CN108610759B - Preparation method of crosslinked polyethylene coating film and composite material - Google Patents
Preparation method of crosslinked polyethylene coating film and composite material Download PDFInfo
- Publication number
- CN108610759B CN108610759B CN201710001797.0A CN201710001797A CN108610759B CN 108610759 B CN108610759 B CN 108610759B CN 201710001797 A CN201710001797 A CN 201710001797A CN 108610759 B CN108610759 B CN 108610759B
- Authority
- CN
- China
- Prior art keywords
- coating film
- crosslinking
- polyethylene
- crosslinked
- crosslinked polyethylene
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 158
- 239000011248 coating agent Substances 0.000 title claims abstract description 155
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 55
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- -1 polyethylene Polymers 0.000 claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 claims abstract description 30
- 229920000573 polyethylene Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 18
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 7
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- WPRNSVPBMNJRBQ-UHFFFAOYSA-N tris[(2,2,6,6-tetramethylpiperidin-1-yl)oxy] phosphite Chemical compound CC1(C)CCCC(C)(C)N1OOP(OON1C(CCCC1(C)C)(C)C)OON1C(C)(C)CCCC1(C)C WPRNSVPBMNJRBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 description 34
- 239000010959 steel Substances 0.000 description 34
- 238000001125 extrusion Methods 0.000 description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000009501 film coating Methods 0.000 description 7
- 239000007888 film coating Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000012963 UV stabilizer Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- 229910001141 Ductile iron Inorganic materials 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C09D123/08—Copolymers of ethene
- C09D123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09D123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of forming a crosslinked polyethylene coating film on a metal surface, and discloses a preparation method of a crosslinked polyethylene coating film and a composite material. The method comprises the following steps: (1) carrying out melt blending on a polyvinyl polymer, a polyolefin grafted polar monomer copolymer, a crosslinking agent and a crosslinking assistant to obtain a crosslinkable polyethylene mixture A; (2) grinding the mixture A into crosslinkable powder B, (3) coating the crosslinkable powder B on a preheated metal base material to form a coating film C, and (4) heating the coating film C at normal pressure to perform pre-crosslinking to form a coating film D; (5) carrying out infrared irradiation crosslinking on the coating film D under normal pressure to form a crosslinked coating film F, wherein the gel content of the crosslinked coating film F is 30-85 wt%; the polyvinyl polymer is an ethylene homopolymer, or ethylene and C4～C8Copolymers of olefins; the polyolefin grafted polar monomer copolymer is a polymer obtained by graft copolymerization of polyolefin and polar monomers. Can obtain a crosslinked polyethylene coating film with high crosslinking degree and enhance the adhesion with metal.
Description
Technical Field
The invention relates to the field of crosslinked polyethylene coating films, in particular to a preparation method of a crosslinked polyethylene coating film and a composite material.
Background
The metallic material with the polyethylene coating can provide the metal with better corrosion resistance.
CN104089106A discloses a ductile cast iron pipe with corrosion resistance, which comprises a pipe matrix, wherein the inner wall of the pipe matrix is coated with an internal polyethylene coating, and the outer wall of the pipe matrix is sequentially coated with a metal coating and an external polyethylene coating from inside to outside. The manufacturing method comprises the steps of polishing the inner wall and the outer wall of the pipeline substrate, heating the pipeline substrate to 200-350 ℃, then carrying out arc spraying on the technical coating on the outer wall of the pipeline substrate, and finally respectively coating the inner polyethylene coating and the outer polyethylene coating on the inner wall and the metal coating of the pipeline substrate. After the spraying of the inner polyethylene coating and the outer polyethylene coating is finished, the pipeline matrix is placed into a curing furnace, so that the inner polyethylene coating and the outer polyethylene coating are leveled, and the temperature of the curing furnace is 180-220 ℃. The method adopts a mode of spraying polyethylene powder and then obtains the nodular cast iron pipe with the corrosion resistance by a high-temperature curing method. The use of crosslinked polyethylene is not disclosed and merely provides corrosion protection and does not suggest improved adhesion.
CN103721916A discloses a method for producing a polyvinyl chloride pipe modified by a crosslinked polyethylene coating, comprising the following steps: (1) preparing a polyethylene decalin coating solution added with a silane coupling agent KH151 and benzophenone; (2) spraying the coating solution on the outer surface of the polyvinyl chloride pipe; (3) and then placing the sprayed pipe under an ultraviolet irradiation device, and irradiating for 5-10min to form a crosslinked polyethylene coating on the surface of the polyvinyl chloride pipe. Ultraviolet irradiation is adopted to form a crosslinked polyethylene coating on the surface of the polyvinyl chloride pipe. The problem of adhesion between different materials in the preparation of the metal composite material cannot be solved.
CN1749303A discloses an infrared radiation crosslinked polyethylene plastic for pipes, wires and cables and a preparation method thereof. The polymer comprises polyethylene resin, a peroxide crosslinking agent, an antioxidant, an auxiliary crosslinking agent, a lubricant and a filler. Mixing the above mixture, granulating, drying the granulated product to water content below 200ppm, and storing in vacuum bag. When in use, the granules are put into an extruder to be made into pipes or electric wires and cables, and then put into special infrared irradiation equipment in a hot state to be irradiated and crosslinked at 180-300 ℃ to form crosslinked polyethylene pipe and electric wire and cable products. The method is used for preparing the cross-linked polyethylene pipe, and can not solve the problem of caking property among different materials when preparing the metal composite material.
CN103865142A discloses a crosslinkable polyethylene blend composition comprising (a)100 parts by weight of a polyethylene-based resin; (b)0.5 to 12 parts by weight of an unsaturated carboxylic acid, an anhydride and/or an ester derivative thereof-grafted polyolefin; and (c)0.2 to 6 parts by weight of a peroxide crosslinking agent. The invention also provides an article comprising a metal part and a product prepared by crosslinking the composition. However, in this invention, there is no disclosure of how the composition is crosslinked to obtain a crosslinked product, but in describing the measurement of adhesion, it is disclosed that the composition is hot-pressed on an aluminum plate, then cured at 200 ℃ and 10MPa for 10min for crosslinking, and then the peel strength of the crosslinked polyethylene film from the metal is measured. However, the method of forming a crosslinked polyethylene film on a metal surface by hot pressing cannot be applied to a processing technique in which pressure curing is not possible, and it is difficult to obtain a crosslinked polyethylene coating film having a high degree of crosslinking and high adhesion on a metal surface.
Disclosure of Invention
The invention aims to solve the problems that a crosslinked polyethylene coating formed on the surface of a metal by a coating process has low crosslinking degree and the coating has insufficient adhesion to a metal substrate, and provides a preparation method of the crosslinked polyethylene coating and a composite material.
In the process of researching the metal surface composite crosslinked polyethylene film, the inventor of the invention finds that in the processing technology of forming a crosslinked polyethylene coating film on the metal surface by coating crosslinkable powder containing polyethylene, a crosslinking agent and other components, high-temperature pressure crosslinking cannot be carried out by adopting a conventional hot-pressing method, and high crosslinking degree of the crosslinked polyethylene coating film cannot be obtained, so that the heat resistance and chemical resistance of the coating film are influenced. And the coating film cannot have good bonding strength with the metal substrate. Accordingly, the inventors have studied a crosslinking method particularly suitable for obtaining a crosslinked polyethylene coating film on a metal surface by a coating method, thereby obtaining the present invention.
In order to achieve the above object, the present invention provides a method for preparing a crosslinked polyethylene coating film, comprising:
(1) carrying out melt blending on a polyvinyl polymer, a polyolefin grafted polar monomer copolymer, a crosslinking agent and a crosslinking assistant to obtain a crosslinkable polyethylene mixture A;
(2) grinding the mixture A into crosslinkable powder B;
(3) coating the crosslinkable powder B on a preheated metal base material to form a coating film C;
(4) heating the coating film C under normal pressure to perform pre-crosslinking to form a coating film D;
(5) carrying out infrared irradiation crosslinking on the coating film D under normal pressure to form a crosslinked coating film F, wherein the gel content of the crosslinked coating film F is 30-85 wt%;
the polyethylene-based polymer is an ethylene homopolymer, or ethylene and C4-8Copolymers of olefins; the polyolefin grafted polar monomer copolymer is a polymer obtained by graft copolymerization of polyolefin and polar monomers.
The invention also provides a composite material, which comprises a metal base material and a crosslinked polyethylene coating film formed on the surface of the metal base material, wherein the gel content of the crosslinked polyethylene coating film is 30-85 wt%; the thickness of the crosslinked polyethylene coating film is 0.1-1.5 mm; the crosslinked polyethylene coating film is prepared by the method for preparing the crosslinked polyethylene coating film.
According to the technical scheme, for the polyethylene coating film formed by coating on the metal surface, the crosslinking process comprises two steps of heating pre-crosslinking and infrared radiation crosslinking, and the crosslinked polyethylene coating film can be formed under the condition without pressurization (under normal pressure). The obtained crosslinked polyethylene coating has high crosslinking degree, has the gel content of 30-85 wt%, and can provide better heat resistance and chemical corrosion resistance; the resulting crosslinked polyethylene coating film can exhibit strong metal adhesion to a metal substrate, and according to CJ/T120-2008, the peel strength between the metal substrate and the crosslinked polyethylene coating film is 85N/10mm or more.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
A first object of the present invention is to provide a method for preparing a crosslinked polyethylene coating film, comprising:
(1) carrying out melt blending on a polyvinyl polymer, a polyolefin grafted polar monomer copolymer, a crosslinking agent and a crosslinking assistant to obtain a crosslinkable polyethylene mixture A;
(2) grinding the mixture A into crosslinkable powder B;
(3) coating the crosslinkable powder B on a preheated metal base material to form a coating film C;
(4) heating the coating film C under normal pressure to perform pre-crosslinking to form a coating film D;
(5) carrying out infrared irradiation crosslinking on the coating film D under normal pressure to form a crosslinked coating film F, wherein the gel content of the crosslinked coating film F is 30-85 wt%;
the polyethylene-based polymer is an ethylene homopolymer, or ethylene and C4-8Copolymers of olefins; the polyolefin grafted polar monomer copolymer is a polymer obtained by graft copolymerization of polyolefin and polar monomers.
According to the invention, the polyethylene-based polymer preferably has a density of 0.85g/cm3～0.965g/cm3The melt index of the polyethylene-based polymer at 190 ℃ under the condition of 2.16kg load is 0.1g/10 min-100 g/10 min. Preferably, the polyethylene-based polymer has a melt index of 1g/10min to 20g/10min at 190 ℃ under a load of 2.16 kg. In particular, the polyethylene-based polymer may be selected from LDPE, HDPE, LLDPE, ethylene-butene copolymer or ethylene-octene copolymer. The polyvinyl polymers are knownThe biomass is commercially available as HDPE (density 0.948 g/cm) available from Shenhua corporation under the trade designation DMDA80073HDPE with melt index of 8.5g/10min) and DMDA8920 (density of 0.954 g/cm)3LLDPE (density of 0.918 g/cm) with a melt index of 20g/10min and Dushan petrochemical designation DFDA70423Melt index 2g/10min), POE8100 from Dow chemical company.
According to the invention, the polyolefin grafted polar monomer copolymer can be a product obtained by graft copolymerization of polyolefin and polar monomer, and can be a product with polyolefin as a main chain and polar monomer forming a straight chain. Preferably, in the polyolefin grafted polar monomer copolymer, the polyolefin may be selected from low density polyethylene, high density polyethylene, ethylene propylene rubber, ethylene propylene diene monomer rubber, ethylene-C4-8At least one of olefin copolymers; the polar monomer is selected from (meth) acrylic acid and/or maleic anhydride.
Preferably, the melt index of the polyolefin grafted polar monomer copolymer at 190 ℃ under the condition of 2.16kg of load is 1g/10 min-60 g/10min, and preferably 1.5g/10 min-15 g/10 min.
Preferably, the grafting rate of the polyolefin grafted polar monomer copolymer is 0.4-2 wt%; preferably 0.7 to 1.2% by weight.
In the present invention, the polyolefin grafted polar monomer copolymer is a known material and can be obtained commercially, for example, MA-g-POE with the Dow chemical company brand GR216, has a melt index of 1.5g/10min and a grafting ratio of 0.7 wt%, MA-g-HDPE with the Dow chemical company brand GR204, has a melt index of 12g/10min and a grafting ratio of 1.2 wt%.
According to the present invention, it is preferable that the crosslinking agent is at least one selected from the group consisting of 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, dicumyl peroxide, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3,5,7, 7-pentamethyl-1, 2, 4-trioxepane and 1, 4-di-tert-butylperoxyisopropylbenzene.
According to the present invention, it is preferable that the crosslinking assistant is at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and tris (2,2,6, 6-tetramethylpiperidinyloxy) phosphite.
According to the present invention, it is preferable that the polyolefin graft polar monomer copolymer is 1 to 20 parts by weight, the crosslinking agent is 0.5 to 5 parts by weight, and the crosslinking assistant is 0.01 to 10 parts by weight, based on 100 parts by weight of the polyethylene-based polymer.
In the invention, other common components can be further added into the method, for example, 0.05-5 parts by weight of crosslinking accelerator, 0.01-3 parts by weight of scorch retarder, 0.01-2.5 parts by weight of UV stabilizer and 0.01-2 parts by weight of antioxidant can be added.
In the present invention, the crosslinking accelerator may be at least one selected from the group consisting of 1, 2-polybutadiene, triallylene cyanate and triallylene isocyanate. The scorch retarder may be at least one selected from the group consisting of organic antioxidants, hydroquinones, and substituted hydroquinones. The UV stabilizer may be at least one selected from the group consisting of a benzotriazole-based stabilizer, a hindered amine-based stabilizer, and a benzophenone-based stabilizer. The antioxidant can be selected from high molecular weight hindered phenolic compounds (e.g., antioxidant 1010 or 1076), and hindered phenol complexes with phosphites and thioesters (e.g., Irganox B and Irganox C). The crosslinking accelerator, scorch retarder, UV stabilizer and antioxidant may be known substances and are commercially available.
According to the present invention, the melt blending process in step (1) can be performed by means of extrusion molding, and can be performed on twin-screw extrusion. Preferably, in the step (1), the melt blending temperature is 140 to 160 ℃.
According to the invention, the melt blending is only carried out in order to achieve a better dispersion of the components of the mixture A and not to completely crosslink, preferably the gel content of the mixture A is less than 0.5 wt.%. Indicating that no significant cross-linking occurred.
In the invention, the particle size of the crosslinkable powder is less than or equal to 60 meshes, preferably 80-150 meshes.
In the present invention, the material of the metal substrate may be steel, copper or aluminum.
In the invention, the surface of the metal substrate can be subjected to rust removal grade of Sa2 or above. The rust removal grade can be determined according to GB 8923-88.
According to the present invention, it is preferable that, in the step (3), the temperature of the metal base material is 150 to 300 ℃; preferably from 220 ℃ to 300 ℃.
In the present invention, the coating process of step (3) does not cause crosslinking of the coating film, and preferably, the gel content of the coating film C is less than 1 wt%. The method for realizing the coating can be any one of plastic dipping, spraying, electrostatic spraying and fluidized bed coating.
According to the present invention, it is preferable that the pre-crosslinking temperature in the step (4) is 200 ℃ to 280 ℃ and the pre-crosslinking time is within 6 min. The temperature and time of pre-crosslinking are controlled to reduce the heat effect on the coating film.
According to the invention, the pre-crosslinking is controlled to achieve only a certain degree of crosslinking. Preferably, the gel content of the coating film D is less than 15 wt%.
According to the invention, the infrared radiation crosslinking is further carried out in cooperation with the pre-crosslinking, so that a coating film with a higher crosslinking degree can be obtained. Preferably, in the step (5), the infrared radiation crosslinking temperature is 90-250 ℃, preferably 145-250 ℃, and more preferably 190-250 ℃; the infrared radiation crosslinking time is within 60 min. The temperature and time of infrared irradiation crosslinking are controlled to obtain proper crosslinking degree without causing excessive thermal damage to the crosslinked coating film.
In steps (4) and (5) of the present invention, the pre-crosslinking and the infrared irradiation crosslinking are carried out without applying pressure. The pressure referred to is expressed as gauge pressure, i.e., normal pressure, i.e., no pressurization, and is usually 0.1 MPa.
A second object of the present invention is to provide a composite material comprising a metal base material and a crosslinked polyethylene coating film formed on a surface of the metal base material, the crosslinked polyethylene coating film having a gel content of 30 to 85 wt%; the thickness of the crosslinked polyethylene coating film is 0.1-1.5 mm; the crosslinked polyethylene coating film is prepared by the method for preparing the crosslinked polyethylene coating film.
In the invention, the method for preparing the crosslinked polyethylene coating film provided by the invention can be preferably applied to forming the crosslinked polyethylene coating film with the thickness of 0.1-1.5 mm on the surface of the metal base material. That is, when a crosslinked polyethylene coating film having the above thickness is to be formed on the surface of a metal substrate, a crosslinked polyethylene coating film having a high degree of crosslinking and strong adhesion can be obtained by a method combining pre-crosslinking and infrared irradiation crosslinking (i.e., the method provided by the present invention).
In the present invention, the material of the metal substrate may be steel, copper or aluminum.
According to the present invention, in the composite material, the above-mentioned crosslinked polyethylene coating film is formed on the surface of the metal base material by the above-mentioned method, it is possible to improve the adhesion between the crosslinked polyethylene coating film and the metal base material in the composite material, and it is preferable that the peel strength between the metal base material and the crosslinked polyethylene coating film coated on the surface of the metal base material is 85N/10mm or more according to CJ/T120-2008.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
the heating light source of the infrared irradiation system-I is a halogen infrared heating tube; the heating light source of the infrared irradiation system-II is a carbon fiber infrared heating tube;
the gel content test was obtained by measuring the xylene insoluble content according to ASTM-D2765. Wrapping a certain amount of polyethylene resin scraps in a 120-mesh copper net, putting the copper net into a conical flask with a reflux device, boiling and refluxing for at least 24 hours by using dimethylbenzene as a solvent, drying to constant weight, and calculating the content of insoluble substances, namely gel content.
The peel strength test of the coating was performed according to CJ/T120-2008. The method comprises the following steps: samples prepared for peel strength testing: on a 100mm x 100mm square plate-like sample coated with crosslinked polyethylene, two cracks reaching as deep as the surface of the substrate tube were cut with a 10mm width using a sharp cutter. One end was lifted off without damaging the coating film and the peel strength was measured at 90 ° on an Instron universal tensile machine. The drawing rate was 50 mm/min.
Polyethylene-based polymer: HDPE (DMDA8007, density 0.948 g/cm)3Melt index of 8.5g/10 min);
HDPE (DMDA8920 density of 0.954g/cm3Melt index of 20g/10 min);
LLDPE (DFDA7042, density 0.918 g/cm)3Melt index of 2g/10 min);
polyolefin graft polar monomer copolymer: MA-g-POE for GR216, melt index of 1.5g/10min, graft ratio of 0.7 wt%;
MA-g-HDPE of GR204, melt index 12g/10min, graft ratio 1.2 wt%;
a crosslinking agent: 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane;
crosslinking assistant agent: triallyl isocyanurate;
antioxidant: irganox 1010 and Irganox 168.
Example 1
(1) 100g of DMDA8007, 5g of GR216, 1.3g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1.1g of triallyl isocyanurate, 0.1g of Irganox 1010 and 0.06g of Irganox 168 are put into a twin-screw extruder to be subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 250 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then the hot steel plate with the coating film C is placed in an oven with the set temperature of 230 ℃ and heated for 5min under normal pressure for pre-crosslinking to form a coating film D;
(5) and (3) placing the steel plate with the coating film D in an infrared irradiation system-I with the set temperature of 235 ℃, and carrying out infrared irradiation heating for 10min under normal pressure to form a cross-linked coating film F.
And finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the xylene-insoluble content of the crosslinked coating film F was 38%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 158N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Example 2
(1) 100g of DFDA7042, 10g of GR204, 1.0g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3g of triallyl isocyanurate, 0.2g of Irganox 1010 and 0.6g of Irganox 168 were fed into a twin-screw extruder and subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 220 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then the hot steel plate with the coating film C is placed in an oven with the set temperature of 200 ℃ and heated for 4min at normal pressure for pre-crosslinking to form a coating film D;
(5) and (3) placing the steel plate with the coating film D in an infrared irradiation system-I with the set temperature of 250 ℃, and carrying out infrared irradiation heating for 20min under normal pressure to form a cross-linked coating film F.
And finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the xylene-insoluble content of the crosslinked coating film F was 49%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 85N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Example 3
(1) 100g of DMDA8920, 3g of GR216, 1.2g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 0.5g of triallyl isocyanurate, 1g of Irganox 1010 and 1g of Irganox 168 are fed into a twin-screw extruder to be subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 300 ℃ for preheating for 8min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then the hot steel plate with the coating film C is placed in an oven with the set temperature of 280 ℃ and heated for 3min at normal pressure for pre-crosslinking to form a coating film D;
(5) and (3) placing the steel plate with the coating film D in an infrared irradiation system-I with the set temperature of 190 ℃, and carrying out infrared irradiation heating for 10min under normal pressure to form a cross-linked coating film F.
And finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the xylene-insoluble content of the crosslinked coating film F was 35%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 92N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Example 4
(1) 100g of DMDA8007, 5g of GR204, 1.3g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1.1g of triallyl isocyanurate, 0.1g of Irganox 1010 and 0.06g of Irganox 168 are put into a twin-screw extruder to be subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 250 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then the hot steel plate with the coating film C is placed in an oven with the set temperature of 230 ℃ and heated for 5min under normal pressure for pre-crosslinking to form a coating film D;
(5) and (3) placing the steel plate with the coating film D in an infrared irradiation system-II with the set temperature of 120 ℃, and carrying out infrared irradiation heating for 40min under normal pressure to form a cross-linked coating film F.
And finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the content of xylene insolubles of the crosslinked coating film F was 34%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 90N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Comparative example 1
(1) 100g of DMDA8007, 5g of GR216, 1.3g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1.1g of triallyl isocyanurate, 0.1g of Irganox 1010 and 0.06g of Irganox 168 are put into a twin-screw extruder to be subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 250 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then the hot steel plate with the coating film C is placed in an oven with the set temperature of 230 ℃ to be heated for 40min for pre-crosslinking to form a coating film D;
and finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the xylene-insoluble content of the crosslinked coating film F was 22%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 61N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Comparative example 2
(1) 100g of DFDA7042, 10g of GR204, 0.5g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3g of triallyl isocyanurate, 0.2g of Irganox 1010 and 0.6g of Irganox 168 were fed into a twin-screw extruder and subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 250 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) and then placing the hot steel plate with the coating film C in an infrared irradiation heating system-I with the set temperature of 235 ℃ for infrared irradiation heating for 10min to form a cross-linked coating film F.
And finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the crosslinked coating film F had a xylene-insoluble content of 32%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 52N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
Comparative example 3
(1) 100g of DMDA8920, 3g of GR216, 5g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3g of triallyl isocyanurate, 1g of Irganox 1010 and 1g of Irganox 168 are put into a twin-screw extruder to be subjected to melt blending, extrusion and granulation to obtain a mixture A;
(2) grinding the mixture A by a pulverizer, sieving the powder by a 80-mesh sieve, and collecting the sieved crosslinkable powder B;
(3) placing the hot rolled steel plate with the surface rust removal grade of Sa2.5 in an oven with the set temperature of 250 ℃ for preheating for 10min, and then dipping the preheated steel plate in the crosslinkable powder B for 10s to form a coating C;
(4) then, the hot steel plate with the coating film C is placed in an oven with the set temperature of 230 ℃ to be heated for 5min for pre-crosslinking to form a coating film D;
and finally, cooling the steel plate subjected to film coating and crosslinking to room temperature.
Gel content test the xylene-insoluble content of the crosslinked coating film F was 13%.
The crosslinked coating film F was tested for metal adhesion by an Instron universal tensile machine and had a peel strength of 52N/10 mm.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 18/1, the rotating speed of the screw is 100 r/min, and the blending temperature of the screw during extrusion is 140 ℃.
The conditions and results of the individual steps are shown in Table 1.
TABLE 1
It can be seen from the results of examples, comparative examples and table 1 that the high crosslinking of the crosslinkable polyethylene mixture coated on the metal substrate can be achieved by combining the thermal pre-crosslinking with the infrared irradiation crosslinking in the examples, a crosslinked polyethylene coating film having a high degree of crosslinking is formed, and the coating film has higher peel strength and better adhesion with the metal substrate.
In comparative example 1, the gel content of the coating film was low and the adhesion was poor using the conventional heat crosslinking process. In comparative example 2, the crosslinking method using only infrared radiation, without pre-crosslinking, could not simultaneously achieve a high degree of crosslinking and improve the adhesion properties of the coating film. Comparative example 3 employs high temperature and short time of heat crosslinking, and also fails to achieve both high crosslinking degree and improvement of adhesion property of the coating film.
Claims (17)
1. A method for preparing a crosslinked polyethylene coating film, comprising:
(1) carrying out melt blending on a polyvinyl polymer, a polyolefin grafted polar monomer copolymer, a crosslinking agent and a crosslinking assistant to obtain a crosslinkable polyethylene mixture A;
(2) grinding the mixture A into crosslinkable powder B;
(3) coating the crosslinkable powder B on a preheated metal base material to form a coating film C;
(4) heating the coating film C under normal pressure to pre-crosslink to form a coating film D, wherein the gel content of the coating film D is less than 15 wt%;
(5) carrying out infrared irradiation crosslinking on the coating film D under normal pressure to form a crosslinked coating film F, wherein the gel content of the crosslinked coating film F is 30-85 wt%;
the polyethylene-based polymer is an ethylene homopolymer, or ethylene and C4-8Copolymers of olefins; the polyolefin grafted polar monomer copolymer is a polymer obtained by graft copolymerization of polyolefin and polar monomers.
2. The method of claim 1, wherein the polyethylene-based polymer has a density of 0.85g/cm3～0.965g/cm3The melt index of the polyethylene-based polymer at 190 ℃ under the condition of 2.16kg load is 0.1g/10 min-100 g/10 min.
3. The method of claim 1, wherein the polyolefin grafted polar monomer copolymer comprises a polyolefin selected from the group consisting of low density polyethylene, high density polyethylene, ethylene propylene rubber, ethylene propylene diene monomer, ethylene-C4-8At least one of olefin copolymers; the polar monomer is selected from (meth) acrylic acid and/or maleic anhydride.
4. The method of claim 3, wherein the polyolefin grafted polar monomer copolymer has a melt index of 1g/10min to 60g/10min at 190 ℃ under a 2.16kg load.
5. The method according to claim 3, wherein the graft ratio of the polyolefin-grafted polar monomer copolymer is 0.4 to 2 wt%.
6. The process of claim 1, wherein the crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, dicumyl peroxide, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3,5,7, 7-pentamethyl-1, 2, 4-trioxepane, and 1, 4-di-tert-butylperoxyisopropyl benzene;
the crosslinking assistant is at least one selected from triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and tris (2,2,6, 6-tetramethylpiperidinyloxy) phosphite.
7. The method according to claim 1, wherein the polyolefin-grafted polar monomer copolymer is 1 to 20 parts by weight, the crosslinking agent is 0.5 to 5 parts by weight, and the crosslinking assistant is 0.01 to 10 parts by weight, relative to 100 parts by weight of the polyethylene-based polymer.
8. The process according to claim 1, wherein in step (1), the melt blending temperature is 140 to 160 ℃.
9. The method of claim 8, wherein the gel content of mixture a is less than 0.5 wt%.
10. The method of claim 1, wherein, in step (3), the temperature of the metal substrate is 150 ℃ to 300 ℃.
11. The method according to claim 10, wherein the gel content of the coating film C is less than 1 wt%.
12. The method according to claim 1, wherein, in the step (4), the pre-crosslinking temperature is 200 ℃ to 280 ℃ and the pre-crosslinking time is within 6 min.
13. The method according to claim 1, wherein, in the step (5), the infrared irradiation crosslinking temperature is 90 ℃ to 250 ℃; the infrared radiation crosslinking time is within 60 min.
14. The method according to claim 13, wherein, in the step (5), the infrared irradiation crosslinking temperature is 145 ℃ to 250 ℃.
15. The method according to claim 13, wherein, in the step (5), the infrared irradiation crosslinking temperature is 190 ℃ to 250 ℃.
16. A composite material comprises a metal base material and a crosslinked polyethylene coating film formed on the surface of the metal base material, wherein the gel content of the crosslinked polyethylene coating film is 30-85 wt%; the thickness of the crosslinked polyethylene coating film is 0.1-1.5 mm; the crosslinked polyethylene coating film is obtained by the method for producing a crosslinked polyethylene coating film according to any one of claims 1 to 15.
17. The composite material as claimed in claim 16, wherein the peel strength between the metal substrate and the crosslinked polyethylene coating film coated on the surface of the metal substrate is 85N/10mm or more in accordance with CJ/T120-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710001797.0A CN108610759B (en) | 2017-01-03 | 2017-01-03 | Preparation method of crosslinked polyethylene coating film and composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710001797.0A CN108610759B (en) | 2017-01-03 | 2017-01-03 | Preparation method of crosslinked polyethylene coating film and composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108610759A CN108610759A (en) | 2018-10-02 |
| CN108610759B true CN108610759B (en) | 2020-05-15 |
Family
ID=63658179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710001797.0A Active CN108610759B (en) | 2017-01-03 | 2017-01-03 | Preparation method of crosslinked polyethylene coating film and composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108610759B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048115B (en) * | 2019-06-06 | 2023-09-26 | 神华(北京)新材料科技有限公司 | Composite material of metal and polyolefin, preparation method and container thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2020225B (en) * | 1978-04-18 | 1982-07-21 | Du Pont Canada | Manufacture of film partially crosslinked polyethylene |
| CN1276043C (en) * | 2003-07-30 | 2006-09-20 | 北京度辰新材料股份有限公司 | High temperature resistance anticorrosive polyolefin composition and its use |
| CN100398595C (en) * | 2004-09-15 | 2008-07-02 | 上海高分子功能材料研究所 | Infrared irridiation crosslinked polyethylene plastic for pipe, wire and cable and its preparing method |
| CN103408844B (en) * | 2013-08-23 | 2015-09-23 | 无锡杰科塑业有限公司 | Radiation crosslinking flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
| CN104987576B (en) * | 2015-07-09 | 2017-09-22 | 神华集团有限责任公司 | The high polymer product of polyethylene composition and preparation method thereof and paintable high-impact heatproof |
-
2017
- 2017-01-03 CN CN201710001797.0A patent/CN108610759B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108610759A (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11390699B2 (en) | Crosslinkable polymer composition and cable with advantageous electrical properties | |
| CN101128520B (en) | Process for preparing crosslinked polymers | |
| US20210027912A1 (en) | Polymer composition for w&c application with advantageous electrical properties | |
| CA2290318C (en) | Crosslinked compositions containing silane-grafted polyolefins and polypropylene | |
| CN107857932B (en) | Chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| KR101847326B1 (en) | Polymer blends | |
| CN101842439B (en) | Silane-functionalised polyolefin compositions, products thereof and preparation processes thereof for wire and cable applications | |
| CA2792990A1 (en) | Polyethylene polymer composition and power cable with improved electrical properties | |
| WO2012150285A1 (en) | Polymer composition for electrical devices | |
| US20220204734A1 (en) | Compositions comprising ldpe, polypropylene and functionalised polyolefins | |
| CN114040941B (en) | Polymer composition comprising polyolefin mixture | |
| US10679769B2 (en) | Cable with improved electrical properties | |
| CA2695313A1 (en) | Moisture-crosslinked polyolefin compositions | |
| US20220235211A1 (en) | Compositions comprising ldpe and functionalised polyolefins | |
| CN109313960B (en) | Cable with advantageous electrical properties | |
| JP6865225B2 (en) | Methods for Producing Functionalized Ethylene Polymers with Low Gel Content | |
| CN108610759B (en) | Preparation method of crosslinked polyethylene coating film and composite material | |
| TWI701684B (en) | Processes for preparing cables with a crosslinked insulation layer and cables prepared by those processes | |
| RU2818291C2 (en) | Ldpe-containing compositions and functionalised polyolefins | |
| CN108264646B (en) | Preparation method of crosslinked polyethylene film | |
| RU2816841C2 (en) | Compositions containing ldpe, polypropylene and functionalised polyolefins | |
| CN113929998A (en) | Polyolefin composition for rotational molding, polyolefin powder for rotational molding, and preparation method and application thereof | |
| CN118580802A (en) | Adhesive for anti-corrosion polyethylene composite belt for bent pipe, preparation method of adhesive and polyethylene composite belt | |
| CN102093498A (en) | Special polyethylene material and preparation method thereof |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 100011 Beijing, Dongcheng District Anwai Binhe West Road No. 22 Applicant after: CHINA ENERGY INVESTMENT CORPORATION Ltd. Applicant after: Beijing low carbon clean energy research institute Address before: 100011 Beijing, Dongcheng District Anwai Binhe West Road No. 22 Shenhua building Applicant before: SHENHUA GROUP CORPORATION Ltd. Applicant before: NATIONAL INSTITUTE OF CLEAN-AND-LOW-CARBON ENERGY |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |