CN113915423A - Corrosion-resistant pipeline and application - Google Patents
Corrosion-resistant pipeline and application Download PDFInfo
- Publication number
- CN113915423A CN113915423A CN202010664089.7A CN202010664089A CN113915423A CN 113915423 A CN113915423 A CN 113915423A CN 202010664089 A CN202010664089 A CN 202010664089A CN 113915423 A CN113915423 A CN 113915423A
- Authority
- CN
- China
- Prior art keywords
- butyl
- peroxy
- corrosion
- polyethylene
- dimethyl
- 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
- 238000005260 corrosion Methods 0.000 title claims abstract description 48
- 230000007797 corrosion Effects 0.000 title claims description 24
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- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
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- 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 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 3
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- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 claims description 2
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- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
- F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
- F16L58/04—Coatings characterised by the materials used
- F16L58/10—Coatings characterised by the materials used by rubber or plastics
- F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
- F16L58/1063—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being a sheet wrapped around the pipe
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
- F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
- F16L58/04—Coatings characterised by the materials used
- F16L58/10—Coatings characterised by the materials used by rubber or plastics
- F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
- F16L58/1072—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being a sprayed layer
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
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Abstract
The invention relates to the field of anti-corrosion pipelines, and discloses an anti-corrosion pipeline and application thereof in natural gas and oil product transportation. The anti-corrosion pipeline comprises a metal pipe and an anti-corrosion layer attached to the outer surface of the metal pipe; the anti-corrosion layer comprises a high-cohesiveness polyethylene layer and a high-density polyethylene layer which are sequentially laminated from the outer surface of the metal pipe to the outside; the high adhesion polyethylene layer is prepared from a crosslinkable polyethylene composition comprising: (a)100 parts by weight of a polyethylene base resin; (b)0.5-12 parts by weight of a polar molecule; (c)0.01 to 1 part by weight of a peroxide crosslinking agent; (d)1-10 parts by weight of an anticorrosive filler; the polar molecule is selected from one or more of epoxy resin, polyester resin, isocyanate oligomer, acrylate and acrylate oligomer. The pipeline coating has the characteristics of high adhesive force and good cathode stripping resistance.
Description
Technical Field
The invention relates to the field of anti-corrosion pipelines, in particular to an anti-corrosion pipeline and application thereof in natural gas and oil product transportation.
Background
Corrosion resistant pipelines are commonly used as transportation vehicles for long distance transport of liquid and gaseous materials. The main application fields are gas pipelines and oil pipelines. The 3PE anti-corrosion pipeline is widely applied at present. The pipeline is provided with a 3PE anticorrosive layer which consists of bottom layer epoxy powder (FBE), middle layer Adhesive (AD) and surface layer Polyethylene (PE). In the process of preparing the 3PE anticorrosive layer, the 3PE anticorrosive pipeline needs to be coated with the 3 layers of substances respectively, the processing technology is complex, the cost is high, the energy consumption is high, and meanwhile, the epoxy powder layer and the adhesive bonding layer still have the phenomenon of debonding.
The prior art also discloses 2PE corrosion-resistant pipelines, which are formed by combining an adhesive layer and a polyethylene layer which is treated by corona treatment into a whole to form an outer corrosion-resistant layer of a metal pipeline.
However, there is still a need in the art for corrosion resistant pipes having improved adhesion between the corrosion resistant layer and the metal pipe.
Disclosure of Invention
The invention aims to overcome the problem of poor adhesion between an anticorrosive coating of an anticorrosive pipeline and a metal pipe, and provides an anticorrosive pipeline and application.
In order to achieve the above objects, a first aspect of the present invention provides an anti-corrosive pipe comprising a metal pipe and an anti-corrosive layer attached to an outer surface of the metal pipe, wherein the anti-corrosive layer comprises a high-adhesion polyethylene layer and a high-density polyethylene layer which are sequentially laminated from the outer surface of the metal pipe to the outside, wherein the high-adhesion polyethylene layer is made of a crosslinkable polyethylene composition comprising:
(a)100 parts by weight of a polyethylene base resin;
(b)0.5-12 parts by weight of a polar molecule;
(c)0.01 to 1 part by weight of a peroxide crosslinking agent;
(d)1-10 parts by weight of an anticorrosive filler;
wherein the polar molecule is selected from one or more of epoxy resin, polyester resin, isocyanate oligomer, acrylate and acrylate oligomer.
Preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, phenolic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, vinyl epoxy resin and silicone epoxy resin, wherein the epoxy value of the epoxy resin is more than 0.1; the polyester resin is selected from saturated polyester resin and/or unsaturated polyester resin, wherein the weight average molecular weight of the polyester resin is less than 5000; the isocyanate is selected from one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI); the isocyanate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; the isocyanate oligomer has a weight average molecular weight of less than 2000; the acrylate is selected from one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate; the acrylate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate; preferably, the acrylate oligomer has a weight average molecular weight of less than 2000.
Preferably, the anti-corrosion filler is selected from one or more of zinc phosphate, molybdenum zinc phosphate, aluminum zinc phosphate, iron molybdenum phosphate, iron aluminum phosphate, glass flake, graphite, graphene, titanium dioxide, zinc powder, montmorillonite and mica powder.
The second aspect of the invention provides an application of the corrosion-resistant pipeline provided by the invention in natural gas and oil product transportation.
According to the technical scheme, the anti-corrosion pipeline provided by the invention is provided with the anti-corrosion layer formed by the high-adhesion polyethylene layer made of the high-density polyethylene layer and the crosslinkable polyethylene composition, wherein the high-adhesion polyethylene layer directly adhered to the outer surface of the metal pipe adopts specific polar molecules, so that the anti-corrosion layer can be prepared and compounded with the metal pipe, the anti-corrosion layer and the metal pipe have better adhesion, the metal pipe has better anti-corrosion performance, and the anti-corrosion pipeline has the characteristic of good cathodic disbonding resistance.
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 invention provides an anti-corrosion pipeline, which comprises a metal pipe and an anti-corrosion layer attached to the outer surface of the metal pipe, wherein the anti-corrosion layer comprises a high-cohesiveness polyethylene layer and a high-density polyethylene layer which are sequentially laminated from the outer surface of the metal pipe to the outside; wherein the high tack polyethylene layer is prepared from a crosslinkable polyethylene composition comprising:
(a)100 parts by weight of a polyethylene base resin;
(b)0.5-12 parts by weight of a polar molecule;
(c)0.01 to 1 part by weight of a peroxide crosslinking agent;
(d)1-10 parts by weight of an anticorrosive filler;
wherein the polar molecule is selected from one or more of epoxy resin, polyester resin, isocyanate oligomer, acrylate and acrylate oligomer.
In some embodiments provided herein, a crosslinkable polyethylene composition is provided that is capable of forming a high adhesion polyethylene layer with better adhesion to metal parts via crosslinking at the surface of the metal parts. The polar molecule is specifically selected to enable improved adhesion. Preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, phenolic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, vinyl epoxy resin and silicone epoxy resin, wherein the epoxy value of the epoxy resin is greater than 0.1. The epoxy resin is solid or liquid with the viscosity of less than 2000Pa & s. The epoxy resins do not contain various types of curing agents. Commercially available, for example, epoxy resin E20, a solid having an epoxy value of 0.18 to 0.23. The vinyl-based epoxy resin is commercially available as the vinyl resin 901.
The polyester resin is selected from saturated polyester resin and/or unsaturated polyester resin, wherein the weight average molecular weight of the polyester resin is less than 5000. The polyester resin is solid or liquid with the viscosity of less than 2000Pa & s. The polyester resins do not contain various types of curing agents. Commercially available, for example, unsaturated polyester resin HS-156, a liquid having a weight average molecular weight of 1500-2000 and a viscosity of 700-1100 Pa.s.
The isocyanate is selected from one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI). The isocyanates do not contain various types of curing agents. Preferably diphenylmethane diisocyanate (MDI), which is commercially available.
The isocyanate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; preferably, the isocyanate oligomer has a weight average molecular weight of less than 2000. The isocyanate oligomer does not contain various types of curing agents.
The acrylate is selected from one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate. None of the acrylates contains various types of curing agents.
The acrylate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate; the acrylate oligomer has a weight average molecular weight of less than 2000. None of the acrylate oligomers contain various types of curing agents.
In some embodiments provided herein, the polyethylene matrix resin is selected to provide a final high-cohesiveness polyethylene layer capable of excellent high temperature resistance, chemical resistance, and impact strength. Preferably, the polyethylene matrix resin is selected from ethylene homopolymers and/or ethylene copolymers.
In some embodiments provided herein, preferably, the polyethylene matrix resin has a density of 0.85 to 0.965g/cm3The melt index of the polyethylene matrix resin at 190 ℃ under the load of 2.16kg is 0.01-50g/10 min; preferably, the polyethylene matrix resin has a density of 0.92 to 0.965g/cm3The polyethylene matrix resin has a melt index of 2-30g/10min at 190 ℃ and under a load of 2.16 kg.
In some embodiments of the present invention, preferably, the polyethylene matrix resin is selected from the group consisting of low density polyethylene, high density polyethylene, ethylene propylene rubber, ethylene propylene diene monomer, ethylene and C4-8In olefin copolymers toOne of them is less. The resin specifically selected may be commercially available, for example HDPE 8920 (melt index 20g/10min, density 0.960 g/cm) available from Monoshan corporation, China petrochemical3) LLDPE 7042 supplied by Shenhua corporation (melt index of 2g/10min, density of 0.924 g/cm)3)。
Still further, in the embodiment of the present invention, it is preferable that the polyethylene matrix resin is a mixture of low density polyethylene and high density polyethylene, wherein the weight ratio of the low density polyethylene to the high density polyethylene is 1 to 10: 1, preferably 1.5-9: 1. So that the density, the melt index at 190 ℃ and a load of 2.16kg of the polyethylene base resin of the blend composition are within the above-mentioned ranges.
In some embodiments, the peroxide crosslinking agent is selected to graft polar molecules in the composition with the polyethylene matrix resin on the surface of the metal part under heating, so as to improve the adhesion between the polyethylene matrix resin and the metal part. Preferably, the peroxide crosslinking agent is selected from at least one of alkyl peroxides, aryl peroxides, acyl peroxides, and ketone peroxides.
More preferably, the peroxide crosslinking agent is selected from dibenzoyl peroxide, acetylbenzoyl peroxide, dicumyl peroxide, di-tert-butylperoxy-dicumyl, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, 2, 5-dimethyl-2, 5-benzoylperoxy-hexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-hexane, 2, 5-dimethyl-2, 5-dihydroperoxy-hexane, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 7-dimethyl-2, 7-di (peroxy ethyl carbonate) -3, 5-octadiyne, 3, 6-dimethyl-3, 6-bis (peroxyethyl carbonate) -4-octyne, 3, 6-dimethyl-3, 6-di (tert-butylperoxy) -4-octyne, 2, 5-dimethyl-2, 5-di (peroxybenzoate) -3-hexyne, 2, 5-dimethyl-2, 5-di (n-propyl peroxycarbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (peroxyisobutyl carbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (peroxyethyl carbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (alpha-cumylperoxy) -3-hexyne, 2, 5-dimethyl-2, 5-bis (peroxy-beta-chloroethyl carbonate) -3-hexyne, di-2, 4-dichlorobenzoyl peroxide, di-4-methylbenzoyl peroxide, di-tert-butylperoxyisopropyl benzene, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxy-3, 5, 5-trimethyl hexanoate, tert-butyl peroxybenzoate.
In some embodiments of the present invention, the peroxide crosslinking agent and the polar molecule are used in amounts to provide crosslinking of the polyethylene matrix resin and grafting of the polar molecule to the polyethylene matrix resin. Preferably, the composition comprises: 0.05-0.8 parts by weight of a peroxide crosslinking agent and 1-10 parts by weight of said polar molecule. In particular, the peroxide crosslinking agent may be used in an amount of 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8 parts by weight in combination, and the polar molecule may be used in an amount of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight in combination. More preferably, the composition comprises: 0.05-0.5 parts by weight of a peroxide crosslinking agent and 5-10 parts by weight of said polar molecule.
In some embodiments provided herein, preferably, the composition comprises 1 to 8.1 parts by weight of the corrosion inhibiting filler, wherein the amount of the corrosion inhibiting filler can be any combination of 1, 2, 3, 4, 5, 6, 7, 8, and 8.1 parts by weight.
In some embodiments, the present invention provides an anti-corrosive filler included in the composition to enhance the cathodic disbondment resistance of a high-adhesion polyethylene layer produced from the crosslinkable polyethylene composition. Preferably, the anti-corrosion filler is selected from one or more of zinc phosphate, molybdenum zinc phosphate, aluminum zinc phosphate, iron molybdenum phosphate, iron aluminum phosphate, glass flake, graphite, graphene, titanium dioxide, zinc powder, montmorillonite and mica powder.
In some embodiments provided herein, it is preferred that the composition further comprises an antioxidant, such as at least one selected from the group consisting of antioxidants 1010, 168, 1076, 164, 1330, and DSTDP. Preferably, the antioxidant in the composition is 0.01-0.5 parts by weight, preferably 0.2 parts by weight.
In some embodiments provided herein, the composition further comprises a color masterbatch, such as commercially available black masterbatch UN5014 (available from North chemical advanced).
In some embodiments provided herein, the high adhesion polyethylene layer can be prepared in situ on the outer surface of the metal tube. Preferably, the high-adhesion polyethylene layer is prepared by the following method: the crosslinkable polyethylene composition is subjected to melt blending at the temperature of 130-160 ℃, then the obtained polymer powder is coated on the outer surface of the metal pipe in a powder spraying, curtain coating or extrusion winding manner, and then the metal pipe is subjected to heating crosslinking at the temperature of 180-250 ℃. And granulating the product obtained by melt blending to obtain crosslinkable polyethylene particles, and grinding the crosslinkable polyethylene particles to obtain polymer powder. The heating crosslinking can realize crosslinking and polar molecule grafting of the crosslinkable polyethylene composition in situ on the outer surface of the metal pipe, and better bonding of the obtained high-adhesion polyethylene layer and the outer surface of the metal pipe is realized.
In some embodiments provided herein, preferably, the temperature for the thermal crosslinking is 180-250 ℃; preferably, the metal part is made of carbon steel, stainless steel, aluminum, zinc and the like; preferably, the bonding strength between the metal part and the high-bonding polyethylene layer is 120-280N/cm, preferably 180-240N/cm; the high-cohesiveness polyethylene layer has an impact strength of 30-60kJ/m2Preferably 31-54kJ/m2(ii) a The cathode stripping length of the anticorrosive layer is 2.6-10 mm; the degree of crosslinking is 60 to 65%. .
In some embodiments, the high-density polyethylene layer as the outer layer of the corrosion protection layer may be organically combined with the high-cohesiveness polyethylene layer by applying powder of high-density polyethylene resin to the surface of the high-cohesiveness polyethylene layer by spraying or spin-winding. The high density polyethylene resin is commercially available, preferably the high density polyethylene may be a commercially available pipeline grade high density polyethylene, such as HDPE B5703 (available from medium petrochemicals).
The second aspect of the invention provides an application of the corrosion-resistant pipeline provided by the invention in natural gas and oil product transportation.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
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 polar molecule is epoxy resin E20, available from Stannless resin factories; vinyl 901, available from febuxostat, wako polymer incorporated; unsaturated polyester resin HS-156, available from Henzhou Huake Polymer Ltd;
the cross-linking agent is dicumyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne;
the anticorrosive filler is zinc-molybdenum phosphate, zinc powder and graphene;
the antioxidants are 1010 and 168;
the color master batch is black master batch UN 5014. (ii) a
The outer high density polyethylene layer was HDPE B5703, available from the medium petrochemical industry.
The degree of crosslinking of the high-tack polyethylene layer was determined according to ASTM D2765. The test method is as follows: a sample piece having a mass of W1 (about 0.300 ± 0.015g) was cut from the high-tack polyethylene layer, chopped and placed into a 100mL stainless steel mesh bag (specification for mesh bag refer to requirements of astm d 2765). 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.
Degree of crosslinking ═ 100% of (W2/W1).
The peel strength (N/cm) of the anticorrosive coating is measured according to GB/T23257-2017, and the test method is as follows: and scribing a long strip with the width of 1cm on the anticorrosive coating of the composite material product, wherein the length of the long strip is more than 20cm, and the scratch depth reaches the metal part. Peeling one end of the strip at least 2cm from the metal part, and pulling the peeled strip at a speed of 10mm/min by using a tensile machine; and reading the stress value of the tensile machine, and taking the average value of the stable tensile force as the peeling strength after the stable tensile force is stable.
The cathodic disbonding length (mm) of the anticorrosive coating is determined according to GB/T23257-2017, and the test method is as follows: placing a sample piece with the coating thickness of 300-400 mu m and the artificial defect diameter of 3.2mm in NaCl solution with the concentration of 3 weight percent, applying a voltage of-3.50V, keeping the temperature at 65 ℃ for 24 hours, taking down the sample piece and cooling to room temperature; and (4) cutting the coating outwards by a knife with eight equal divisions of the test hole as the center along the circumference of 360 degrees, wherein the anti-corrosion layer needs to be cut through to expose the base material, and the cutting distance is at least 20 mm. 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.
The impact strength of the anticorrosive coating is determined according to GB/T1843-2008, the specification of the test sheet is 100X 20X 4mm, and the gap is 2 mm.
Example 1
The components of the crosslinkable polyethylene composition constituting the inner layer as listed in table 1 were pelletized by extrusion at 160 c and 120rpm using a twin-screw extruder as shown in table 1, and the resulting pellets were ground into polymer powder using a plastic mill. And directly spraying polymer powder on the outer surface of the steel pipe, and heating and crosslinking at 180 ℃ to form a high-cohesiveness polyethylene layer. The degree of crosslinking of the high-tack polyethylene layer was determined according to ASTM D2765.
The components constituting the outer layer listed in table 1 were melt-blended to obtain high-density polyethylene powder, which was sprayed on the surface of the high-adhesion polyethylene layer to form an anticorrosive layer, and an anticorrosive pipeline was produced. The peel strength (N/cm) and the cathodic peel length (mm) of the anticorrosive layer were measured according to GB/T23257-2017, and the impact strength of the anticorrosive layer was measured according to GB/T1843-2008, the results of which are shown in Table 2.
Example 2
The components of the crosslinkable polyethylene composition constituting the inner layer as listed in table 1 were pelletized by extrusion at 140 c and 150rpm using a twin-screw extruder as shown in table 1, and the resulting pellets were ground into polymer powder using a plastic mill. And directly spraying polymer powder on the outer surface of the steel pipe, and heating and crosslinking at 200 ℃ to form a high-cohesiveness polyethylene layer. The degree of crosslinking of the high-tack polyethylene layer was determined according to ASTM D2765.
The components constituting the outer layer listed in table 1 were melt-blended to obtain high-density polyethylene powder, which was sprayed on the surface of the high-adhesion polyethylene layer to form an anticorrosive layer, and an anticorrosive pipeline was produced. The peel strength (N/cm) and the cathodic peel length (mm) of the anticorrosive layer were measured according to GB/T23257-2017, and the impact strength of the anticorrosive layer was measured according to GB/T1843-2008, the results of which are shown in Table 2.
Examples 3 to 4
The process according to example 1 was followed except that the various components of the crosslinkable polyethylene composition constituting the inner layer were replaced as indicated in table 1.
The degree of crosslinking of the high-tack polyethylene layer was measured according to ASTM D2765 for the resulting corrosion-resistant pipe. The peel strength (N/cm) and the cathodic peel length (mm) of the anticorrosive layer were measured according to GB/T23257-2017, and the impact strength of the anticorrosive layer was measured according to GB/T1843-2008, the results of which are shown in Table 2.
Example 5
The process according to example 2, except that the components of the crosslinkable polyethylene composition constituting the inner layer were replaced as indicated in table 1.
The degree of crosslinking of the high-tack polyethylene layer was measured according to ASTM D2765 for the resulting corrosion-resistant pipe. The peel strength (N/cm) and the cathodic peel length (mm) of the anticorrosive layer were measured according to GB/T23257-2017, and the impact strength of the anticorrosive layer was measured according to GB/T1843-2008, the results of which are shown in Table 2.
TABLE 1
Comparative example 1
The comparative example is a commercially available 3PE steel pipe, the inner layer is epoxy powder coating, the middle layer is PE adhesive, and the outer layer is high density polyethylene.
The peel strength (N/cm) and the cathodic peel length (mm) of the anticorrosive layer were measured according to GB/T23257-2017, and the impact strength of the anticorrosive layer was measured according to GB/T1843-2008, the results of which are shown in Table 2.
TABLE 2
It can be seen from the results in tables 1-2 that the composite anticorrosive piping product having superior combination properties of higher adhesive strength and impact strength can be obtained by using the examples of the method provided by the present invention.
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 (10)
1. An anti-corrosion pipeline comprises a metal pipe and an anti-corrosion layer attached to the outer surface of the metal pipe, wherein the anti-corrosion layer comprises a high-cohesiveness polyethylene layer and a high-density polyethylene layer which are sequentially laminated from the outer surface of the metal pipe to the outside; wherein the high tack polyethylene layer is prepared from a crosslinkable polyethylene composition comprising:
(a)100 parts by weight of a polyethylene base resin;
(b)0.5-12 parts by weight of a polar molecule;
(c)0.01 to 1 part by weight of a peroxide crosslinking agent;
(d)1-10 parts by weight of an anticorrosive filler;
wherein the polar molecule is selected from one or more of epoxy resin, polyester resin, isocyanate oligomer, acrylate and acrylate oligomer.
2. The corrosion protected pipe of claim 1 wherein the polyethylene matrix resin is selected from ethylene homopolymers and/or ethylene copolymers;
preferably, the polyethylene base resin has a density of 0.85 to 0.965g/cm3The melt index of the polyethylene matrix resin at 190 ℃ under the load of 2.16kg is 0.01-50g/10 min; preferably, the polyethylene matrix resin has a density of 0.92 to 0.965g/cm3The polyethylene matrix resin has a melt index of 2-30g/10min at 190 ℃ and under a load of 2.16 kg.
3. A corrosion protected pipe as claimed in claim 1 or claim 2, wherein the polyethylene matrix resin is selected from low density polyethylene, high density polyethylene, ethylene propylene rubber, ethylene propylene diene monomer, ethylene and C4-8At least one of olefin copolymers.
4. A corrosion protected pipe as claimed in any one of claims 1 to 3, wherein the peroxide cross-linking agent is selected from at least one of alkyl peroxides, aryl peroxides, acyl peroxides and ketone peroxides.
5. The corrosion protected pipe of claim 4 wherein the peroxide crosslinking agent is selected from dibenzoyl peroxide, acetyl benzoyl peroxide, dicumyl peroxide, di-t-butylperoxy dicumyl, 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, 2, 5-dimethyl-2, 5-benzoyl-peroxy-hexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-dihydroperoxy-hexane, 1-di (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 7-dimethyl-2, 7-di (peroxy ethyl carbonate) -3, 5-octadiyne, di-n-butyl peroxy-2, 7-di (peroxy ethyl carbonate) -3, 5-octadiyne, di-butyl peroxy-2, 5-butyl peroxy-hexane, di-butyl peroxy-2, 5-n-butyl peroxy-2, di-2, 5-butyl peroxy-2, di-n-yl peroxy-3, di-butyl peroxy-2, di-n-2, di-butyl peroxy-2, di-butyl-2, peroxy-2, di-butyl-2, 5-peroxy-2, di-butyl-n-butyl-2, di-2, di-butyl-2, di-butyl peroxy-2, di-2, di-butyl-peroxy-2, di-butyl-2, di-butyl-peroxy-tert-butyl-2, di-butyl-peroxy-2, di-butyl, and, 3, 6-dimethyl-3, 6-di (peroxy ethyl carbonate) -4-octyne, 3, 6-dimethyl-3, 6-di (tert-butylperoxy) -4-octyne, 2, 5-dimethyl-2, 5-di (peroxy benzoate) -3-hexyne, 2, 5-dimethyl-2, 5-di (n-propyl peroxycarbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (peroxy isobutyl carbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (peroxy ethyl carbonate) -3-hexyne, 2, 5-dimethyl-2, 5-di (alpha-cumylperoxy) -3-hexyne, di (alpha-cumylperoxy) ethyl carbonate, di (tert-butyl peroxy ethyl carbonate) -3-hexyne, di (tert-butyl peroxy-2, 5-butyl peroxy benzoate) -3-hexyne, di (n-propyl peroxyn-propyl carbonate) -3-hexyne, di (tert-butyl peroxy-2, 5-butyl peroxy-3-butyl peroxy-ethyl carbonate), di (o-butyl peroxy-3-hexyl-2, di-butyne), di (ethyl peroxyl-3-butyne), di (iso-butyl peroxy-2, di (o-butyl peroxy-3-butyne) 3-2, di-2, 5-butyne) 3-butyne, di (o-2, di (di-2, di (o-2, di-butyne) 3-2, 5-butyne) 3-butyne) or di (o-butyne) or di-2, 5-2, 5-di-2, 5-di-2, 5-di (o-di-2, di-2, 5-di-2, di-butyne, 2, di-n-di-n-2, 5-di-2, 5-di-2, 5, 2, 5-dimethyl-2, 5-di (peroxy beta-chloroethyl carbonate) -3-hexyne, di-2, 4-dichlorobenzoyl peroxide, di-4-methylbenzoyl peroxide, di-tert-butylperoxyisopropyl benzene, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxy-3, 5, 5-trimethyl hexanoate and tert-butyl peroxybenzoate.
6. A corrosion protected pipe as claimed in any one of claims 1 to 5, wherein the composition comprises: 0.5-10 parts by weight of said polar molecule.
7. The corrosion protected pipe of any one of claims 1 to 6, wherein the epoxy resin is selected from one or more of bisphenol A epoxy resins, novolac epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, aliphatic epoxy resins, vinyl epoxy resins, silicone epoxy resins, wherein the epoxy value of the epoxy resin is greater than 0.1;
the polyester resin is selected from saturated polyester resin and/or unsaturated polyester resin, wherein the weight average molecular weight of the polyester resin is less than 5000;
the isocyanate is selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate;
the isocyanate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; preferably, the isocyanate oligomer has a weight average molecular weight of less than 2000;
the acrylate is selected from one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate;
the acrylate oligomer is selected from oligomers obtained by self-polymerization or copolymerization of one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate; preferably, the acrylate oligomer has a weight average molecular weight of less than 2000.
8. The corrosion protected pipe of any one of claims 1 to 7, wherein the corrosion protecting filler is selected from one or more of zinc phosphate, molybdenum zinc phosphate, aluminum zinc phosphate, iron molybdenum phosphate, iron aluminum phosphate, glass flake, graphite, graphene, titanium dioxide, zinc powder, montmorillonite, mica powder.
9. Anti-corrosion pipe according to any of claims 1 to 8, wherein the high adhesion polyethylene layer is produced by: the crosslinkable polyethylene composition is subjected to melt blending at the temperature of 130-160 ℃, then the obtained polymer powder is coated on the outer surface of the metal pipe in a powder spraying, curtain coating or extrusion winding manner, and then the metal pipe is subjected to heating crosslinking at the temperature of 180-250 ℃.
10. Use of a corrosion-resistant pipeline according to any one of claims 1 to 9 in the transportation of natural gas and oil.
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| CN202010664089.7A CN113915423A (en) | 2020-07-10 | 2020-07-10 | Corrosion-resistant pipeline and application |
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| CN202010664089.7A CN113915423A (en) | 2020-07-10 | 2020-07-10 | Corrosion-resistant pipeline and application |
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Cited By (1)
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| CN118307933A (en) * | 2024-06-11 | 2024-07-09 | 河北品华管业有限公司 | Corrosion-resistant spiral seam steel pipe and preparation method thereof |
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