CN102506241A - Heat-insulation oxygen-blocking antibacterial high impact polypropylene tube and manufacturing method thereof - Google Patents

Heat-insulation oxygen-blocking antibacterial high impact polypropylene tube and manufacturing method thereof Download PDF

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CN102506241A
CN102506241A CN2011103769996A CN201110376999A CN102506241A CN 102506241 A CN102506241 A CN 102506241A CN 2011103769996 A CN2011103769996 A CN 2011103769996A CN 201110376999 A CN201110376999 A CN 201110376999A CN 102506241 A CN102506241 A CN 102506241A
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polypropylene
oxygen
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heat
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程全山
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JIANGSU BAIANJU PIPES CO Ltd
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JIANGSU BAIANJU PIPES CO Ltd
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Abstract

The invention discloses a heat-insulation oxygen-blocking antibacterial high impact polypropylene tube and a manufacturing method thereof, which belong to the technical field of tubes. The heat-insulation oxygen-blocking antibacterial high impact polypropylene tube is manufactured by the multi-layer coextrusion technology, a tube wall is a five-layer coextrusion composite structure, and the heat-insulation oxygen-blocking antibacterial high impact polypropylene tube comprises a surface oxygen-blocking layer, a core layer foaming heat-insulation layer, a core layer oxygen-blocking layer, a glass fiber reinforcing layer and an antibacterial layer. The heat-insulation oxygen-blocking antibacterial high impact polypropylene tube has the advantages of capability of overcoming the shortcoming of low-temperature brittleness of an existing polypropylene tube, oxygen-blocking antibacterial property, corrosion resistance, ageing resistance, heat resistance, processability, heat insulation, energy conservation and the like. Performances of the heat-insulation oxygen-blocking antibacterial high impact polypropylene tube meet the safety evaluation criterion for drinking water delivery and distribution equipment and protection materials. The tube can be widely applied to fields of water supply of municipal administration and buildings, heating and gas supply, electric power, communication, industry, agriculture and the like.

Description

Insulation resistance antibiotic high impact resistance polypropylene tubing of oxygen and production method thereof
Technical field
The invention belongs to the pipeline field, specifically is a kind of insulation resistance antibiotic high impact resistance polypropylene tubing of oxygen and production method thereof.Be mainly used in farmland water-carriage system, water supply system for building, heating system and chemical engineering piping systems etc.
Background technique
Characteristics such as that polypropylene pipe has is high temperature resistant, pipeline is easy to connect (thermal fusion welding, electric-fusion, pipe fitting connect), recyclable are mainly used in farmland water-carriage system, water supply system for building, heating system and chemical engineering piping systems etc.Can it be divided into HOPP (PP-H), block copolymerization polypropylene (PP-B) and atactic copolymerized polypropene (PP-R) according to different PP polymerization process conditions.Because PP-H tubing fragility has at low temperatures limited its use, is replaced by PP-B tubing, PP-R tubing gradually in some applications.Wherein the PP-B pipe is mainly used in chilled water system, ground heating system, and the application of PP-R pipe is then more extensive.PP-B, PP-R tubing also have following characteristic except having general plastic tube characteristics: good sanitation performance is heat-resisting, energy-conservation; Easy for installation, connect reliable; Raw material is recyclable, and equipment requirements is simple, production technology is easy to be easy to control, and pipeline is laid arbitrarily.
On the one hand, the creep resisting ability of polypropylene pipe, low-temperature flexibility are relatively poor.When temperature is reduced to 32 ℃, can also keep moderate impact strength, and when temperature was reduced to-4 ℃, toughness was just limited.
On the other hand, early 1980s, American-European technician finds that in the hot water cyclesystem of using plastic pipe, the metal parts in the equipment corrodes easily, causes equipment to damage fast.Nineteen eighty-two, the expert reaches a conclusion: after the tubing heating, oxygen molecule sees through plastic layer more easily, and is deep in the water in the pipe, causes the quick corrosion of metal parts in the equipment.Developed resistance oxygen pipe therefrom.The America and Europe, the utilization rate to 70% of resistance oxygen pipeline in the heating system, through the practical experience of recent two decades, the metal parts life-span in the resistance oxygen pipe-line system can prolong 10-20.
Therefore keep polypropylene pipe original excellent performance; Improve its toughness deficiency, thermal insulation property, resistance oxygen mold resistance and resistance solvent penetrability; Improve its impact resistance, splitting resistance, prolongation system working life, intercept oxygen and solvent penetrates in the tubing; Just having become one of problem of polypropylene pipe innovation and development, also is to break through the circumscribed key of polypropylene pipe.
At present, the main direction of polypropylene pipe technological innovation is in the world: through the technological innovation of material, MULTILAYER COMPOSITE and processing technology, produce better than conventional polypropylene tube performance, have the pipe-line system of insulation, antibiotic, the high tenacity of resistance oxygen and high tenacity concurrently.Main mode has physical blending modification and chemical copolymerization modification.The modification of resistance oxygen is mainly the interpolation barrier resins and carries out multi-layer co-extruded.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing technology; Provide a kind of insulation resistance oxygen antibiotic high impact resistance polypropylene tubing; Adopt multi-layer compound structure, problems such as the low temperature brittleness of solution polypropylene pipe, resistance oxygen antibiotic property, corrosion resistance, ageing resistance, heat resistance, processability, heat preservation energy-saving.
The present invention is achieved in that the antibiotic high impact resistance polypropylene tubing of a kind of insulation resistance oxygen, adopts multi-layer co-extruded method to process, and described tube wall is five layers of composite structure; Ecto-entad is followed successively by: surperficial oxidation prevention layer, core layer foaming thermal insulation layer, sandwich layer oxidation prevention layer; Glass fiber reinforced layer, antibiotic layer.
Said surperficial oxidation prevention layer and sandwich layer oxidation prevention layer use acrylic resin PP, ethylene-vinyl alcohol copolymer EVOH, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC comprehensively modifying to form, and each constituent mass component is:
Figure BSA00000619629800021
Said core layer foaming thermal insulation layer uses acrylic resin PP, the agent of polypropylene special-purpose foaming, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC comprehensively modifying to form, and each constituent mass part is:
Figure BSA00000619629800022
Said glass enhancement layer uses 30% fiber glass reinforced polypropylene resin, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC to form as the main raw material comprehensively modifying, and each constituent mass part is:
Figure BSA00000619629800031
Said antibiotic layer uses acrylic resin PP, nano-antibacterial master batch, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC to form as the main raw material comprehensively modifying, and each constituent mass component is:
Figure BSA00000619629800032
A kind of method of making the antibiotic high impact resistance polypropylene tubing of above-mentioned insulation resistance oxygen; Be by the described material rate of each layer formula requirement; Adding each layer material mixer after weighing respectively stirred 10-15 minute; Respectively each layer mixture added the extruder granulation, make each layer pellet, each layer pellet added co-extrusion extruder drying, multi-layer co-extruded Vacuum shaping, coding, cutting, check, packing, warehouse-in; Extrusion temperature is: feed zone is 150-180 ℃, and the compressing section is 190-200 ℃, and fluxing zone is 200-210 ℃, and homogenizing zone is 200-220 ℃, and die temperature is 190-210 ℃, cooling water temperature 15-20 ℃; The cooling and shaping vacuum is 0.4MPa.
Used the PP resin among the present invention, its abundant raw material, it is good to have excellent mechanical property, corrosion-resistant, anti-ageing chemical combination pliability, and energy-conservation, hygienic environment-protecting, can be widely used in multiple field.
Used ethylene-vinyl alcohol copolymer (EVOH) among the present invention; Be import high barrier EVOH resin; Have excellent mechanical strength, surface hardness, gas barrier property, organic solvent resistance, its processability and weatherability and radiation hardness ability are good, and stronger antistatic behaviour is arranged; This non-toxic, pollution-free is prone to advantages such as reclaiming and modification simultaneously.Improve mechanical property, resistance oxygen gas barrier properties, aging quality resistance, the decay resistance of tubing.
Used ethylene-alpha-octylene block copolymer (OBC) among the present invention; Thermoplastic olefin based block copolymer for the exploitation of U.S. Dow chemical company; Show the new type polyolefin elastomer of applications well prospect in the automotive applications field, not only can be used as pure resin use but also can be used as the impact modifying agent use, compare with traditional metallocene polyolefin elastomers; OBC has about 120 ℃ of high fusing point; Its glass transition temperature is similar to ethylene atactic copolymer, and OBC has the wearability that low compressive deformation is become reconciled simultaneously, because its shear flow sex change and melt strength and random copolymer are similar; Therefore, OBC can adopt the processing method of random copolymer to carry out shaping operation.Have excellent ageing-resistant, ultraviolet resistance, good mechanical performance and processing rheological property;, price performance advantages of higher outstanding with good, the high low-temperature flexibility of polyolefin compatibility; Make that it is effective at polyolefinic toughening modifying, be widely used, efficiently solve toughness, the receptance of tubing, the problem of ageing resistance difference.
Used maleic anhydride inoculated polypropylene nucleator (PP-g-MAH) among the present invention; Be self-control co-mixing system nucleator; Be a kind of new function additive, improve the co-mixing system compatibility, see through the crystallization behavior that changes resin; Accelerate crystalline rate, increase crystal density and impel the crystallite dimension imperceptibility, reach combination properties such as shortening molding cycle, the raising tubing transparency, lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance.
Used the nano-antibacterial master batch among the present invention; Selecting high-quality PP raw material for use is carrier; The mother particles of antibacterial plastics that cooperates advanced dispersion technology and be prepared into manufacturing process adopts advanced nanometer preparation technology, and silver is coated on carrier surface or is adsorbed in the carrier; Silver ion is slowly discharged, thus obtain lasting, efficient, safe antibiotic.
The invention has the beneficial effects as follows: with existing polypropylene pipe, the present invention has excellent mechanical property, decay resistance, aging quality resistance, resistance oxygen mold resistance, processibility, thermal characteristics, good heat insulating; Degree of finish is good, and cost performance is high, and water does not flow for a long time and undergoes no deterioration yet; Suppress the generation of bacterium, prevent the infiltration of solvent, withstand voltage safety; Long service life, the energy-saving clean environmental protection.The present invention is incubated resistance oxygen antibiotic high impact resistance polypropylene tubing can be widely used in fields such as municipal administration and building water supply, heating air feed, electric power, communication, industry, agricultural, and purposes very extensively.
Description of drawings
Accompanying drawing is a cross-sectional structure schematic representation of the present invention.
Among the figure: 1, surperficial oxidation prevention layer, 2, the core layer foaming thermal insulation layer, 3, the sandwich layer oxidation prevention layer, 4-glass enhancement layer, 5, antibiotic layer.
Embodiment
Raw material
Surface oxidation prevention layer and sandwich layer: 80 parts of polypropylene PP, 50 parts of ethylene-vinyl alcohol copolymer EVOH, 14 parts of ethylene-alpha-octylene block copolymer OBC, 1.5 parts of maleic anhydride inoculated polypropylene PP-g-MAH, look female 2-3 part.
Insulating foam layer: 100 parts of polypropylene PP, 2.0 parts of polypropylene special-purpose foaming agent, 15 parts of ethylene-alpha-octylene block copolymer OBC, 1.5 parts of maleic anhydride inoculated polypropylenes (PP-g-MAH).
Glass enhancement layer: 100 parts of 30% fiber glass reinforced polypropylene resins, ethylene-alpha-octylene block copolymer OBC15 part, 1.5 parts of maleic anhydride grafted polypropylene PP-g-MAH, 2 parts of looks female.
Antibiotic layer: 80 parts of polypropylene PP, 30 parts of nano-antibacterial master batches, 15 parts of ethylene-alpha-octylene block copolymer OBC, 1.2 parts of maleic anhydride inoculated polypropylene PP-g-MAH, 2 parts of looks female.
By the described material rate of each layer formula requirement; Adding each layer material mixer after weighing respectively stirred 10-15 minute; Respectively each layer mixture added the extruder granulation; Make each layer pellet, each layer pellet added co-extrusion extruder drying, multi-layer co-extruded Vacuum shaping, coding, cutting, check, packing, warehouse-in; Extrusion temperature is: feed zone is 160 ℃, and the compressing section is 200 ℃, and fluxing zone is 200 ℃, and homogenizing zone is 220 ℃, and die temperature is 200 ℃, 15 ℃ of cooling water temperatures; The cooling and shaping vacuum is 0.4MPa.
The appearance pipe is through detecting, and tensile yield pressure is 48MPa, and 0 ℃ of charpy impact test damage percentage is that 0,40 ℃ of oxygen transmission rate is 0.02g/ (m 3.d); Antibacterium rate 99.8%, vertical relaxation shrinkage 0.8%, melt mass flow rate variance ratio 18%; Heat stabilization test ne-leakage, crack-free under hydrostatic test and the hydrostatic state, tubing meet " the safety evaluatio standard of Drinking Water transmission & distribution wetting system and protection material ".

Claims (6)

1. the antibiotic high impact resistance polypropylene tubing of insulation resistance oxygen adopts multi-layer co-extruded method to process, and it is characterized in that; Described tube wall is five layers of composite structure; Ecto-entad is followed successively by: surperficial oxidation prevention layer (1), core layer foaming thermal insulation layer (2), sandwich layer oxidation prevention layer (3); Glass fiber reinforced layer (4), antibiotic layer (5).
2. by the antibiotic high impact resistance polypropylene tubing of the described insulation resistance oxygen of claim 1; It is characterized in that surperficial oxidation prevention layer and sandwich layer oxidation prevention layer use acrylic resin PP, ethylene-vinyl alcohol copolymer EVOH, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC comprehensively modifying to form, each constituent mass component is:
Figure FSA00000619629700011
3. by the antibiotic high impact resistance polypropylene tubing of the described insulation resistance oxygen of claim 1; It is characterized in that the core layer foaming thermal insulation layer uses acrylic resin PP, the agent of polypropylene special-purpose foaming, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC comprehensively modifying to form, each constituent mass part is:
Figure FSA00000619629700012
4. by the antibiotic high impact resistance polypropylene tubing of the described insulation resistance oxygen of claim 1; It is characterized in that the glass enhancement layer uses 30% fiber glass reinforced polypropylene resin, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC to form as the main raw material comprehensively modifying, each constituent mass part is:
Figure FSA00000619629700013
Figure FSA00000619629700021
5. by the antibiotic high impact resistance polypropylene tubing of the described insulation resistance oxygen of claim 1; It is characterized in that antibiotic layer uses acrylic resin PP, nano-antibacterial master batch, maleic anhydride inoculated polypropylene nucleator PP-g-MAH, novel polypropylene toughening agent ethylene-alpha-octylene block copolymer OBC to form as the main raw material comprehensively modifying, each constituent mass component is:
6. method of making claim 1 or the antibiotic high impact resistance polypropylene tubing of 2 or 3 or 4 or 5 described insulations resistance oxygen; It is characterized in that; Be by the described material rate of each layer formula requirement, add each layer material mixer after weighing respectively and stirred 10-15 minute, respectively each layer mixture added the extruder granulation; Make each layer pellet, each layer pellet added co-extrusion extruder drying, multi-layer co-extruded Vacuum shaping, coding, cutting, check, packing, warehouse-in; Extrusion temperature is: feed zone is 150-180 ℃, and the compressing section is 190-200 ℃, and fluxing zone is 200-210 ℃, and homogenizing zone is 200-220 ℃, and die temperature is 190-210 ℃, cooling water temperature 15-20 ℃; The cooling and shaping vacuum is 0.4MPa.
CN2011103769996A 2011-11-19 2011-11-19 Heat-insulation oxygen-blocking antibacterial high impact polypropylene tube and manufacturing method thereof Pending CN102506241A (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN104154344A (en) * 2013-05-13 2014-11-19 上海蓝翎管业科技有限公司 Compound EVOH-type PPR pipe and manufacturing process and manufacturing equipment thereof
CN107215007A (en) * 2017-06-26 2017-09-29 宁波波尔管业开发有限公司 High-strength polypropylene conduit and preparation method thereof
CN108424575A (en) * 2017-02-14 2018-08-21 万宁 A kind of method for toughening of PP materials
CN110408128A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of wear-resisting PPR pipe and its production method
CN110406065A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of β-PPR pipe and its processing method
CN110408127A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof
CN114714674A (en) * 2022-04-22 2022-07-08 安徽源锂高新材料有限公司 Reinforced three-layer corrugated structure RFOBC pipe and preparation method thereof
CN115403844A (en) * 2022-06-07 2022-11-29 浙江中财型材有限责任公司 Impact-resistant ultrahigh oxygen-resistant antibacterial pipe and preparation method thereof

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CN201795181U (en) * 2010-03-18 2011-04-13 上海天净管业有限公司 Nano antibiotic antioxidant pipe
CN202338702U (en) * 2011-11-19 2012-07-18 江苏百安居管业有限公司 Thermal insulation and oxidation prevention antibiotic HIPP (high impact polypropylene) pipe

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JP2001173846A (en) * 1999-12-22 2001-06-29 Sekisui Chem Co Ltd Synthetic resin pipe
US20100218839A1 (en) * 2009-02-27 2010-09-02 Flexpipe Systems Inc. High temperature fiber reinfoced pipe
CN201795181U (en) * 2010-03-18 2011-04-13 上海天净管业有限公司 Nano antibiotic antioxidant pipe
CN102002191A (en) * 2010-11-02 2011-04-06 徐州百安居建材科技有限公司 PPR/EVOH/POE (Pentatricopeptide Repeats/Ethylene-Vinyl Alcohol/Polyolefin Elastomer) blending high-impact barrier pipe and manufacturing method thereof
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104154344A (en) * 2013-05-13 2014-11-19 上海蓝翎管业科技有限公司 Compound EVOH-type PPR pipe and manufacturing process and manufacturing equipment thereof
CN108424575A (en) * 2017-02-14 2018-08-21 万宁 A kind of method for toughening of PP materials
CN107215007A (en) * 2017-06-26 2017-09-29 宁波波尔管业开发有限公司 High-strength polypropylene conduit and preparation method thereof
CN107215007B (en) * 2017-06-26 2019-06-18 宁波波尔管业开发有限公司 High-strength polypropylene conduit and preparation method thereof
CN110408127A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof
CN110406065A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of β-PPR pipe and its processing method
CN110408128A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of wear-resisting PPR pipe and its production method
CN110406065B (en) * 2018-04-28 2023-10-20 上海伟星新型建材有限公司 beta-PPR pipe and processing method thereof
CN110408128B (en) * 2018-04-28 2023-10-24 上海伟星新型建材有限公司 Wear-resistant PPR pipe and production method thereof
CN114714674A (en) * 2022-04-22 2022-07-08 安徽源锂高新材料有限公司 Reinforced three-layer corrugated structure RFOBC pipe and preparation method thereof
CN114714674B (en) * 2022-04-22 2023-09-12 安徽源锂高新材料有限公司 Enhanced three-layer corrugated structure pipe and preparation method thereof
CN115403844A (en) * 2022-06-07 2022-11-29 浙江中财型材有限责任公司 Impact-resistant ultrahigh oxygen-resistant antibacterial pipe and preparation method thereof
CN115403844B (en) * 2022-06-07 2023-08-22 浙江中财型材有限责任公司 Impact-resistant ultrahigh-oxygen-resistant antibacterial pipe and preparation method thereof

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Application publication date: 20120620