CN114921010A - Oxygen-resistant irradiation crosslinked polyethylene material and polyethylene pipe thereof - Google Patents
Oxygen-resistant irradiation crosslinked polyethylene material and polyethylene pipe thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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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
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- C08L2312/06—Crosslinking by radiation
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Abstract
The invention belongs to the field of IPC 08L23/08, and particularly relates to an oxygen-resistant irradiation crosslinked polyethylene material and a polyethylene pipe thereof. The preparation raw materials comprise polyethylene, anhydride modified polyethylene, inorganic dispersoid and fluorine-containing siloxane; the weight ratio of the anhydride modified polyethylene to the polyethylene is 1: (24-45): (0.3-2): (0.01-0.08); the particle size of the inorganic dispersion is 100-1600 meshes. The oxygen-blocking irradiation crosslinked polyethylene material disclosed by the invention has excellent oxygen molecule blocking performance, and simultaneously maintains higher strength, low temperature resistance and heat resistance.
Description
Technical Field
The invention belongs to the field of IPC 08L23/08, and particularly relates to an oxygen irradiation resistant cross-linked polyethylene material and a polyethylene pipe thereof.
Background
The polyethylene pipe has excellent mechanical properties, is easy to process, and is a hot choice for engineering materials such as air-conditioning pipelines, industrial heat exchange pipelines, low-temperature radiation floor heating systems and the like. The prior art has the defects that the oxygen resistance of the common polyethylene pipe is poor, and the oxygen permeability at 40 ℃ is generally over 150mg/m 2 D, failing to satisfy the German standardThe oxygen permeability of the oxygen-resistant pipe in quasi DIN4726:2008 is less than or equal to 0.32mg/m 2 D, oxygen molecules enter the pipeline after long-term use, and bacteria and microorganisms are bred in the pipeline to block the pipeline, so that the use is influenced. Aiming at the characteristic, an oxygen barrier pipe is usually arranged on a polyethylene pipe, the traditional oxygen barrier pipe generally adopts three to five oxygen barrier layers, and an EVOH oxygen barrier layer and a bonding layer are added on the basis of a common pipe, so that the hydrophilicity and the hygroscopicity of the material are difficult to inhibit by the method, the gas barrier property can be greatly reduced after moisture is absorbed, and the oxygen barrier pipe can absorb moisture in different media and finally completely lose the oxygen barrier capability after being used in humid environments in the fields of air-conditioning floor heating, cold and hot water supply, industrial heat exchange and the like for a long time; in another method, graphite powder and flaky metal powder are added into a polyethylene pipe, the oxygen resistance of the polyethylene pipe is improved to a certain extent, but the addition amount is large, so that the transportation and construction of the polyethylene pipe are difficult after the density of the polyethylene pipe is increased, and the flexibility and the impact resistance of the polyethylene pipe are also reduced rapidly, so that the polyethylene pipe cannot be used for a long time. Chinese patent No. CN201910272794.X discloses a high-oxygen-resistance polyethylene composite material and a preparation method and application thereof, and Chinese patent No. CN201210466697.2 discloses a preparation method of a high-heat-conductivity heat-resistant polyethylene pipe with an oxygen-resistance layer, which are both improved aiming at the oxygen-resistance property of the polyethylene material, but the problems of the balance of the mechanical strength and the oxygen-resistance property of the polyethylene pipe cannot be solved, and the service life of the polyethylene pipe cannot be fundamentally prolonged. The invention aims to further improve the mechanical strength of the polyethylene pipe and improve the practicability of the polyethylene pipe while improving the barrier property of the material.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides an oxygen-resistant radiation cross-linked polyethylene material, which is prepared from polyethylene, anhydride modified polyethylene, fluorine-containing siloxane and inorganic dispersoid; the weight ratio of the anhydride modified polyethylene to the polyethylene is 1: (24-45): (0.3-2): (0.01-0.08); the particle size of the inorganic dispersion is 100-1600 meshes.
In one embodiment, the raw materials for preparing the oxygen-blocking radiation crosslinked polyethylene material further comprise a sensitizer, an impact modifier and an auxiliary agent.
Polyethylene (PE)
Polyethylene is a thermoplastic resin obtained by polymerizing ethylene. Has excellent low temperature resistance, good chemical stability and can resist most of acid and alkali erosion (not resist acid with oxidation property). Is insoluble in common solvents at room temperature, has low water absorption and excellent electrical insulation.
In some embodiments, the polyethylene comprises at least one of High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), chlorinated polyethylene, chlorosulfonated polyethylene, blend-modified polyethylene.
Preferably, the polyethylene comprises c) polyethylene having a crystallinity of 80 to 95%, d) polyethylene having a crystallinity of 70 to 80% and e) polyethylene having a crystallinity of 55 to 65%.
Further preferably, the weight ratio of c), d) and e) is (1.5-30): (1.5-20): 1; more preferably, the weight ratio of c), d) and e) is 5: 3: 1.
the polyethylene with the crystallinity of 80-95% has good heat resistance and cold resistance, good chemical stability, insolubility in any organic solvent, acid resistance, alkali resistance and corrosion resistance of various salts; also has higher rigidity and toughness and good mechanical strength. The dielectric property and the environmental stress cracking resistance are also better. The hardness, tensile strength and creep property are superior to those of low density polyethylene; the wear resistance, the electrical insulation, the toughness and the cold resistance are all better than those of low-density polyethylene; polyethylene having a crystallinity of 80 to 95% has low permeability to water vapor and air and low water absorption.
In one embodiment, the polyethylene having a crystallinity of 80 to 95% has a melt index at 190 ℃/2.16kg of 0.1 to 5g/10 min.
Preferably, the polyethylene having a crystallinity of 80 to 95% has a melt index of 0.7g/10min at 190 ℃/2.16 kg.
In one embodiment, the polyethylene having a crystallinity of from 70 to 80% has a density of from 0.926 to 0.94g/cm 3 。
Preferably, the polyethylene having a crystallinity of 70 to 80% has a density of 0.93g/cm 3 。
The polyethylene with the crystallinity of 70-80% enables the pipe to have certain flexibility and low temperature resistance.
In one embodiment, the polyethylene having a crystallinity of from 55 to 65% has a density of from 0.91 to 0.93g/cm 3 。
Preferably, the polyethylene having a crystallinity of 55 to 65% has a density of 0.92g/cm 3 。
Preferably, the polyethylene with the crystallinity of 55 to 65 percent has a melt index of 0.2 to 5g/10min at 190 ℃/2.16kg, and more preferably, the polyethylene with the crystallinity of 55 to 65 percent has a melt index of 0.8g/10min at 190 ℃/2.16 kg.
The polyethylene with the crystallinity of 55-65% has good flexibility, extensibility, electrical insulation, transparency, easy processing property and certain air permeability, and has good chemical stability, alkali resistance and common organic solvent resistance.
In the application, polyethylene with the crystallinity of 80-95%, polyethylene with the crystallinity of 70-80% and polyethylene with the crystallinity of 55-65% are subjected to irradiation crosslinking under the condition of specific proportion to obtain the polyethylene pipe with excellent crosslinking density, mechanical property and heat resistance. The applicant believes that a possible reason is that polyethylene with a crystallinity of 70-80% and polyethylene with a crystallinity of 55-65% with varying length of the branches avoids the decrease in the degree of crosslinking caused by polyethylene with regular molecular arrangement and close packing of crystallinity of 80-95%.
Anhydride modified polyethylene
In one embodiment, the acid anhydride-modified polyethylene is a cyclic alkylene acid anhydride.
Preferably, the saponification value of the anhydride-modified polyethylene is 5-10 mg/KOH; more preferably, the saponification number of the acid anhydride-modified polyethylene is 6 mg/KOH.
Preferably, the viscosity of the anhydride modified polyethylene at 140 ℃ is 300-600 cps; more preferably, the anhydride-modified polyethylene has a viscosity of 500cps at 140 ℃.
The anhydride modified polyethylene with the viscosity of 300-600cps and the saponification value of 5-10mg/KOH enables the inorganic dispersoid in the polyethylene material to be uniformly dispersed in the mixed material, so that the compatibility dispersibility and the affinity are improved.
In one embodiment, the anhydride-modified polyethylene is a maleic anhydride-modified polyethylene.
The maleic anhydride-modified polyethylene described herein is available from sigma aldrich (shanghai) trade, ltd.
In one embodiment, the weight ratio of the anhydride-modified polyethylene to the polyethylene is 1: (24-45).
Preferably, the weight ratio of the anhydride modified polyethylene to the polyethylene is 1: 36.
inorganic dispersion
In one embodiment, the weight ratio of the inorganic dispersion to the polyethylene is (0.01-0.08): 1.
preferably, the weight ratio of the inorganic dispersion to the polyethylene is 0.04: 1.
in one embodiment, the inorganic dispersion is selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, silicon carbide, aluminum nitride, boron nitride, aluminum hydroxide, magnesium hydroxide, talc, graphite, and graphene.
In one embodiment, the inorganic dispersion comprises a) an inorganic dispersion having a platelet structure.
Preferably, the inorganic dispersion with a sheet structure is an inorganic dispersion with a monoclinic system and a pseudo-hexagonal or rhombohedral sheet structure.
In one embodiment, the particle size of a) is 400-1500 meshes.
Preferably, the particle size of the a) is 1000 meshes.
In one embodiment, the inorganic dispersion further comprises b) an inorganic dispersion of regular tetrahedral structure.
Preferably, the weight ratio of a) to b) is (8-15): 1; more preferably, the weight ratio of a) to b) is 12: 1.
the monoclinic system of the invention is one of seven crystal systems, and belongs to the lower crystal family. The symmetry is characterized in that no higher-order axis exists, and the number of the second-order symmetry axis and the number of the symmetry plane are not more than one. The crystal is found with this second order axis of symmetry or plane of symmetry as the b-axis. The b axis is orthogonal to the a axis and the c axis, the a axis and the c axis are oblique, the axis angle α ═ γ ≠ 90 °, and the axis unit a is not equal to b but not equal to c. Belonging to the monoclinic system and having beta-S, CaSO 4 ·2H 2 O, and the like. Prismatic crystals with bottom axial faces are common in such crystal systems.
The tetragonal system, known as tetragonal system, belongs to the middle-grade crystal family. The characteristic symmetry element is a quadruple axis. The crystal with quadruple axis or quadruple reverse axis characteristic symmetric elements in the direction of the only c-axis main axis with higher minor axis belongs to a tetragonal system.
In one embodiment, said a) is talc; b) is silicon dioxide.
The inorganic dispersion with monoclinic system and pseudo hexagonal or rhombohedral sheet structure and the inorganic dispersion with regular tetrahedral structure effectively improve the oxygen barrier property of the polyethylene pipe in the application at a specific ratio.
In one embodiment, the inorganic dispersion is a fluorosilicone modified inorganic dispersion.
Preferably, the fluorosilicone has the following structure:
n is 3 or 6 or 9.
More preferably, the fluorosilicone has the following structure:
n＝3。
in one embodiment, the fluorosilicone is polytrifluoropropylmethylsiloxane.
In one embodiment, the polytrifluoropropylmethylsiloxane is prepared as follows:
in a 100mL single-neck bottle, 11.7g D was added 3 F, protecting the glass by using nitrogen,and then adding 10mL of solvent tetrahydrofuran into the single-neck flask by using an injector, placing the single-neck flask in an ice water bath, then adding 10mL of n-butyllithium-n-hexane solution by using the injector, reacting for 2 hours, adding 2.99mL of trifluoropropylmethylsiloxane coupling agent by using the injector for end capping, wherein the end capping time is 12 hours, washing by using n-hexane after the reaction is finished, and separating to obtain an organic phase. The organic phase was washed 3 times with deionized water and then dried over anhydrous sodium sulfate. The solvent and unreacted monomers were removed by distillation under reduced pressure to obtain a colorless and transparent polytrifluoropropylmethylsiloxane having a polymerization degree of 3.
According to the application, polytrifluoropropylmethylsiloxane modified inorganic dispersoid is adopted, and simultaneously, anhydride modified polyethylene in the application is combined, so that a polyethylene pipe obtained after irradiation crosslinking has excellent oxygen resistance at 40 ℃.
In one embodiment, the method of preparing the polytrifluoropropylmethylsiloxane modified inorganic dispersion comprises: 1g of polytrifluoropropylmethylsiloxane and 600ml of benzotrifluoride are weighed to prepare a solution, the solution is stirred until the solution is clear, the solution is poured into a container filled with 60g of inorganic dispersion, the stirring is carried out for 1.5 hours, and then the inorganic dispersion is placed into a water bath at 85 ℃ for reaction for 1.5 hours. And cooling, filtering and washing the reaction product, and then drying the reaction product in a forced air drying oven at 110 ℃ for 9 hours to obtain the inorganic dispersion modified by the polytrifluoropropylmethylsiloxane coupling agent.
Fluorosiloxanes
In some preferred embodiments, the average molecular weight of the fluorosilicone is 180-280.
Further preferably, the fluorine-containing siloxane includes at least one of (3,3, 3-trifluoropropyl) methyldichlorosilane, (3,3, 3-trifluoropropyl) methyldimethoxysilane, (3,3, 3-trifluoropropyl) methyldiethoxysilane, 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) -cyclotrisiloxane, (3,3, 3-trifluoropropyl) trifluorosilane, (3,3, 3-trifluoropropyl) trimethoxysilane, and (3,3, 3-trifluoropropyl) triethoxysilane.
Still more preferably, the fluorosilicone is (3,3, 3-trifluoropropyl) trimethoxysilane with CAS number 429-60-7.
Sensitizers
In one embodiment, the sensitizer is a photosensitizer which is a substance that absorbs radiation energy and upon excitation undergoes a photochemical change to produce a reactive intermediate (radical or cation) having the ability to initiate polymerization. The photosensitizer is a key component of the photocurable material and plays a decisive role in the photocuring speed of the photocurable material.
Preferably, the photosensitizer is an ionic photosensitizer and/or a free radical photosensitizer.
In one embodiment, the ionic photosensitizer may be exemplified by Ar 2 N 2 BF 4 、Ar 2 N 2 AsF 6 、Ar 2 N 2 PF 6 、Ar 2 N 2 SbF 6 、Ar 2 IBF 4 、Ar 2 IAsF 6 、Ar 2 IPF 6 、Ar 2 ISbF 6 、Ar 3 SBF 4 、Ar 3 SAsF 6 、Ar 3 SPF 6 、Ar 3 SbF 6 And the like.
In one embodiment, the radical photosensitizer is selected from one or more of glycol esters, benzoin and derivatives thereof, acetophenone derivatives, aromatic ketones, and acylphosphine oxides.
Preferably, the photosensitizer is a mixture of benzophenone and 4,4' -dimethylamino benzophenone in a weight ratio of 1: 1.
In one embodiment, the weight ratio of the sensitizer to polyethylene is (0.001-0.05): 1.
preferably, the weight ratio of the sensitizer to the polyethylene is 0.01: 1.
impact modifier
The impact modifier is a chemical for improving low-temperature embrittlement of a high polymer material and endowing the high polymer material with higher toughness.
In one embodiment, the impact modifier comprises at least one of Chlorinated Polyethylene (CPE), methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), EVA, ACR, acrylonitrile, butadiene random copolymer (NBR), and rigid particles.
Preferably, the impact modifier is a butadiene random copolymer.
In one embodiment, the weight ratio of the impact modifier to polyethylene is (0.01-0.05): 1.
preferably, the weight ratio of the impact modifier to the polyethylene is 0.03: 1.
auxiliary agent
The auxiliary agent of the present invention is not particularly limited, and those skilled in the art can make routine selections according to actual needs.
In some embodiments, the adjuvant comprises an antioxidant and a lubricant.
In some embodiments, the antioxidants may be exemplified by antioxidant 1010, antioxidant 168, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, antioxidant 264 and the like.
In one embodiment, the lubricant comprises at least one of a mineral lubricant, a vegetable lubricant, an animal lubricant, and a synthetic lubricant.
Examples of the lubricant include PP wax, PE wax, EBS, zinc stearate, calcium stearate, silicone oil, fatty acid amide, oleic acid, polyester, synthetic ester, carboxylic acid, polytetrafluoroethylene wax, and the like.
In a preferred embodiment, the auxiliary agent is antioxidant 168 and polytetrafluoroethylene wax in a weight ratio of 1 (0.5-3).
Preferably, the polytetrafluoroethylene wax has a viscosity of 200-500cps, 140 ℃.
In one embodiment, the weight ratio of the adjuvant to the polyethylene is (0.01-0.1): 1.
preferably, the weight ratio of the auxiliary agent to the polyethylene is 0.05: 1.
the invention provides a polyethylene pipe prepared from the oxygen-resistant irradiation crosslinked polyethylene material in a second aspect.
The polyethylene pipe described herein may be single-layered, double-layered, or multi-layered.
The preparation method of the present invention is not particularly limited, and those skilled in the art can make routine selections.
In one embodiment, a method of making a monolayer tubing includes the steps of:
s1, mixing polyethylene, anhydride modified polyethylene, inorganic dispersoid, impact modifier, sensitizer and auxiliary agent by a high-speed stirrer according to the formula, adding the mixture into a granulator after uniform mixing, and obtaining modified polyethylene after drawing, cooling and granulating;
s2, adding the modified polyethylene obtained in the step S1 into an extruder according to the formula, and extruding at 185-225 ℃ to obtain a modified polyethylene pipe;
and S3, irradiating and crosslinking the modified polyethylene pipe obtained by the S2 with the irradiation dose of 1-10 Mrad, and thus obtaining the modified polyethylene pipe.
In one embodiment, a method of making a three layer tubing includes the steps of:
s1, mixing polyethylene, a sensitizer and an auxiliary agent by a high-speed mixer according to the formula, adding the mixture into a granulator after uniform mixing, and obtaining a first layer (inner layer) of modified polyethylene through drawing, cooling and granulating;
s2, mixing polyethylene, anhydride modified polyethylene, inorganic dispersoid, impact modifier, sensitizer and auxiliary agent by a high-speed stirrer according to the formula, adding the mixture into a granulator after uniform mixing, and obtaining second layer (middle layer) modified polyethylene by drawing, cooling and granulating;
s3, mixing polyethylene, a sensitizer and an auxiliary agent by a high-speed mixer according to the formula, adding the mixture into a granulator after uniform mixing, and obtaining a third layer (outer layer) of modified polyethylene by drawing, cooling and granulating;
s4, adopting a co-extrusion technology for one-step forming, and carrying out one-step extrusion forming on the first layer mixed material, the second layer mixed material and the third layer mixed material in a single-screw extruder of a co-extrusion die at 185-225 ℃ to obtain a double-layer co-extruded pipe, thus obtaining a three-layer pipe;
and S4, irradiating and crosslinking the three-layer pipe obtained by S3 with the irradiation dose of 1-10 Mrad.
Has the advantages that:
(1) the polyethylene with the crystallinity of 80-95% enables the pipe to have certain heat resistance, cold resistance and chemical stability, and meanwhile, the pipe is small in permeability to water vapor and air and low in water absorption;
(2) the polyethylene with the crystallinity of 70-80% enables the pipe to have certain flexibility and low temperature resistance.
(3) The polyethylene with the crystallinity of 55-65% has good flexibility, extensibility, electrical insulation, transparency, easy processability and certain air permeability, and has good chemical stability, alkali resistance and common organic solvent resistance.
(4) In the application, polyethylene with the crystallinity of 80-95%, polyethylene with the crystallinity of 70-80% and polyethylene with the crystallinity of 55-65% are subjected to irradiation crosslinking under the condition of specific proportion to obtain the polyethylene pipe with excellent crosslinking density, mechanical property and heat resistance.
(5) The anhydride modified polyethylene with the viscosity of 300-600cps and the saponification value of 5-10mg/KOH enables the inorganic dispersoid in the polyethylene material to be uniformly dispersed in the mixed material, so that the compatibility, dispersibility and affinity are improved.
(6) The oxygen barrier performance of the polyethylene pipe material is effectively improved by the inorganic dispersion with monoclinic system and pseudo hexagonal or rhombohedral sheet structure and the inorganic dispersion with regular tetrahedral structure in a specific ratio.
(7) According to the method, the polytrifluoropropylmethylsiloxane modified inorganic dispersoid is adopted, the anhydride modified polyethylene is combined, and the polyethylene pipe obtained after irradiation crosslinking has excellent oxygen resistance at 40 ℃.
Detailed Description
Examples
Example 1
The embodiment 1 of the invention provides an oxygen-resistant irradiation cross-linked polyethylene material, which is prepared from the following raw materials: polyethylene, anhydride modified polyethylene, inorganic dispersion, a sensitizing agent, an impact modifier, fluorine-containing siloxane and an auxiliary agent.
The polyethylene is c) polyethylene with the crystallinity of 80-95%, d) polyethylene with the crystallinity of 70-80% and e) polyethylene with the crystallinity of 55-65%, and the weight ratio is 1.5: 1.5: 1. the density of c) is 0.95g/cm 3 The product has a melt index of 0.9g/10min at 190 ℃/2.16kg, is purchased from Daqing petrochemical, and has a mark of 5000S; the density of b) is 0.939g/cm 3 The melt index at 190 ℃/2.16kg is 0.6g/10min, purchased from the Dow company under the designation DNDA-1796; the density of the c) is 0.92g/cm3, the melt index of 190 ℃/2.16kg is 0.8g/10min, and the product is purchased from Shanghai Teng jin plastication Limited and has the model number of 2426F.
The anhydride-modified polyethylene is maleic anhydride-modified polyethylene, the saponification value is 6mg/KOH, the viscosity at 140 ℃ is 500cps, and the weight ratio of the anhydride-modified polyethylene to the polyethylene is 1: maleic anhydride modified polyethylene was purchased from sigma aldrich trade ltd.
The inorganic dispersion is poly (trifluoropropylmethylsiloxane) -modified talcum powder and poly (trifluoropropylmethylsiloxane) -modified silicon dioxide, and the weight ratio is 8: 1, the particle size of the talcum powder is 1000 meshes and is purchased from Guangdong source epitaxial powder company Limited; the silicon dioxide is spherical, has an average particle size of 200nm and is purchased from synthetic fertilizer Zhonghang nanometer science and technology development limited company; the weight ratio of the inorganic dispersion to the polyethylene is 0.04: 36.
the preparation method of the polytrifluoropropylmethylsiloxane comprises the following steps:
in a 100mL single-neck bottle, 11.7g D was added 3 And F, using nitrogen for protection, then using a syringe to add 10mL of solvent tetrahydrofuran into the single-neck flask, placing the single-neck flask into an ice water bath, then using the syringe to add 10mL of n-butyllithium-n-hexane solution, reacting for 2h, using the syringe to add 2.99mL of trifluoropropylmethylsiloxane coupling agent for end capping, wherein the end capping time is 12h, after the reaction is finished, using n-hexane for washing, and separating to obtain an organic phase. The organic phase was washed 3 times with deionized water and then dried over anhydrous sodium sulfate. By steaming under reduced pressureThe solvent and unreacted monomers were distilled off to obtain a colorless transparent polytrifluoropropylmethylsiloxane having a polymerization degree of 3.
The preparation method of the polytrifluoropropylmethylsiloxane modified inorganic dispersion comprises the following steps: 1g of polytrifluoropropylmethylsiloxane and 600ml of benzotrifluoride are weighed to prepare a solution, the solution is stirred until the solution is clear, the solution is poured into a container filled with 60g of inorganic dispersion, the stirring is carried out for 1.5 hours, and then the inorganic dispersion is placed into a water bath at 85 ℃ to react for 1.5 hours. And cooling, filtering and washing the reaction product, and then drying the reaction product in a forced air drying oven at 110 ℃ for 9 hours to obtain the inorganic dispersion modified by the poly (trifluoropropylmethylsiloxane) coupling agent.
The sensitizer is a mixture of benzophenone and 4,4' -dimethylamino benzophenone in a weight ratio of 1: 1; the weight ratio of the sensitizer to the polyethylene is 0.01: 1.
the impact modifier is a butadiene random copolymer available from JSR, japan, under the designation N230S, and the weight ratio of impact modifier to polyethylene is 0.03: 1.
the fluorine-containing siloxane is (3,3, 3-trifluoropropyl) trimethoxy silane, and the CAS number is 429-60-7; the weight ratio of the fluorine-containing siloxane to the polyethylene is 1: 36.
the auxiliary agent is antioxidant 168 and polytetrafluoroethylene wax with the weight ratio of 1: 2.5; the viscosity of the polytetrafluoroethylene wax is 375cps (140 ℃), and the polytetrafluoroethylene wax is from New Gekko material Co., of Fushan City, and the model is Honeywell AC 6A. The weight ratio of the auxiliary agent to the polyethylene is 0.05: 1.
the preparation method of the polyethylene pipe comprises the following steps:
s1, mixing the polyethylene, the sensitizer and the auxiliary agent according to the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining a first layer (inner layer) of modified polyethylene through drawing, cooling and granulating;
s2, mixing the polyethylene, the anhydride modified polyethylene, the inorganic dispersoid, the fluorine-containing siloxane, the impact modifier, the sensitizer and the auxiliary agent in the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining the second layer (middle layer) modified polyethylene after drawing, cooling and granulating;
s3, mixing the polyethylene, the sensitizer and the auxiliary agent according to the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining a third layer (outer layer) of modified polyethylene by drawing, cooling and granulating;
s3, adopting a co-extrusion technology to perform one-step molding, and performing one-step extrusion molding on the obtained first layer of modified polyethylene, the second layer of modified polyethylene and the third layer of modified polyethylene in a single-screw extruder of a co-extrusion die at the temperature of 200 ℃ to obtain a double-layer co-extruded pipe, thus obtaining a three-layer pipe;
s4, and irradiating and crosslinking the three-layer pipe obtained by the S3 by using the irradiation dose of 7 Mrad.
Example 2
The embodiment 1 of the invention provides an oxygen-resistant irradiation cross-linked polyethylene material, which is prepared from the following raw materials: polyethylene, anhydride modified polyethylene, inorganic dispersion, a sensitizing agent, an impact modifier, fluorine-containing siloxane and an auxiliary agent.
The polyethylene comprises c) polyethylene with the crystallinity of 80-95%, d) polyethylene with the crystallinity of 70-80% and e) polyethylene with the crystallinity of 55-65%, and the weight ratio is 5: 3: 1. the density of c) is 0.95g/cm 3 The product has a melt index of 0.9g/10min at 190 ℃/2.16kg, is purchased from Daqing petrochemical, and has a mark of 5000S; the density of b) is 0.939g/cm 3 The melt index at 190 ℃/2.16kg is 0.6g/10min, purchased from the Dow company under the designation DNDA-1796; the density of the c) is 0.92g/cm3, the melt index at 190 ℃/2.16kg is 0.8g/10min, and the density is purchased from Shanghai Teng jin plastication Co., Ltd, and the model is 2426F.
The anhydride-modified polyethylene is maleic anhydride-modified polyethylene, the saponification value is 6mg/KOH, the viscosity at 140 ℃ is 500cps, and the weight ratio of the anhydride-modified polyethylene to the polyethylene is 1: maleic anhydride-modified polyethylene was purchased from sigma aldrich trade ltd.
The inorganic dispersoid is poly trifluoropropyl methyl siloxane modified talcum powder and poly trifluoropropyl methyl siloxane modified silicon dioxide, and the weight ratio is 8: 1, the particle size of the talcum powder is 1000 meshes and is purchased from Guangdong source epitaxial powder Co., Ltd; the silicon dioxide is spherical, has an average particle size of 200nm and is purchased from synthetic fertilizer Zhonghang nanometer science and technology development limited company; the weight ratio of the inorganic dispersion to the polyethylene is 0.04: 36.
the preparation method of the polytrifluoropropylmethylsiloxane comprises the following steps:
in a 100mL single-neck bottle, 11.7g D was added 3 And F, under the protection of nitrogen, adding 10mL of solvent tetrahydrofuran into the single-neck flask by using an injector, placing the single-neck flask in an ice water bath, adding 10mL of n-butyllithium-n-hexane solution by using the injector, reacting for 2 hours, adding 2.99mL of trifluoropropylmethylsiloxane coupling agent by using the injector for end capping, wherein the end capping time is 12 hours, washing by using n-hexane after the reaction is finished, and separating to obtain an organic phase. The organic phase was washed 3 times with deionized water and then dried over anhydrous sodium sulfate. The solvent and unreacted monomers were removed by distillation under reduced pressure to obtain a colorless and transparent polytrifluoropropylmethylsiloxane having a polymerization degree of 3.
The preparation method of the polytrifluoropropylmethylsiloxane modified inorganic dispersion comprises the following steps: 1g of polytrifluoropropylmethylsiloxane and 600ml of benzotrifluoride are weighed to prepare a solution, the solution is stirred until the solution is clear, the solution is poured into a container filled with 60g of inorganic dispersion, the stirring is carried out for 1.5 hours, and then the inorganic dispersion is placed into a water bath at 85 ℃ to react for 1.5 hours. And cooling, filtering and washing the reaction product, and then drying the reaction product in a forced air drying oven at 110 ℃ for 9 hours to obtain the inorganic dispersion modified by the poly (trifluoropropylmethylsiloxane) coupling agent.
The sensitizer is a mixture of benzophenone and 4,4' -dimethylamino benzophenone in a weight ratio of 1: 1; the weight ratio of the sensitizer to the polyethylene is 0.01: 1.
the impact modifier is a butadiene random copolymer available from JSR, japan, under the designation N230S, and the weight ratio of impact modifier to polyethylene is 0.03: 1.
the fluorine-containing siloxane is (3,3, 3-trifluoropropyl) trimethoxy silane, and the CAS number is 429-60-7; the weight ratio of the fluorine-containing siloxane to the polyethylene is 1: 36.
the auxiliary agent is antioxidant 168 and polytetrafluoroethylene wax with the weight ratio of 1: 2.5; the polytetrafluoroethylene wax has a viscosity of 375cps (140 deg.C), and is from new Gekko material Co., Ltd, Fushan City, and has a model of HONEYWELL AC 6A. The weight ratio of the auxiliary agent to the polyethylene is 0.05: 1.
the preparation method of the polyethylene pipe comprises the following steps:
s1, mixing the polyethylene, the sensitizer and the auxiliary agent in the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining a first layer (inner layer) of modified polyethylene through drawing, cooling and granulating;
s2, mixing polyethylene, anhydride modified polyethylene, inorganic dispersoid, fluorine-containing siloxane, impact modifier, sensitizer and auxiliary agent in the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining second layer (middle layer) modified polyethylene after drawing, cooling and granulating;
s3, mixing the polyethylene, the sensitizer and the auxiliary agent according to the proportion by a high-speed stirrer, adding the mixture into a granulator after uniform mixing, and obtaining a third layer (outer layer) of modified polyethylene by drawing, cooling and granulating;
s3, adopting a co-extrusion technology to perform one-step molding, and performing one-step extrusion molding on the obtained first layer of modified polyethylene, the second layer of modified polyethylene and the third layer of modified polyethylene in a single-screw extruder of a co-extrusion die at the temperature of 200 ℃ to obtain a double-layer co-extruded pipe, thus obtaining a three-layer pipe;
s4, irradiating and crosslinking the three-layer pipe obtained by S3 with the irradiation dose of 7Mrad, and obtaining the composite pipe.
Example 3
Embodiment 3 of the present invention provides an oxygen-blocking radiation-crosslinked polyethylene material, which is different from embodiment 1 in that the preparation raw material of the oxygen-blocking radiation-crosslinked polyethylene material is anhydride-free modified polyethylene.
The specific embodiment of the preparation method of the polyethylene pipe is the same as that of example 3.
Example 4
The embodiment 4 of the invention provides an oxygen-blocking irradiation cross-linked polyethylene material, which is the same as the embodiment 1 in the specific implementation manner, and is characterized in that the inorganic dispersion is talcum powder and silicon dioxide, and the weight ratio is 12: 1, the particle size of the talcum powder is 1000 meshes and is purchased from Guangdong source epitaxial powder company Limited; the silicon dioxide is spherical, has an average particle size of 200nm and is purchased from synthetic fertilizer Zhonghang nanometer science and technology development limited company; the weight ratio of the inorganic dispersion to the polyethylene is 0.06: 1.
the specific embodiment of the preparation method of the polyethylene pipe is the same as that of example 3.
Example 5
Embodiment 5 of the present invention provides an oxygen-blocking radiation cross-linked polyethylene material, which is the same as embodiment 1 in specific implementation manner, except that the inorganic dispersion is poly trifluoropropylmethylsiloxane-modified talc powder.
The specific embodiment of the preparation method of the polyethylene pipe is the same as that of example 3.
Example 6
Embodiment 6 of the present invention provides an oxygen-blocking radiation-crosslinked polyethylene material, which is the same as embodiment 1 in specific implementation, except that the inorganic dispersion is a polytrifluoropropylmethylsiloxane-modified silica.
The specific implementation mode of the preparation method of the polyethylene pipe is the same as that of the example 3.
Example 7
The embodiment 7 of the invention provides an oxygen-blocking radiation-crosslinked polyethylene material, which is the same as the embodiment 1 in the specific implementation manner, and is characterized in that the inorganic dispersion is poly (trifluoropropylmethylsiloxane) -modified kaolin and poly (trifluoropropylmethylsiloxane) -modified silicon dioxide, and the weight ratio of the poly (trifluoropropylmethylsiloxane) -modified kaolin to the poly (trifluoropropylmethylsiloxane) -modified silicon dioxide is 12: 1, the particle size of the kaolin is 1000 meshes, and the kaolin is purchased from Shijiazhuang Mayun building materials Co.Ltd; the silicon dioxide is spherical, has an average particle size of 200nm and is purchased from synthetic fertilizer Zhonghang nanometer science and technology development limited company; the weight ratio of the inorganic dispersion to the polyethylene is 0.06: 1.
the specific embodiment of the preparation method of the polyethylene pipe is the same as that of example 3.
Performance evaluation
1. And (3) testing the strength: the strength of each of the polyethylene pipes obtained in examples 1 to 7 was measured. The hydrostatic pressure at 80 ℃ is tested according to GB/T13663-2000, the ring stress is 5.5MPa and 165h, the polyethylene material does not crack, no leakage is marked as qualified, otherwise, the polyethylene material is marked as unqualified, and the results are shown in Table 1.
2. And (3) testing the crosslinking degree: 100m polyethylene pipes were prepared according to the examples and the degree of crosslinking was determined according to GB 18474-2001. The test results are shown in Table 1.
3. Oxygen barrier properties: the oxygen barrier properties at 40 ℃ of the polyethylene pipes obtained in examples 1 to 7 were respectively tested according to the GB/T28799.2 standard, and the test results are shown in Table 1.
TABLE 1
Claims (10)
1. The oxygen radiation resistant cross-linked polyethylene material is characterized in that the preparation raw materials comprise polyethylene, anhydride modified polyethylene, fluorine-containing siloxane and inorganic dispersoid; the weight ratio of the anhydride modified polyethylene to the polyethylene is 1: (24-45): (0.3-2): (0.01-0.08); the particle size of the inorganic dispersion is 100-1600 meshes.
2. The oxygen radiation resistant crosslinked polyethylene material according to claim 1, wherein the acid anhydride in the acid anhydride-modified polyethylene is a cyclic alkylene acid anhydride.
3. The oxygen radiation resistant crosslinked polyethylene material according to claim 2, wherein the saponification number of the anhydride-modified polyethylene is 5 to 10 mg/KOH.
4. The oxygen radiation resistant cross-linked polyethylene material as claimed in claim 3, wherein the viscosity of the anhydride modified polyethylene at 140 ℃ is 300-600 cps.
5. The oxygen-blocking radiation crosslinked polyethylene material according to any of claims 1 to 4 wherein said inorganic dispersion comprises a) an inorganic dispersion of a lamellar structure; the weight ratio of the inorganic dispersion to the polyethylene is (0.01-0.05): 1.
6. the oxygen-resistant radiation-crosslinked polyethylene material according to claim 5, wherein the inorganic dispersion of a lamellar structure is an inorganic dispersion of a monoclinic system and a crystal having a lamellar structure of pseudo-hexagonal or rhombohedral shape.
7. The oxygen-blocking radiation-crosslinked polyethylene material according to claim 6, wherein said inorganic dispersion further comprises b) an inorganic dispersion of regular tetrahedral structure, said a) and b) being present in a weight ratio of (8-15): 1.
8. the oxygen-blocking radiation crosslinked polyethylene material according to claim 5, wherein the inorganic dispersion is a fluorosilicone-modified inorganic dispersion.
9. The oxygen-blocking radiation crosslinked polyethylene material according to any of claims 6 to 8, wherein said polyethylene comprises c) polyethylene having a crystallinity of 80 to 95%, d) polyethylene having a crystallinity of 70 to 80% and e) polyethylene having a crystallinity of 55 to 65%.
10. A polyethylene pipe prepared from the oxygen-blocking radiation crosslinked polyethylene material according to any one of claims 1 to 9.
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