CN105065792A - Cold-resistant high impact strength unplasticized polyvinyl chloride (PVC-U) composite pipe and preparation method thereof - Google Patents

Cold-resistant high impact strength unplasticized polyvinyl chloride (PVC-U) composite pipe and preparation method thereof Download PDF

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Publication number
CN105065792A
CN105065792A CN201510468226.9A CN201510468226A CN105065792A CN 105065792 A CN105065792 A CN 105065792A CN 201510468226 A CN201510468226 A CN 201510468226A CN 105065792 A CN105065792 A CN 105065792A
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pvc
cold
parts
layer
sections
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CN201510468226.9A
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Inventor
王冲
保功辉
李娇
张超奇
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Dayu Water Saving Tianjin Co Ltd
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Dayu Water Saving Tianjin Co Ltd
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Priority to CN201510468226.9A priority Critical patent/CN105065792A/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00Rigid pipes
    • F16L9/12Rigid pipes of plastics with or without reinforcement
    • F16L9/121Rigid pipes of plastics with or without reinforcement with three layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/06Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/12Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
    • F16L11/125Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00Thermal insulation in general
    • F16L59/02Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00Thermal insulation in general
    • F16L59/02Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • F16L59/028Composition or method of fixing a thermally insulating material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92009Measured parameter
    • B29C2948/92209Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a cold-resistant high impact strength unplasticized polyvinyl chloride (PVC-U) composite pipe and a preparation method thereof. The pipe is of a three-layer structure which sequentially includes an inner PVC layer, a middle foaming polyethylene (PE) layer and an outer PE layer. The preparation method includes the following steps that raw materials of the PVC layer are uniformly mixed, added into a PVC pipe production line and subjected to extrusion, setting, cooling, pulling, cutting and the like, so that an inner pipe layer is obtained; the middle foaming PE layer is composited on the inner PVC layer through a composite production line; meanwhile, the outer PE layer is composited on the middle layer, and a finished product is obtained. By means of the cold-resistant high impact strength PVC-U composite pipe and the preparation method thereof, cold resistance, shock resistance and thermal insulation property of the pipe are extremely improved; the adaptability of the plastic pipe to the environment is enhanced; meanwhile, the defect of poor cold resistance of the PVC-U pipe is overcome; excellent properties of PVC and PE pipes are integrated.

Description

A kind of cold-resistant high-impact PVC-U composite pipe and preparation method thereof
Technical field
The invention belongs to plastic tube technical field, especially relate to a kind of cold-resistant high-impact PVC-U composite pipe and preparation method thereof.
Background technique
Along with the advanced irrigation technique such as drip irrigation and spray irrigation, microspray irrigation is in the fast development of China, the tubing matched with it have also been obtained fast development, especially PVC-U tubing, PVC-U tubing have lightweight, corrosion-resistant, the advantage such as resistance to water-flow is little, energy saving, installation is fast, cost is low is widelyd popularize, and is a part indispensable in water-saving irrigation.But, there is the problems such as winter hardiness, heat insulating ability and low temperature impact performance difference in current PVC-U tubing, especially northeastward and the performance of colder place particularly outstanding, such as to break and the phenomenons such as bursting by freezing appear in buried pipeline during tubing handling, this has had a strong impact on the normal operation of irrigation system to a certain extent, increase the cost of investment of system, therefore, a kind of cold-resistant high-impact PVC-U composite pipe of exploitation and preparation method thereof seems particularly urgent simultaneously.
Summary of the invention
The present invention is mainly for defects such as PVC-U tubing low-temperature flexibility, winter hardiness and heat insulating ability differences, provide a kind of cold-resistant high-impact PVC-U composite pipe, this pipeline has obvious winter hardiness and low temperature impact performance, northeast and the irrigation system in colder place and the normal operation of city planting ductwork are played a role, also reduces cost of investment simultaneously.
The technological scheme adopted is:
A kind of cold-resistant high-impact PVC-U composite pipe, this composite pipe is three-decker, is followed successively by PVC internal layer, foaming PE mesosphere and PE skin, and described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Stabilizer 3-3.5 part; Filler 8-12 part; Oiling agent 0.3-0.65 part; Processing aid 1.3-1.5 part; Plasticizer 2.2-2.8 part; Carbon black 0.06-0.1 part.
Preferably, described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Stabilizer 3.1 parts; Filler 9 parts; Oiling agent 0.4 part; Processing aid 1.35 parts; Plasticizer 2.3 parts; Carbon black 0.1 part.
Preferred, described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Calcium zinc stabilizer 3.1 parts; Precipitated calcium carbonate filler 9 parts; Stearic acid and/or 0.4 part, PE wax; Processing aid ACR1.35 part; Toughening agent C PE2.3 part; Carbon black 0.1 part.
ACR (Acryliccopolymer) is acrylate rubber, and CPE is haloflex.
Preferably, described foaming PE mesosphere is microvesicle cellular structure, and it mainly plays the effect of insulation and buffering.
Preferably, described PE skin selects 100 level high-density polyethylenes, and it mainly plays scratch-resistant effect.
Preferably, this PVC-U tubing each layer thickness difference from inside to outside: 2.1mm-2.3mm, 2.2mm-2.5mm, 1.9mm-2.1mm, most preferred, each layer thickness is respectively 2.3mm, 2.4mm, 2.0mm.
The present invention also provides a kind of method preparing any one cold-resistant high-impact PVC-U composite pipe above-mentioned, and the method comprises the steps:
(1) by polyvinyl chloride resin powder, stabilizer, filler, oiling agent, processing aid, plasticizer and carbon black precise in proportion, then join in mixing device that to carry out heat mixed and cold mixed sequentially successively;
(2) material that step (1) mixes is joined PVC production line by automatic charging machine, through extruding, shaping, cool, draw, cutting action obtains Inner tubing layers;
(3) by composite foamed production line composite foamed PE mesosphere on step (2) PVC internal layer, compound one deck PE is outer on the intermediate layer simultaneously, namely obtains finished product.
Preferably, the mixed temperature of heat is 125 DEG C in step (1), and heat is done time 20-25min, and cold mixed temperature is 45 DEG C, the cold 10-15min that does time.
Preferably, barrel one section in step (2), two sections, three sections and four sections of temperature are respectively 180 DEG C, 175 DEG C, 170 DEG C, 165 DEG C, head one section, two sections, and three sections and four sections of temperature are respectively 165 DEG C, 175 DEG C, 180 DEG C, 185 DEG C.
Preferably, the blowing temperature in foaming PE mesosphere is 130-175 DEG C.
Preferably, the outer field mold temperature of PE is 150-220 DEG C.
The advantage that the present invention has and good effect are: the present invention is by compound and foam process, improve the winter hardiness of tubing, impact resilience and thermal insulation property, this kind of tubing is prepared into pipeline, the destruction that pipeline causes because of environmental factor is decreased in using process, extend the working life of pipeline, reduce the holistic cost of pipe-line system.
Embodiment
Embodiment 1
A kind of cold-resistant high-impact PVC-U composite pipe, comprises three-decker, PVC internal layer, foaming PE mesosphere and PE skin, and wherein, PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Calcium zinc stabilizer 3.1 parts; Precipitated calcium carbonate filler 9 parts; Stearic acid and/or 0.4 part, PE wax; Processing aid ACR1.35 part; Toughening agent C PE2.3 part; Carbon black 0.1 part.
The preparation method of this tubing is:
First, each component of preparation PVC internal layer is weighed, then joins in batch mixing pot successively according to sequencing, first carry out heat and mix, the mixed temperature 125 DEG C of heat, mixing 20-25min, then carry out cold mixed, cold mixed temperature 45 C, mixing 10-15min.
Secondly, the material mixed is joined PVC production line by automatic charging machine, through extruding, sizing, cooling, traction, the operations such as cutting obtain Inner tubing layers, in this step, barrel temperature is divided into four sections, barrel one section, two sections, three sections, four sections of temperature are respectively 180 DEG C, 175 DEG C, 170 DEG C, 165 DEG C, head temperature is divided into four sections, head one section, two sections, three sections, four sections of temperature are respectively 165 DEG C, 175 DEG C, 180 DEG C, 185 DEG C.
Finally, by composite foamed production line, the foaming PE mesosphere of limit foaming compound is extruded in PVC internal layer top, simultaneously, compound one deck has 100 level high-density polyethylenes skins of high Scratch Resistance energy on the intermediate layer, namely obtain finished product, outer field mold temperature is 150-220 DEG C, and the blowing temperature in mesosphere is 130-175 DEG C.In gained finished product, outer layer thickness 2.0mm, intermediate layer thickness is 2.4mm, and internal layer thickness is 2.3mm.
Embodiment 2
In this embodiment, layer of PVC is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Calcium zinc stabilizer 3.1 parts; Precipitated calcium carbonate filler 11 parts; 0.5 part, PE wax; Processing aid ACR1.35 part; Toughening agent C PE2.3 part; Carbon black 0.1 part.
Other are identical with embodiment 1.
Carry out erosion-resisting characteristics to the tubing prepared by said method, thermal insulation property and cold tolerance test, result is as follows:
Above 2 embodiments of the present invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.

Claims (10)

1. a cold-resistant high-impact PVC-U composite pipe, is characterized in that: this composite pipe is three-decker, is followed successively by PVC internal layer, foaming PE mesosphere and PE skin, and described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Stabilizer 3-3.5 part; Filler 8-12 part; Oiling agent 0.3-0.65 part; Processing aid 1.3-1.5 part; Plasticizer 2.2-2.8 part; Carbon black 0.06-0.1 part.
2. cold-resistant high-impact PVC-U composite pipe according to claim 1, is characterized in that: described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Stabilizer 3.1 parts; Filler 9 parts; Oiling agent 0.4 part; Processing aid 1.35 parts; Plasticizer 2.3 parts; Carbon black 0.1 part.
3. cold-resistant high-impact PVC-U composite pipe according to claim 2, is characterized in that: described PVC internal layer is prepared by each component of following parts by weight:
Polyvinyl chloride resin 100 parts; Calcium zinc stabilizer 3.1 parts; Precipitated calcium carbonate filler 9 parts; Stearic acid and/or 0.4 part, PE wax; Processing aid ACR1.35 part; Toughening agent C PE2.3 part; Carbon black 0.1 part.
4., according to the arbitrary described cold-resistant high-impact PVC-U composite pipe of claim 1-3, it is characterized in that: described foaming PE mesosphere is microvesicle cellular structure.
5. cold-resistant high-impact PVC-U composite pipe according to claim 4, is characterized in that: described PE skin selects 100 level high-density polyethylenes.
6. prepare the method for the arbitrary described cold-resistant high-impact PVC-U composite pipe of claim 1-5, it is characterized in that, comprise the steps:
(1) by polyvinyl chloride resin powder, stabilizer, filler, oiling agent, processing aid, plasticizer and carbon black precise in proportion, then join in mixing device that to carry out heat mixed and cold mixed sequentially successively;
(2) material that step (1) mixes is joined PVC production line by automatic charging machine, through extruding, shaping, cool, draw, cutting action obtains Inner tubing layers;
(3) by composite production line composite foamed PE mesosphere on step (2) PVC internal layer, compound one deck PE is outer on the intermediate layer simultaneously, namely obtains finished product.
7. method according to claim 6, is characterized in that: the mixed temperature of heat is 125 DEG C in step (1), and heat is done time 20-25min, and cold mixed temperature is 45 DEG C, the cold 10-15min that does time.
8. method according to claim 6, is characterized in that: in step (2), barrel temperature is 180-165 DEG C, and head temperature is 160-185 DEG C; Preferably, barrel temperature is divided into four sections, barrel one section, two sections, three sections, and four sections of temperature are respectively 180 DEG C, 175 DEG C, 170 DEG C, 165 DEG C, and head temperature is divided into four sections, head one section, two sections, three sections, and four sections of temperature are respectively 165 DEG C, 175 DEG C, 180 DEG C, 185 DEG C.
9. method according to claim 6, is characterized in that: the blowing temperature in foaming PE mesosphere is 130-175 DEG C.
10. method according to claim 6, is characterized in that: the outer field mold temperature of PE is 150-220 DEG C.
CN201510468226.9A 2015-07-31 2015-07-31 Cold-resistant high impact strength unplasticized polyvinyl chloride (PVC-U) composite pipe and preparation method thereof Pending CN105065792A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860229A (en) * 2016-06-15 2016-08-17 潘海云 Core-layer foamed composite tubular product and preparation process thereof
CN106188984A (en) * 2016-08-28 2016-12-07 肖丽燕 A kind of low temperature resistant antivibration fretting map PVC board its preparation method
CN106641585A (en) * 2016-12-20 2017-05-10 浙江伟星新型建材股份有限公司 PPR insulating composite tube for home decoration and preparation method of composite tube
CN108794922A (en) * 2018-05-31 2018-11-13 安徽玉发塑业有限公司 The drainpipe of high impact strength under a kind of low temperature environment
CN111059365A (en) * 2019-11-12 2020-04-24 中兆建工集团有限公司 Underground long-distance water delivery pipe for municipal engineering and production process thereof
JP2021143731A (en) * 2020-03-12 2021-09-24 積水化学工業株式会社 Multilayer pipe

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CN104045901A (en) * 2014-07-02 2014-09-17 中国石油化工股份有限公司 Ultra-high molecular weight polyethylene composition and process method for producing an ultra-high molecular weight polyethylene composition tubular product
CN104650501A (en) * 2015-02-09 2015-05-27 杭州波达塑料科技股份有限公司 High-temperature-resistant high-toughness PVC-U (unplasticized polyvinyl chloride) double-wall corrugated pipe and preparation method thereof

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CN1267801A (en) * 2000-04-13 2000-09-27 陈仁慈 Metal pipe with heat-insulating foamed plastic coating and its manufacture
CN2477920Y (en) * 2000-12-15 2002-02-20 上海宝洋塑业有限公司 Foamed thermal insulating plastic composite tube
US20020189697A1 (en) * 2001-06-06 2002-12-19 Jyri Jarvenkyla Multilayer pipe and method for manufacturing one
CN101451007A (en) * 2007-11-29 2009-06-10 福建亚通新材料科技股份有限公司 High impact polychloroethylene pressure tube
CN201348099Y (en) * 2008-09-18 2009-11-18 浙江伟星新型建材股份有限公司 Building drainage PE sandwich layer foaming mute pipe
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CN201306532Y (en) * 2008-09-22 2009-09-09 浙江伟星新型建材股份有限公司 Pe-rt composite pipe
CN101531794A (en) * 2009-04-14 2009-09-16 漯河科莱堡洁具配件有限公司 Composite of nanometer grade calcium carbonate modified spiral winded PVC hose for sanitary ware and preparation method thereof
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860229A (en) * 2016-06-15 2016-08-17 潘海云 Core-layer foamed composite tubular product and preparation process thereof
CN106188984A (en) * 2016-08-28 2016-12-07 肖丽燕 A kind of low temperature resistant antivibration fretting map PVC board its preparation method
CN106641585A (en) * 2016-12-20 2017-05-10 浙江伟星新型建材股份有限公司 PPR insulating composite tube for home decoration and preparation method of composite tube
CN108794922A (en) * 2018-05-31 2018-11-13 安徽玉发塑业有限公司 The drainpipe of high impact strength under a kind of low temperature environment
CN111059365A (en) * 2019-11-12 2020-04-24 中兆建工集团有限公司 Underground long-distance water delivery pipe for municipal engineering and production process thereof
CN111059365B (en) * 2019-11-12 2022-03-22 中兆建工集团有限公司 Underground long-distance water delivery pipe for municipal engineering and production process thereof
JP2021143731A (en) * 2020-03-12 2021-09-24 積水化学工業株式会社 Multilayer pipe
JP7479877B2 (en) 2020-03-12 2024-05-09 積水化学工業株式会社 Multilayer Pipe

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Application publication date: 20151118