizer is 1-15 parts by weight, the using amount of the peroxide crosslinking agent is 0.5-3 parts by weight, and the using amount of the filler is 1-12 parts by weight;
the filler comprises platy filler or/and phosphate; the D90 of the flaky filler is less than or equal to 100 mu m, and the diameter-thickness ratio is more than or equal to 8.
2. The crosslinkable polyethylene composition according to claim 1, wherein said platy filler has a D90 ≤ 50 μm and a aspect ratio ≥ 10;
preferably, the platy filler is selected from at least one of mica powder, glass flake, graphene and graphene oxide;
preferably, the phosphate is selected from at least one of zinc phosphate hydrate, aluminum tripolyphosphate hydrate, modified zinc phosphate, and ultra-phosphorous zinc white powder.
3. The crosslinkable polyethylene composition according to claim 1 or 2, wherein said filler further comprises reducing metal particles; the electrode potential of the reductive metal particles is less than-0.409V, and the reductive metal particles do not react with water at the temperature of 20-30 ℃;
preferably, the reducing metal particles are selected from at least one of zinc powder, aluminum powder and magnesium powder;
preferably, the amount ratio of the platy filler to the reducing metal particles is 0.1-6:0.5-10, preferably 0.5-5: 1-8.
4. The crosslinkable polyethylene composition according to any one of claims 1-3, wherein the compatibilising agent is used in an amount of 1-10 parts by weight, the peroxide crosslinking agent is used in an amount of 0.5-2 parts by weight and the filler is used in an amount of 1-10 parts by weight, relative to 100 parts by weight of the polyethylene base resin.
5. The crosslinkable polyethylene composition according to any one of claims 1-4, wherein the polyethylene base resin is selected from ethylene homopolymers and/or ethylene-C4-8An olefin copolymer;
preferably, the polyethylene base resin has a density of 0.85 to 0.965g/cm3A melt index at 190 ℃ under a load of 2.16kg of 0.5 to 50g/10min；
More preferably, the polyethylene base resin has a density of 0.92 to 0.965g/cm3And a melt index at 190 ℃ under a load of 2.16kg of 2 to 30g/10 min.
6. The crosslinkable polyethylene composition according to any one of claims 1-5, wherein said compatibility promoter is a modifier grafted polyolefin and/or a coupling agent;
preferably, the modifier is selected from unsaturated carboxylic acids and/or anhydrides;
preferably, the compatibility promoter is a modifier grafted polyolefin and a coupling agent;
more preferably, the modifier-grafted polyolefin and the coupling agent are used in a ratio of 3 to 15:0.3 to 3, preferably 4 to 12:0.6 to 3.
7. The crosslinkable polyethylene composition according to claim 6, wherein said modifier is selected from at least one of (meth) acrylate monomers, acrylic monomers and maleic anhydride;
preferably, the grafting yield of the modifier is greater than 0.1 wt%, preferably from 0.5 to 1.8 wt%;
preferably, the coupling agent is a silane coupling agent;
more preferably, the silane coupling agent is selected from at least one of an alkyl silane coupling agent, a vinyl silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, and a methacryloxy silane coupling agent.
8. The crosslinkable polyethylene composition according to any one of claims 1-7, wherein said peroxide crosslinking agent is selected from at least one of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -3-hexyne, bis (2, 4-dichlorobenzoyl) peroxide, bis (4-methylbenzoyl) peroxide, bis (tert-butylperoxyisopropyl) benzene, dibenzoyl peroxide, dodecyl peroxide, tert-butylcumyl peroxide and dodecyl peroxide.
9. The crosslinkable polyethylene composition according to any one of claims 1-8, wherein said composition further comprises a crosslinking accelerator and an antioxidant;
preferably, the crosslinking accelerator is used in an amount of 0.1 to 3 parts by weight and the antioxidant is used in an amount of 0.1 to 2 parts by weight, relative to 100 parts by weight of the polyethylene base resin;
more preferably, the crosslinking accelerator is used in an amount of 0.1 to 2 parts by weight and the antioxidant is used in an amount of 0.1 to 1 part by weight, relative to 100 parts by weight of the polyethylene base resin.
10. The crosslinkable polyethylene composition according to claim 9, wherein said crosslinking promoter is selected from at least one of 1,2 polybutadiene, diallyl terephthalate, divinylbenzene, triallyl cyanurate and triallyl isocyanate;
preferably, the antioxidant is selected from 2, 4-diphenyl-4-methyl-1-pentene, 4,4' -thiobis (6-tert-butyl-3-methyl-phenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 2' -thiobis (2-tert-butyl-p-cresol), 2' -thiobis (4-chloro-6-isopropyl-3-methylphenol), 4' -thiobis (6-tert-butyl-m-cresol), 4' -thiobis (2-methyl-6-tert-butylphenol) and 4,4' -thiobis (2-tert-butyl-5-methylphenol).
11. A crosslinked polyethylene, wherein the crosslinked polyethylene is produced from the crosslinkable polyethylene composition according to any one of claims 1-10.
12. Crosslinked polyethylene according to claim 11, wherein the crosslinked polyethylene has a degree of crosslinking of more than 20%, preferably of 25-85%.
13. A process for preparing the crosslinked polyethylene of claim 11 or 12, wherein the process comprises: in a double-screw extruder, carrying out melt blending, extrusion granulation or tape casting on a crosslinkable polyethylene composition to form a film, so as to obtain a crosslinkable primary mixture A, wherein the gel content of the primary mixture A is less than 5%;
the crosslinkable polyethylene composition of any one of claims 1-8;
preferably, the temperature of the melt blending is 130-150 ℃.
Coating the primary mixture A on a metal matrix, and curing at high temperature to obtain a crosslinked polyethylene coating product B;
wherein the high-temperature curing temperature is 180-240 ℃;
the gel content of the crosslinked polyethylene film-coated product B is more than 20 percent, and preferably between 25 and 85 percent.
14. A crosslinked polyethylene article, wherein said crosslinked polyethylene article comprises at least one metal substrate and a crosslinked polyethylene coating;
the crosslinked polyethylene coating is made from the crosslinkable polyethylene composition according to any one of claims 1-8.
15. The article of claim 14, wherein the metal in the metal matrix is selected from at least one of aluminum, steel, and copper.
16. A method for preparing a crosslinked polyethylene article, wherein the method comprises applying the crosslinkable polyethylene composition of any one of claims 1-10 on the surface of a metal substrate, and crosslinking to obtain the crosslinked polyethylene article;
preferably, the coating is at least one selected from the group consisting of roll coating, spray coating, and coating;
preferably, the conditions for crosslinking include: the crosslinking temperature is 180 ℃ and 240 ℃, and the crosslinking time is 3-300 min.
17. Use of the crosslinkable polyethylene composition of any one of claims 1-10, the crosslinked polyethylene of claim 11 or 12 or the crosslinked polyethylene article of claim 14 or 15 in oil and gas transport pipelines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010661450.0A CN113913053A (en) | 2020-07-10 | 2020-07-10 | Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010661450.0A CN113913053A (en) | 2020-07-10 | 2020-07-10 | Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113913053A true CN113913053A (en) | 2022-01-11 |
Family
ID=79232112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010661450.0A Pending CN113913053A (en) | 2020-07-10 | 2020-07-10 | Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113913053A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911961A (en) * | 1986-11-06 | 1990-03-27 | Siemens Aktiengesellschaft | Plastic covering for anti-corrosion protection of articles and the like |
| CN102504391A (en) * | 2011-11-03 | 2012-06-20 | 中国石油大学(北京) | Novel crossing pipeline outer layer material and preparation method |
| CN103031024A (en) * | 2012-11-22 | 2013-04-10 | 杭州五源科技实业有限公司 | Marine anticorrosive powdered paint and preparation method thereof |
| CN103865142A (en) * | 2012-12-11 | 2014-06-18 | 神华集团有限责任公司 | Crosslinkable polyethylene co-mixed composition |
| CN104327367A (en) * | 2014-10-17 | 2015-02-04 | 上海至正道化高分子材料股份有限公司 | Low-smoke low-halogen flame retardant irradiation crosslinking material for great-section wires and cables |
-
2020
- 2020-07-10 CN CN202010661450.0A patent/CN113913053A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911961A (en) * | 1986-11-06 | 1990-03-27 | Siemens Aktiengesellschaft | Plastic covering for anti-corrosion protection of articles and the like |
| CN102504391A (en) * | 2011-11-03 | 2012-06-20 | 中国石油大学(北京) | Novel crossing pipeline outer layer material and preparation method |
| CN103031024A (en) * | 2012-11-22 | 2013-04-10 | 杭州五源科技实业有限公司 | Marine anticorrosive powdered paint and preparation method thereof |
| CN103865142A (en) * | 2012-12-11 | 2014-06-18 | 神华集团有限责任公司 | Crosslinkable polyethylene co-mixed composition |
| CN104327367A (en) * | 2014-10-17 | 2015-02-04 | 上海至正道化高分子材料股份有限公司 | Low-smoke low-halogen flame retardant irradiation crosslinking material for great-section wires and cables |
Non-Patent Citations (3)
| Title |
|---|
| 于世林等: "《新世纪少年百科 知识博览创新发明》", 31 July 2011, 中国少年儿童出版社 * |
| 孙小杰等: "滚塑用交联聚乙烯材料及其在化学品储运领域的应用", 《中国塑料》 * |
| 王荣等: "《市政公用工程新技术概论》", 西北工业大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5894710B2 (en) | Method for reducing peroxide migration in crosslinkable ethylene polymer compositions | |
| CN103865142B (en) | A kind of crosslinkable polyethylene blend composition | |
| CN1276043C (en) | High temperature resistance anticorrosive polyolefin composition and its use | |
| KR102032037B1 (en) | Adhesive Composition | |
| US9852826B2 (en) | Cable with semiconductive layer made of polypropylene composition and improved long term thermal stability | |
| CN1856844B (en) | Insulating shielding composition, electric cable comprising the composition and its preparation method | |
| WO2007088737A1 (en) | Process for producing modified propylene polymer, modified propylene polymer obtained by the production process, and composition containing the modified propylene polymer | |
| AU706987B2 (en) | Polyamide-based powder composition for coating metal substrates | |
| US20200347210A1 (en) | Polymer compositions for thermal spray coating | |
| KR101655931B1 (en) | Hybrid powder coating material | |
| CN109880445B (en) | High-adhesion polyethylene powder coating and preparation method and application thereof | |
| CA2529944A1 (en) | A metal-cured polyethylene-metal laminate | |
| CN113913053A (en) | Cross-linkable polyethylene composition, cross-linked polyethylene and preparation method thereof, cross-linked polyethylene product and preparation method and application thereof | |
| CN1358205A (en) | Polyolefin compositions, method for the production and use thereof | |
| CN101402812B (en) | Conductive thermoplastic powder, preparation and uses thereof | |
| CN113913054A (en) | Crosslinkable polyethylene composition, crosslinkable polyethylene blend and composite article | |
| KR101862721B1 (en) | Coating powder for coating steel pipe, coated steel pipe, and method for coating steel pipe | |
| CN113915423A (en) | Corrosion-resistant pipeline and application | |
| CN115895347B (en) | Weld cracking-resistant low-temperature leveling polyethylene powder and preparation method and application thereof | |
| CN116829658A (en) | Melt fluororesin primer | |
| KR20150034572A (en) | Powder coating composition | |
| CN115772372A (en) | Hot melt adhesive composition for aluminum-plastic composite pipe and preparation method thereof | |
| CN1054387C (en) | Polyvinyl composition of cladding metal pipe and preparing technology | |
| CN101768394A (en) | Polar modified polymer material and preparation method thereof | |
| RU2368637C1 (en) | Mastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |