WO2022088230A1 - 用于塑料管道的改性再生聚乙烯塑料及其制备方法 - Google Patents

用于塑料管道的改性再生聚乙烯塑料及其制备方法 Download PDF

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WO2022088230A1
WO2022088230A1 PCT/CN2020/127119 CN2020127119W WO2022088230A1 WO 2022088230 A1 WO2022088230 A1 WO 2022088230A1 CN 2020127119 W CN2020127119 W CN 2020127119W WO 2022088230 A1 WO2022088230 A1 WO 2022088230A1
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plastic
parts
modified
waste
recycled
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PCT/CN2020/127119
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English (en)
French (fr)
Inventor
许开华
吕怀兴
秦玉飞
牛远航
陈龙
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江西格林美资源循环有限公司
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Priority to CH000919/2022A priority Critical patent/CH718493B1/de
Publication of WO2022088230A1 publication Critical patent/WO2022088230A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • B29B7/426—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix with consecutive casings or screws, e.g. for charging, discharging, mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/66—Recycling the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/885—Adding charges, i.e. additives with means for treating, e.g. milling, the charges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/94—Liquid charges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2262—Oxides; Hydroxides of metals of manganese
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • 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
    • C08L2207/066—LDPE (radical process)
    • 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
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to the technical field of resource regeneration, in particular to a modified regenerated polyethylene plastic used for plastic pipes and a preparation method thereof.
  • waste plastics With the development of my country's plastics industry, a large amount of plastic waste is generated.
  • the annual amount of waste plastics produced in my country is about 14 million tons. They cannot be naturally decomposed or rotted, which has become a social problem that attracts attention.
  • the recycling of waste plastics can turn industrial waste into extremely valuable raw materials for industrial production, and realize the recycling and utilization of resources, which has potential significance that cannot be ignored.
  • all countries in the world pay attention to and support the recycling and reuse of waste plastics.
  • waste plastics account for about 10% to 20%.
  • Polyolefins mainly PE and PP
  • plastic pipes There are many types of plastic pipes, among which polyethylene (PE) pipes are often used in buried applications such as gas transmission, water supply and drainage, cable and optical cable jackets, etc.
  • PE polyethylene
  • This type of plastic pipes is compared with traditional cast iron pipes, galvanized steel pipes, cement pipes and other pipes. It has the advantages of energy saving and material saving, environmental protection, light weight and high strength, corrosion resistance, smooth inner wall and no scaling, easy construction and maintenance, and long service life. It is widely used in building water supply and drainage, urban and rural water supply and drainage, urban gas, electricity and optical cable protection. Construction, municipal, industrial and agricultural fields such as casing, industrial fluid conveying, agricultural irrigation, etc.
  • PE plastic pipes also have some shortcomings.
  • plastics, as a petrochemical synthetic material, are still high in cost;
  • Regenerated waste plastic PE can be added as a raw material for production to reduce costs, but due to the complex and unstable source of waste plastics, the performance of PE plastic pipe products is also unstable, which poses a hidden danger to the safety of pipe use.
  • a first aspect of the present invention provides a modified recycled polyethylene plastic for plastic pipes, comprising a plastic substrate, a modified reinforcing and toughening additive and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: 50-80 parts of HDPE waste plastics, 10-20 parts of LDPE waste plastics, 0-10 parts of LLDPE waste plastics, and 5-25 parts of ethylene copolymer waste plastics;
  • the modification, strengthening and toughening additives include: 0.1-0.5 parts of silane compounds, 0-0.4 parts of maleic anhydride, 0.02-0.05 parts of graft initiators, 0.01-0.04 parts of dehydration catalysts, and 0.01-0.03 parts of antioxidants;
  • the processing aids include: 5-15 parts of rigid fillers, 0.02-0.05 parts of internal lubricant, and 0.2-1 part of external lubricant.
  • a second aspect of the present invention provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • the modified strengthening and toughening additives are mixed uniformly to form pre-mixed liquid additives
  • the modified recycled polyethylene plastic for plastic pipes is granulated by a single-screw-counter-conical twin-screw two-stage extrusion granulator.
  • the preparation method of the modified recycled polyethylene plastic for plastic pipes provided by the second aspect of the present invention is used to obtain the modified recycled polyethylene plastic for plastic pipes provided by the first aspect of the present invention.
  • the modified recycled PE plastic is prepared by adopting the plastic base material, the modified reinforcing and toughening additive and the processing aid, and the obtained modified recycled PE plastic has high impact strength and stable performance;
  • PE-type waste plastics that can be obtained by multi-channel recycling are mainly selected, and the ratio of recycled plastics + fillers accounts for more than 90% of the components, and no new material PE is required, which is beneficial to reduce production costs.
  • a first aspect of the present invention provides a modified recycled polyethylene plastic for plastic pipes, comprising a plastic base material, a modified reinforcing and toughening additive and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: 50-80 parts of HDPE waste plastics, 10-20 parts of LDPE waste plastics, 0-10 parts of LLDPE waste plastics, and 5-25 parts of ethylene copolymer waste plastics;
  • the modification, strengthening and toughening additives include: 0.1-0.5 parts of silane compounds, 0-0.4 parts of maleic anhydride, 0.02-0.05 parts of graft initiators, 0.01-0.04 parts of dehydration catalysts, and 0.01-0.03 parts of antioxidants;
  • the processing aids include: 5-15 parts of rigid fillers, 0.02-0.05 parts of internal lubricant, and 0.2-1 part of external lubricant.
  • the modified recycled polyethylene plastic used for plastic pipes includes a plastic base material, a modified reinforcing and toughening additive and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: 50-80 parts of HDPE waste plastics, 10-20 parts of LDPE waste plastics, 5-10 parts of LLDPE waste plastics, and 5-25 parts of ethylene copolymer waste plastics;
  • the modification, strengthening and toughening additives include: 0.1-0.5 parts of silane compounds, 0.1-0.4 parts of maleic anhydride, 0.02-0.05 parts of graft initiators, 0.01-0.04 parts of dehydration catalysts, and 0.01-0.03 parts of antioxidants;
  • the processing aids include: 5-15 parts of rigid fillers, 0.02-0.05 parts of internal lubricants, and 0.3-1 parts of external lubricants.
  • HDPE waste plastic is the crushed material of HDPE hollow blow molding products after being crushed and cleaned;
  • LDPE waste plastic is particles obtained by granulating various waste LDPE films;
  • LLDPE waste plastic is various waste LLDPE Particles obtained by film granulation;
  • ethylene copolymer waste plastics are recycled waste EVA waste sheets and supplies, as well as ethylene propylene copolymer waste paint buckets and daily injection products after crushing and cleaning.
  • PE-type waste plastics that can be obtained by multi-channel recycling are mainly selected, and the ratio of recycled plastics + fillers accounts for more than 90% of the components, and no new material PE is required, which is beneficial to reduce production costs.
  • the silane compound is one or a mixture of alkyltriethoxysilane, methyltrimethoxysilane, triacetoxysilane and propyltriacetoxysilane ;
  • Maleic anhydride is solid or powdery substance;
  • Grafting initiator is one or more of benzoyl peroxide (BPO), dicumyl peroxide (DCPO), tert-butyl hydroperoxide (DHPO) A mixture of species;
  • the dehydration catalyst is one or more of manganese oxide (MnO 2 ), iron oxide (Fe 2 O 3 ), copper oxide (CuO), cuprous oxide (Cu 2 O), and zinc oxide (ZnO)
  • the antioxidant is one or a mixture of antioxidants 168 and 1010.
  • the present invention can improve the compatibility of rigid fillers, improve the cross-linking effect of polyethylene molecular chains, etc. by adding modified and toughening additives, and at the same time, play a synergistic effect, greatly improve the rigidity and toughness of the material, and improve the preparation of modified materials.
  • the impact strength of the regenerated particles is increased by 1 to 2 times, and the flexural modulus is increased by more than 50% compared with the ordinary recycled particles.
  • the rigid filler is an inorganic filler, specifically one or a mixture of talc powder, calcium carbonate powder, diatomite powder, silica fume powder, and mica powder, and the mesh number is 1250-2000 mesh;
  • the lubricant is one or more mixtures of EBS (ethylene bis-stearamide) and PE wax;
  • the external lubricant is one of stearic acid, stearic acid metal salt, aliphatic hydrocarbon wax, and oxidized polyethylene. species or a mixture of several.
  • a second aspect of the present invention provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • S1 mixes the modified strengthening and toughening additive uniformly to form a pre-mixed liquid additive
  • the modified recycled polyethylene for plastic pipes is granulated by a single-screw-counter-conical twin-screw two-stage extrusion granulator plastic.
  • the method for preparing the modified regenerated polyethylene plastic for plastic pipes provided in the second aspect of the present invention is used to obtain the modified regenerated polyethylene plastic for plastic pipes provided in the first aspect of the present invention.
  • the present invention can improve the activity and uniformity of the reactive components by pre-mixing reactive components such as silane compounds, and introducing a dehydration catalyst, and then mixing with other raw materials, thereby greatly improving the improvement of materials by the reactive components. Effect.
  • the present invention can be very It can well realize the stable feeding of large-sized waste plastic sheets, and can achieve better mixing effect of formula materials and obtain greater extrusion pressure, greatly improving the effect of modification, strengthening and toughening additives, thereby improving material properties; It can also improve the performance stability of continuously produced products.
  • the invention adopts a high-speed mixer to uniformly mix the blending formula of the plastic base material, the processing aid and the pre-mixed liquid additive.
  • the conical twin-screw adopts a granulation die head with a diameter of 3 to 6 mm, and adopts a rotary cutting granulation method
  • the cooling method adopts water circulation cooling, and is equipped with a drying machine
  • the first-stage single screw 150 ⁇ 170°C in the first zone, 160 ⁇ 180°C in the second zone, 170 ⁇ 200°C in the third zone, 170 ⁇ 200°C in the conveying section; speed setting: the extrusion speed is 20 ⁇ 70r/min.
  • the second-order counter-conical twin-screw 140 ⁇ 160°C in the first zone, 150 ⁇ 180°C in the second zone, 165 ⁇ 190°C in the third zone, 160 ⁇ 180°C in the confluence core, 135 ⁇ 160°C in the first die, 120 in the second die ⁇ 160°C; speed setting: extrusion speed 8 ⁇ 26r/min, rotary cutting speed 30 ⁇ 60r/min.
  • This embodiment provides a modified recycled polyethylene plastic for plastic pipes, including a plastic base material, a modified reinforcing and toughening additive, and a processing aid; wherein, in parts by weight,
  • the plastic substrates include: 45 pieces of recycled oil can HDPE crushed material, 20 pieces of recycled big blue bucket HDPE crushed material, 15 pieces of recycled LDPE film granulation material, 10 pieces of recycled paint bucket (ethylene propylene copolymer) crushed material;
  • Modified strengthening and toughening additives include: 0.3 part of methyltrimethoxysilane, 0.02 part of DCPO, 0.01 part of MnO 2 , 0.01 part of CuO, 0.015 part of antioxidant 168, 0.015 part of antioxidant 1010;
  • Processing aids include: 8 parts of talc, 0.03 part of EBS, 0.1 part of stearic acid, and 0.1 part of zinc stearate.
  • the present embodiment also provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • High-speed mixer setting the rotating speed is 900r/min, and the mixing time is 2min.
  • the first-stage single screw the first zone is 150 °C, the second zone is 160 °C, the third zone is 170 °C, and the conveying section is 170 °C; speed setting: extrusion speed 50r/min.
  • Second-order counter-conical twin-screw 140°C in the first zone, 150°C in the second zone, 165°C in the third zone, 160°C in the confluence core, 135°C in the first die, and 120°C in the second die; speed setting: extrusion speed 22r /min, rotary speed 40r/min.
  • This embodiment provides a modified recycled polyethylene plastic for plastic pipes, including a plastic base material, a modified reinforcing and toughening additive, and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: 40 pieces of recycled variegated daily necessities HDPE hollow container crushed material, 20 pieces of recycled blue HDPE hollow barrel crushed material, 10 pieces of recycled LDPE mixed film granulation material, and 5 recycled blue mixed film granulated material of recycled LLDPE 10 pieces of EVA sheet crushing material, 3 pieces of recycled EPDM recycled crushing material;
  • Modified strengthening and toughening additives include: 0.2 part of triacetoxysilane, 0.2 part of propyltriacetoxysilane, 0.2 part of maleic anhydride, 0.02 part of BPO, 0.02 part of DCPO, 0.02 part of CuO, 0.02 part of Fe 2 O 3 , 0.02 part of antioxidant 168, 0.01 part of antioxidant 1010;
  • Processing aids include: 11 parts of mica stone powder, 4 parts of silica fume powder, 0.01 part of EBS, 0.02 part of PE wax, 0.1 part of zinc stearate, and 0.2 part of calcium stearate.
  • the present embodiment also provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • High-speed mixer setting the rotating speed is 900r/min, and the mixing time is 4min.
  • the first-stage single screw the first zone is 170°C, the second zone is 180°C, the third zone is 200°C, and the conveying section is 200°C; speed setting: the extrusion speed is 55r/min.
  • Second-order counter-conical twin-screw first zone 160°C, second zone 180°C, third zone 190°C, confluence core 180°C, die first 160°C, die second 160°C; speed setting: extrusion speed 24r /min, rotary speed 40r/min.
  • This embodiment provides a modified recycled polyethylene plastic for plastic pipes, including a plastic base material, a modified reinforcing and toughening additive, and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: 45 parts of recycled oil can HDPE crushed material, 35 parts of recycled blue HDPE hollow barrel crushed material, 10 parts of recycled LDPE mixed film granulation material, 5 recycled LLDPE mixed film granulated material, recycled EPDM recycled crushed material 5 servings;
  • Modified strengthening and toughening additives include: 0.4 part of methyltrimethoxysilane, 0.1 part of triacetoxysilane, 0.4 part of maleic anhydride, 0.02 part of BPO, 0.03 part of DCPO, 0.01 part of ZnO, 0.005 part of antioxidant 168 , 0.005 parts of antioxidant 1010;
  • Processing aids include: 5 parts of talc, 0.02 part of EBS, 0.3 part of stearic acid, and 0.7 part of oxidized polyethylene.
  • the present embodiment also provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • methyltrimethoxysilane, triacetoxysilane, maleic anhydride, BPO, DCPO, ZnO, antioxidant 168, antioxidant 1010 are pre-mixed uniformly, and then mixed with other materials in a high-speed mixer After homogenization, a single-screw-counter-conical twin-screw second-stage extruder was used to extrude and granulate to prepare dark-colored modified regenerated polyethylene plastic particles for plastic pipes.
  • High-speed mixer setting the rotating speed is 500r/min, and the mixing time is 5min.
  • the first-stage single screw the first zone is 155°C, the second zone is 165°C, the third zone is 175°C, and the conveying section is 175°C; speed setting: the extrusion speed is 25r/min.
  • the second-order counter-conical twin-screw 145°C for the first zone, 155°C for the second zone, 170°C for the third zone, 170°C for the confluence core, 140°C for the first die, 125°C for the second die; speed setting: extrusion speed 10r /min, rotary speed 60r/min.
  • This embodiment provides a modified recycled polyethylene plastic for plastic pipes, including a plastic base material, a modified reinforcing and toughening additive, and a processing aid; wherein, in parts by weight,
  • Plastic substrates include: recycled oil pot HDPE crushed material 20, recycled blue HDPE hollow barrel crushed 30, recycled LDPE mixed film granulation 20, recycled LLDPE mixed film granulation 10, recycled blue EVA sheet 20 pieces of material crushing material, 5 pieces of recycled EPDM recycled crushing material;
  • Modified strengthening and toughening additives include: 0.1 part of methyltrimethoxysilane, 0.1 part of maleic anhydride, 0.01 part of BPO, 0.01 part of DCPO, 0.02 part of ZnO, 0.01 part of Cu 2 O, 0.01 part of antioxidant 168, antioxidant agent 1010 0.01 part;
  • the processing aids include: 5 parts of calcium carbonate powder, 5 parts of mica stone powder, 0.02 part of EBS added, 0.03 part of PE wax, 0.3 part of zinc stearate, and 0.4 part of oxidized polyethylene.
  • the present embodiment also provides a method for preparing a modified regenerated polyethylene plastic for plastic pipes, comprising the following steps:
  • High-speed mixer setting the rotating speed is 1000r/min, and the mixing time is 1min.
  • the first-stage single screw the first zone is 165°C, the second zone is 175°C, the third zone is 195°C, and the conveying section is 195°C; speed setting: the extrusion speed is 70r/min.
  • Second-order counter-conical twin-screw first zone 155°C, second zone 175°C, third zone 185°C, confluence core 175°C, die first 155°C, die second 155°C; speed setting: extrusion speed 24r /min, rotary speed 30r/min.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 2 is only that, in Comparative Example 1, the single-screw second-stage extruder process is used for extrusion granulation, and the single-screw second-stage extruder process is set as follows:
  • the first-stage single screw the first zone is 170°C, the second zone is 180°C, the third zone is 200°C, and the conveying section is 200°C; speed setting: the extrusion speed is 55r/min.
  • Second-stage single screw 170°C in the first zone, 180°C in the second zone, 200°C in the third zone, and 200°C in the conveying section; speed setting: extrusion speed 55r/min.
  • Comparative Example 2 The only difference between Comparative Example 2 and Example 2 is that no dehydration catalyst is added in Comparative Example 2.
  • the plastic base material includes: 20 parts of recycled variegated daily necessities HDPE hollow container crushed material, 10 recycled blue HDPE hollow barrel crushed material, and 20 parts of recycled LDPE mixed film granulation material , 20 parts of recycled LLDPE mixed film granulation material, 17 parts of blue EVA sheet crushed material, 6 parts of recycled EPDM recycled crushed material.
  • the plastic base material includes: 56 parts of recycled variegated daily necessities HDPE hollow container crushed material, 28 recycled blue HDPE hollow barrel crushed material, 3 parts of recycled LDPE mixed film granulation material , 3 parts of recycled LLDPE mixed film granulation material, 2 parts of blue EVA sheet crushed material, 1 part of recycled EPDM recycled crushed material.
  • the modified plastic particles obtained in the above-mentioned Examples 1-4 and Comparative Examples 1-4 were sampled and injection-molded, and the impact strength and bending die of the standard specimens were tested according to GB/T 1043.1-2008 and GB/T 9341-2008 respectively. A performance test was carried out, and the results are shown in Table 1.
  • Example 1 Impact Strength (kJ/m 2 ) Flexural modulus (MPa)
  • Example 1 26 ⁇ 30 530 ⁇ 570
  • Example 2 33 ⁇ 35 680 ⁇ 710
  • Example 3 30 ⁇ 33 660 ⁇ 700
  • Example 4 32 ⁇ 36 690 ⁇ 730 Comparative Example 1 23 ⁇ 31 490 ⁇ 620 Comparative Example 2 16 ⁇ 25 320 ⁇ 550 Comparative Example 3 19 ⁇ 22 340 ⁇ 440 Comparative Example 4 23 ⁇ 27 460 ⁇ 530
  • Comparative Example 1 adopts single-screw-conical twin-screw two-stage extrusion granulation, and the obtained modified recycled polyethylene plastic for plastic pipes has low performance and deviation in stability.
  • Example 2 Compared with Example 2, no dehydration catalyst was added in Comparative Example 2, and the synergistic effect of the dehydration catalyst and the remaining components could not be fully exerted, resulting in poor reaction activity and greatly reduced performance of the obtained modified regenerated polyethylene plastic.
  • Example 2 Compared with Example 2, the amount of waste PE plastic added in Comparative Example 3 and Comparative Example 4 is not within the scope of this application, and the obtained modified recycled polyethylene plastics have lower impact strength and flexural modulus. In the production process, the proportion of waste PE plastics needs to be strictly controlled.

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Abstract

一种用于塑料管道的改性再生聚乙烯塑料及其制备方法。该改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，塑料基材包括：HDPE废塑料、LDPE废塑料、LLDPE废塑料、乙烯共聚物废塑料；改性增强增韧添加剂包括：硅烷化合物、马来酸酐、接枝引发剂、脱水催化剂、抗氧剂；加工助剂包括：刚性填料、内润滑剂、外润滑剂。该方法通过采用塑料基材、改性增强增韧添加剂和加工助剂制备改性再生PE塑料，所得改性再生PE塑料冲击强度高、且性能稳定。

Description

一种用于塑料管道的改性再生聚乙烯塑料及其制备方法 技术领域
本发明涉及资源再生技术领域，尤其涉及一种用于塑料管道的改性再生聚乙烯塑料及其制备方法。
背景技术
随着我国塑料工业的发展，大量的塑料废弃物随之产生。我国每年产生的废弃塑料量约为1400万吨左右，它们不能够自然分解、不腐烂，已成为瞩目的社会问题。废塑料的回收再生利用能够将工业垃圾变成极有价值的工业生产原料，实现了资源再生循环利用，具有不可忽略的潜在意义。目前世界各国对废塑料的回收再生利用方法都很关注和支持，在工业发达国家的固体废弃物中，废塑料约占10％～20％。而聚烯烃(主要是PE和PP)占有相当大的比例，其具有回收利用价值高、耐老化性较好等特点。
塑料管道种类较多，其中聚乙烯(PE)管道常用于输气、给排水、电缆光缆护套等埋地应用，这类塑料管道与传统的铸铁管、镀锌钢管、水泥管等管道相比，具有节能节材、环保、轻质高强、耐腐蚀、内壁光滑不结垢、施工和维修简便、使用寿命长等优点，广泛应用于建筑给排水、城乡给排水、城市燃气、电力和光缆护套、工业流体输送、农业灌溉等建筑业、市政、工业和农业领域。
PE塑料管道同样也有一些缺点，首先由于刚性不足，仍然无法在大口径管道上替代钢管等其他材质塑料管道；其次，塑料作为一种石化合成材料在成本上仍然偏高；最后，PE塑料管道虽然可以添加再生的废塑 料PE作为原料进行生产以降低成本，但由于废塑料的来源复杂与不稳定性，也造成PE塑料管道产品的性能不稳定，给管道使用安全造成隐患。
发明内容
有鉴于此，有必要提供一种用于塑料管道的改性再生聚乙烯塑料及其制备方法，用以解决现有技术中现有的改性再生PE塑料刚性差、性能不稳定的技术问题。
本发明的第一方面提供一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：HDPE废塑料50～80份、LDPE废塑料10～20份、LLDPE废塑料0～10份、乙烯共聚物废塑料5～25份；
改性增强增韧添加剂包括：硅烷化合物0.1～0.5份、马来酸酐0～0.4份、接枝引发剂0.02～0.05份、脱水催化剂0.01～0.04份、抗氧剂0.01～0.03份；
加工助剂包括：刚性填料5～15份、内润滑剂0.02～0.05份、外润滑剂0.2～1份。
本发明的第二方面提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
将改性增强增韧添加剂先混合均匀形成预混合液态添加剂；
将塑料基材、加工助剂与预混合液态添加剂混合均匀后，通过单螺杆-异向锥形双螺杆二阶挤出造粒机造粒制得塑料管道用改性再生聚乙烯塑料。
本发明第二方面提供的用于塑料管道的改性再生聚乙烯塑料的制备方法用于得到本发明第一方面提供的用于塑料管道的改性再生聚乙烯塑 料。
与现有技术相比，本发明的有益效果为：
本发明通过采用塑料基材、改性增强增韧添加剂和加工助剂制备改性再生PE塑料，所得改性再生PE塑料冲击强度高、且性能稳定；
本发明的塑料基材中，主要选用了多途径回收可以得到的PE类废塑料，再生塑料+填料的比例占到组分的90％以上，无需添加新料PE，有利于降低生产成本。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的第一方面提供了一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：HDPE废塑料50～80份、LDPE废塑料10～20份、LLDPE废塑料0～10份、乙烯共聚物废塑料5～25份；
改性增强增韧添加剂包括：硅烷化合物0.1～0.5份、马来酸酐0～0.4份、接枝引发剂0.02～0.05份、脱水催化剂0.01～0.04份、抗氧剂0.01～0.03份；
加工助剂包括：刚性填料5～15份、内润滑剂0.02～0.05份、外润滑剂0.2～1份。
进一步地，用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：HDPE废塑料50～80份、LDPE废塑料10～20份、LLDPE废塑料5～10份、乙烯共聚物废塑料5～25份；
改性增强增韧添加剂包括：硅烷化合物0.1～0.5份、马来酸酐0.1～0.4份、接枝引发剂0.02～0.05份、脱水催化剂0.01～0.04份、抗氧剂0.01～0.03份；
加工助剂包括：刚性填料5～15份、内润滑剂0.02～0.05份、外润滑剂0.3～1份。
本发明塑料基材中，HDPE废塑料为HDPE类中空吹塑制品经破碎、清洗后的破碎料；LDPE废塑料为各类废旧LDPE薄膜经造粒得到的粒子；LLDPE废塑料为各类废旧LLDPE薄膜经造粒得到的粒子；乙烯共聚物废塑料为回收的废旧EVA类废旧片材、用品，以及乙烯丙烯共聚体类废旧涂料桶、日用注塑制品经过破碎、清洗后的破碎料。本发明的塑料基材中，主要选用了多途径回收可以得到的PE类废塑料，再生塑料+填料的比例占到组分的90％以上，无需添加新料PE，有利于降低生产成本。
本发明改性增强增韧添加剂中，硅烷化合物为烷基三乙氧基硅烷、甲基三甲氧基硅烷、三乙酰氧基硅烷、丙基三乙酰氧基硅烷中的一种或几种的混合物；马来酸酐为固体或粉末状物质；接枝引发剂为过氢化苯甲酰(BPO)、过氧化二异丙苯(DCPO)、叔丁基过氧化氢(DHPO)中的一种或几种的混合物；脱水催化剂为氧化锰(MnO 2)、氧化铁(Fe 2O 3)、氧化铜(CuO)、氧化亚铜(Cu 2O)、氧化锌(ZnO)中的一种或或几种的混合物；抗氧剂为抗氧剂168、抗氧剂1010中的一种或或几种的混合物。本发明通过添加改性增强增韧添加剂，可以通过提高刚性填料的相容性、提高聚乙烯分子链的交联作用等方式，同时发挥协同作用，大幅度提高材料的刚性、韧性，制备的改性再生粒子比普通再生粒子的抗冲强度提高1～2倍，弯曲模量提高50％以上。
加工助剂中，刚性填料为无机填料，具体为滑石粉、碳酸钙粉、硅藻土粉、硅灰粉、云母石粉中的一种或几种的混合物，目数在1250～2000目；内润滑剂为EBS(乙撑双硬脂酰胺)、PE蜡中的一种或或几种的混合物；外润滑剂为硬脂酸、硬脂酸金属盐、脂肪烃蜡、氧化聚乙烯中的一种或几种的混合物。
本发明的第二方面提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
S1将改性增强增韧添加剂先混合均匀形成预混合液态添加剂；
S2将塑料基材共混配方、加工助剂与预混合液态添加剂混合均匀后，通过单螺杆-异向锥形双螺杆二阶挤出造粒机造粒制得塑料管道用改性再生聚乙烯塑料。
本发明第二方面提供的用于塑料管道的改性再生聚乙烯塑料的制备方法用于得到本发明第一方面提供的用于塑料管道的改性再生聚乙烯塑料。
本发明通过对硅烷化合物等反应性组分的预混合，并引入脱水催化剂，然后再与其他原料混合，可以提高反应组分的活性和均匀性，从而大幅提高反应性组分对材料的改进提升效果。
本发明采用单螺杆-异向锥形双螺杆挤出机进行挤出加工工艺，结合旋切水冷造粒工艺，比起传统的单螺杆二阶挤出拉条造粒工艺，本工艺既可以很好地实现大尺寸废塑料片的稳定喂料，又可以实现更好地配方物料混炼效果并获得更大的挤出压力，大幅提高改性增强增韧添加剂的作用效果，从而提高材料性能；还能提高连续生产出的产品的性能稳定性。
本发明采用高速搅拌机将塑料基材共混配方、加工助剂与预混合液态添加剂进行均匀混合，高速搅拌机转速500～1000r/min，混合时间 1～5min。
本发明中，单螺杆-异向锥形双螺杆二阶挤出造粒机工艺要求如下：
(a)锥形双螺杆采用3～6mm孔径的造粒模头，采用旋切造粒方式；
(b)冷却方式采用水循环冷却，并配置甩干机；
(c)工艺设定：
第一阶单螺杆：一区150～170℃，二区160～180℃，三区170～200℃，输送段170～200℃；速度设定：挤出转速20～70r/min。
第二阶异向锥形双螺杆：一区140～160℃，二区150～180℃，三区165～190℃，合流芯160～180℃，模头一135～160℃，模头二120～160℃；速度设定：挤出转速8～26r/min，旋切转速30～60r/min。
实施例1
本实施例提供了一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：回收机油壶HDPE破碎料45份、回收大蓝桶HDPE破碎料20份、再生LDPE薄膜造粒料15份、回收涂料桶(乙烯丙烯共聚体)破碎料10份；
改性增强增韧添加剂包括：甲基三甲氧基硅烷0.3份、DCPO 0.02份、MnO 20.01份、CuO 0.01份、抗氧剂168 0.015份、抗氧剂1010 0.015份；
加工助剂包括：滑石粉8份、EBS 0.03份、硬脂酸0.1份、硬脂酸锌0.1份。
本实施例还提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
按上述配方，先将甲基三甲氧基硅烷、DCPO、MnO 2、CuO、抗氧剂168、抗氧剂1010预混合均匀，再与其他物料一起采用高速混合机混合均匀后，用单螺杆-异向锥形双螺杆二阶挤出机挤出造粒制备出深色用 于塑料管道的改性再生聚乙烯塑料粒子。
高速混合机设定：转速为900r/min，混合时间2min。
单螺杆-异向锥形双螺杆二阶挤出机工艺设定：
第一阶单螺杆：一区150℃，二区160℃，三区170℃，输送段170℃；速度设定：挤出转速50r/min。
第二阶异向锥形双螺杆：一区140℃，二区150℃，三区165℃，合流芯160℃，模头一135℃，模头二120℃；速度设定：挤出转速22r/min，旋切转速40r/min。
实施例2
本实施例提供了一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：回收的杂色日用品HDPE中空容器破碎料40份、回收蓝色HDPE中空桶破碎料20份、再生LDPE混合薄膜造粒料10份、再生LLDPE混合薄膜造粒料5份回收蓝色EVA片材破碎料10份、回收EPDM再生破碎料3份；
改性增强增韧添加剂包括：三乙酰氧基硅烷0.2份、丙基三乙酰氧基硅烷0.2份、马来酸酐0.2份、BPO 0.02份、DCPO 0.02份、CuO 0.02份、Fe 2O 30.02份、抗氧剂168 0.02份、抗氧剂1010 0.01份；
加工助剂包括：云母石粉11份、硅灰粉4份、EBS 0.01份、PE蜡0.02份、硬脂酸锌0.1份、硬脂酸钙0.2份。
本实施例还提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
按上述配方，先将三乙酰氧基硅烷、丙基三乙酰氧基硅烷、马来酸酐、BPO、DCPO、CuO、Fe 2O 3、抗氧剂168、抗氧剂1010预混合均匀，再与其他物料一起采用高速混合机混合均匀后，用单螺杆-异向锥形双螺 杆二阶挤出机挤出造粒制备出深色用于塑料管道的改性再生聚乙烯塑料粒子。
高速混合机设定：转速为900r/min，混合时间4min。
单螺杆-异向锥形双螺杆二阶挤出机工艺设定：
第一阶单螺杆：一区170℃，二区180℃，三区200℃，输送段200℃；速度设定：挤出转速55r/min。
第二阶异向锥形双螺杆：一区160℃，二区180℃，三区190℃，合流芯180℃，模头一160℃，模头二160℃；速度设定：挤出转速24r/min，旋切转速40r/min。
实施例3
本实施例提供了一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：回收机油壶HDPE破碎料45份、回收蓝色HDPE中空桶破碎料35份、再生LDPE混合薄膜造粒料10份、再生LLDPE混合薄膜造粒料5份、回收EPDM再生破碎料5份；
改性增强增韧添加剂包括：甲基三甲氧基硅烷0.4份、三乙酰氧基硅烷0.1份、马来酸酐0.4份、BPO 0.02份、DCPO 0.03份、ZnO0.01份、抗氧剂168 0.005份、抗氧剂1010 0.005份；
加工助剂包括：滑石粉5份、EBS 0.02份、硬脂酸0.3份、氧化聚乙烯0.7份。
本实施例还提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
按上述配方，甲基三甲氧基硅烷、三乙酰氧基硅烷、马来酸酐、BPO、DCPO、ZnO、抗氧剂168、抗氧剂1010预混合均匀，再与其他物料一起采用高速混合机混合均匀后，用单螺杆-异向锥形双螺杆二阶挤出机挤出 造粒制备出深色用于塑料管道的改性再生聚乙烯塑料粒子。
高速混合机设定：转速为500r/min，混合时间5min。
单螺杆-异向锥形双螺杆二阶挤出机工艺设定：
第一阶单螺杆：一区155℃，二区165℃，三区175℃，输送段175℃；速度设定：挤出转速25r/min。
第二阶异向锥形双螺杆：一区145℃，二区155℃，三区170℃，合流芯170℃，模头一140℃，模头二125℃；速度设定：挤出转速10r/min，旋切转速60r/min。
实施例4
本实施例提供了一种用于塑料管道的改性再生聚乙烯塑料，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
塑料基材包括：回收机油壶HDPE破碎料20份、回收蓝色HDPE中空桶破碎料30份、再生LDPE混合薄膜造粒料20份、再生LLDPE混合薄膜造粒料10份、回收蓝色EVA片材破碎料20份、回收EPDM再生破碎料5份；
改性增强增韧添加剂包括：甲基三甲氧基硅烷0.1份、马来酸酐0.1份、BPO 0.01份、DCPO 0.01份、ZnO 0.02份、Cu 2O 0.01份、抗氧剂168 0.01份、抗氧剂1010 0.01份；
加工助剂包括：碳酸钙粉5份、云母石粉5份、EBS添加0.02份、PE蜡0.03份、硬脂酸锌0.3份、氧化聚乙烯0.4份。
本实施例还提供了一种用于塑料管道的改性再生聚乙烯塑料的制备方法，包括以下步骤：
按上述配方，先将甲基三甲氧基硅烷、马来酸酐、BPO、DCPO、ZnO、Cu 2O、抗氧剂168、抗氧剂1010预混合均匀，再与其他物料一起采用高速混合机混合均匀后，用单螺杆-异向锥形双螺杆二阶挤出机挤出造粒制 备出深色用于塑料管道的改性再生聚乙烯塑料粒子。
高速混合机设定：转速为1000r/min，混合时间1min。
单螺杆-异向锥形双螺杆二阶挤出机工艺设定：
第一阶单螺杆：一区165℃，二区175℃，三区195℃，输送段195℃；速度设定：挤出转速70r/min。
第二阶异向锥形双螺杆：一区155℃，二区175℃，三区185℃，合流芯175℃，模头一155℃，模头二155℃；速度设定：挤出转速24r/min，旋切转速30r/min。
对比例1
对比例1与实施例2的区别仅在于，对比例1中采用单螺杆二阶挤出机工艺挤出造粒，且单螺杆二阶挤出机工艺设定如下：
第一阶单螺杆：一区170℃，二区180℃，三区200℃，输送段200℃；速度设定：挤出转速55r/min。
第二阶单螺杆：一区170℃，二区180℃，三区200℃，输送段200℃；速度设定：挤出转速55r/min。
对比例2
对比例2与实施例2的区别仅在于，对比例2中未加入脱水催化剂。
对比例3
对比例3与实施例2的区别仅在于，塑料基材包括：回收的杂色日用品HDPE中空容器破碎料20份、回收蓝色HDPE中空桶破碎料10份、再生LDPE混合薄膜造粒料20份、再生LLDPE混合薄膜造粒料20份回收蓝色EVA片材破碎料17份、回收EPDM再生破碎料6份。
对比例4
对比例4与实施例2的区别仅在于，塑料基材包括：回收的杂色日用品HDPE中空容器破碎料56份、回收蓝色HDPE中空桶破碎料28份、 再生LDPE混合薄膜造粒料3份、再生LLDPE混合薄膜造粒料3份回收蓝色EVA片材破碎料2份、回收EPDM再生破碎料1份。
对上述实施例1～4和对比例1～4所得改性塑料粒子取样并进行注塑样条，分别按照GB/T 1043.1-2008和GB/T 9341-2008测试标准样条的冲击强度和弯曲模量，进行性能测试，其结果见表1。
表1
  抗冲强度(kJ/m 2) 弯曲模量(MPa)
实施例1 26～30 530～570
实施例2 33～35 680～710
实施例3 30～33 660～700
实施例4 32～36 690～730
对比例1 23～31 490～620
对比例2 16～25 320～550
对比例3 19～22 340～440
对比例4 23～27 460～530
由表1可以看出，本发明实施例1～4连续生产所得改性再生聚乙烯塑料均具有较高的抗冲击强度和弯曲模量，且性能稳定性好。
与实施例2相比，对比例1采用单螺杆-锥形双螺杆二阶挤出造粒，所得用于塑料管道的改性再生聚乙烯塑料性能偏低且稳定性偏差。
与实施例2相比，对比例2中未加入脱水催化剂，无法充分发挥脱水催化剂与其余组分的协同作用，从而导致反应活性差，所得改性再生聚乙烯塑料性能大幅降低。
与实施例2相比，对比例3和对比例4中废PE塑料的加入量不在本申请的范围内，所得改性再生聚乙烯塑料均具有较低的抗冲击强度和弯曲模量，说明在生产过程中，需严格控制各废PE塑料的配比。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (7)

  1. 一种用于塑料管道的改性再生聚乙烯塑料，其特征在于，包括塑料基材、改性增强增韧添加剂和加工助剂；其中，按重量份计，
    所述塑料基材包括：HDPE废塑料50～80份、LDPE废塑料10～20份、LLDPE废塑料0～10份、乙烯共聚物废塑料5～25份；
    所述改性增强增韧添加剂包括：硅烷化合物0.1～0.5份、马来酸酐0～0.4份、接枝引发剂0.02～0.05份、脱水催化剂0.01～0.04份、抗氧剂0.01～0.03份；
    所述加工助剂包括：刚性填料5～15份、内润滑剂0.02～0.05份、外润滑剂0.2～1份。
  2. 根据权利要求1所述用于塑料管道的改性再生聚乙烯塑料，其特征在于，所述塑料基材中，所述HDPE废塑料为HDPE类中空吹塑制品经破碎、清洗后的破碎料；所述LDPE废塑料为各类废旧LDPE薄膜经造粒得到的粒子；所述LLDPE废塑料为各类废旧LLDPE薄膜经造粒得到的粒子；所述乙烯共聚物废塑料为回收的废旧EVA类废旧片材、用品，以及乙烯丙烯共聚体类废旧涂料桶、日用注塑制品经过破碎、清洗后的破碎料。
  3. 根据权利要求1所述用于塑料管道的改性再生聚乙烯塑料，其特征在于，所述改性增强增韧添加剂中，所述硅烷化合物为烷基三乙氧基硅烷、甲基三甲氧基硅烷、三乙酰氧基硅烷、丙基三乙酰氧基硅烷中的一种或几种的混合物；所述接枝引发剂为过氢化苯甲酰、过氧化二异丙苯、叔丁基过氧化氢中的一种或几种的混合物；所述脱水催化剂为氧化锰、氧化铁、氧化铜、氧化亚铜、氧化锌中的一种或或几种的混合物；所述抗氧剂为抗氧剂168、抗氧剂1010中的一种或或几种的混合物。
  4. 根据权利要求1所述用于塑料管道的改性再生聚乙烯塑料，其特征在于，所述加工助剂中，所述刚性填料为无机填料；所述内润滑剂为 乙撑双硬脂酰胺、PE蜡中的一种或或几种的混合物；所述外润滑剂为硬脂酸、硬脂酸金属盐、脂肪烃蜡、氧化聚乙烯中的一种或几种的混合物。
  5. 一种如权利要求1～4中任一项所述用于塑料管道的改性再生聚乙烯塑料的制备方法，其特征在于，包括以下步骤：
    将改性增强增韧添加剂先混合均匀形成预混合液态添加剂；
    将塑料基材共混配方、加工助剂与所述预混合液态添加剂混合均匀后，通过单螺杆-异向锥形双螺杆二阶挤出造粒机造粒制得塑料管道用改性再生聚乙烯塑料。
  6. 根据权利要求5所述用于塑料管道的改性再生聚乙烯塑料的制备方法，其特征在于，采用高速搅拌机将塑料基材共混配方、加工助剂原料与预混合液态添加剂进行均匀混合，所述高速搅拌机转速500～1000r/min，混合时间1～5min。
  7. 根据权利要求5所述用于塑料管道的改性再生聚乙烯塑料的制备方法，其特征在于，单螺杆-异向锥形双螺杆二阶挤出造粒机工艺要求如下：
    锥形双螺杆采用3～6mm孔径的造粒模头，采用旋切造粒方式；
    冷却方式采用水循环冷却，并配置甩干机；
    工艺设定：
    第一阶单螺杆：一区150～170℃，二区160～180℃，三区170～200℃，输送段170～200℃；速度设定：挤出转速20～70r/min；
    第二阶异向锥形双螺杆：一区140～160℃，二区150～180℃，三区165～190℃，合流芯160～180℃，模头一135～160℃，模头二120～160℃；速度设定：挤出转速8～26r/min，旋切转速30～60r/min。
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