CN102617911A - Reclaimed high-density polyethylene/polypropylene composite material prepared through reaction extruding - Google Patents

Reclaimed high-density polyethylene/polypropylene composite material prepared through reaction extruding Download PDF

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Publication number
CN102617911A
CN102617911A CN2012100801918A CN201210080191A CN102617911A CN 102617911 A CN102617911 A CN 102617911A CN 2012100801918 A CN2012100801918 A CN 2012100801918A CN 201210080191 A CN201210080191 A CN 201210080191A CN 102617911 A CN102617911 A CN 102617911A
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China
Prior art keywords
hdpe
density polyethylene
high density
composite material
reaction
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Pending
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CN2012100801918A
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Chinese (zh)
Inventor
许海燕
顾嘉琦
吴驰飞
彭龙泉
陈甜斌
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East China University of Science and Technology
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East China University of Science and Technology
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Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN2012100801918A priority Critical patent/CN102617911A/en
Publication of CN102617911A publication Critical patent/CN102617911A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention relates to an HDPE (High-Density Polyethylene) /PP (Propene Polymer) composite material, which is prepared from a reclaimed material through reaction extruding. A preparation method for the HDPE/PP composite material comprises the following steps of: drying a reclaimed HDPE material (the content of PP is 5-30 percent); adding the reclaimed material, a crosslinking agent and an assistant crosslinking agent in the ratio of (97.5-99.85):(0.05-0.5):(0.1-2) into a high-speed mixing machine for mixing; adding into the feeding hole of a dual screw extruder; extruding at the rotating speed of 120-300 rpm at the temperature of 140-210 DEG C; and cutting with a granulator to obtain particles. In the method, the assistant crosslinking agent is added into a system for preparing a pipeline by crosslinking reclaimed HDPE, so that the degrading reaction of PP in the presence of a peroxide is restrained, the melt index of the material is lowered, the compatibility of HDPE and PP is improved, a material suitable for extruding a tubular product is obtained, and the mechanical performance of the material is improved.

Description

Recovery high density polyethylene(HDPE)/the PP composite material of preparation is extruded in reaction
Technical field
The present invention relates to a kind of reclaimed materials that utilizes and extrude the HDPE/PP matrix material of preparation, belong to the modification field of reclaiming polymer composite through reaction.
Background technology
Recovery for the HDPE goods can solve white pollution problems to a certain extent, alleviates the pressure of plastic refuse to environment.On the other hand, along with the develop rapidly of city-building, the demand of HDPE tubing increases rapidly, and this has also aggravated expending for petroleum resources.If can the HDPE that reclaim be used to produce tubing, can become " giving up " on the one hand into precious, practice thrift cost, can alleviate the dual-pressure of the environment and the energy on the other hand greatly.The research that utilizes recovery HDPE to prepare special material for tube has report at patent CN101805472A.
Yet, often contain little P P among the HDPE of recovery.When reclaimed materials was carried out the peroxide crosslinking modification, the PP molecular chain ruptured easily, made the melting index of system rise, and was unfavorable for extruding of tubing.On the other hand, the introducing of PP is prone to make the material embrittlement, makes the mechanical property, particularly shock strength of material and elongation at break descend.Bibliographical information is arranged, add additional crosslinker in the PP cross-linking process, can reduce its melting index, improve its mechanical property simultaneously.The present invention considers in the cross-linking modified process of reclaimed materials, to add additional crosslinker, can make PP in the system that degraded does not take place on the one hand and takes place crosslinkedly, reduces the melting index of material; On the other hand, owing in cross-linking process, suppressed the further degraded of PP, make the PP radical to combine with the radical of PE; Form the PE-g-PP graft copolymer; Improve both consistencies, improve the mechanical property of blend, thereby obtain to meet the tube material of performance requriements.
Patent CN101863091A reports the recovery of HDPE and PP wrapping material, in the report depleted Plastic Packaging Materials is recycled, and granulation has again realized the resource circulation utilization.Mainly concentrate on radiation crosslinking (CN1142514) and crosslinked with silicane (CN101158423) about the crosslinked patent report of PP, through crosslinked acquisition mechanical property and the excellent material of resistance to elevated temperatures.The HDPE that also has patent report (CN101805472A) utilization to reclaim carries out cross-linking modified preparation special material for tube.But at present also not about how the recovery HDPE that contains PP when cross-linking modified, is being overcome the report of the existence of PP to crosslinking reaction and final Effect on Performance.
Summary of the invention
The objective of the invention is to solve recovery HDPE adopts the peroxide crosslinking modification to reduce its melting index, improve its performance, widen in the process of its range of application; Cause that owing to containing PP in the raw material melting index rises, the problem of degradation; Proposition adds additional crosslinker in cross-linking system; The melting index of improvement system and mechanical property, thus range of application material more widely obtained.
The present invention realizes through following technical scheme.
Recovery high density polyethylene(HDPE)/the PP composite material of preparation is extruded in a kind of reaction, it is characterized in that, described recovery high density polyethylene(HDPE)/PP composite material prepares through following steps:
The HDPE that contains 5～30%PP that (1) will reclaim carries out drying as reclaimed materials; By following ratio of weight and number; Reclaimed materials: linking agent: additional crosslinker=(97.5～99.85): (0.05～0.5): prepare burden (0.1～2), and the adding high-speed mixer of will preparing burden then mixes; The drying of reclaimed materials is selected 80 ℃ of dry 4h down, and the mixed at high speed time is 10min;
(2) material that mixes that step (1) is obtained adds in the charging opening of twin screw extruder;
(3) utilize twin screw extruder to extrude, the temperature of forcing machine is set to 140～210 ℃, and extruded velocity is 120～300rpm, successively through tank cooling, hair dryer dry up, the dicing machine cutting obtains required crosslinked HDPE/PP matrix material;
Wherein, HDPE: ρ=0.94g/cm 3, M n=21000, M w=228000; PP: ρ=0.91g/cm 3, M n=44000, M w=188000,
Said linking agent adopts one or more in superoxide, vinylsiloxane, the allyl group silica,
Described additional crosslinker adopts the allylic additional crosslinker.
As preferably, described linking agent adopts Di Cumyl Peroxide 99 or Lucidol.
As preferably, described additional crosslinker adopts triallyl cyanurate or iso-cyanuric acid triallyl ester.
As preferably, described recovery HDPE chooses the reclaimed materials that contains 5%PP.
Beneficial effect
The present invention is through adding additional crosslinker in the system of utilizing the crosslinked preparation tubing of HDPE reclaimed materials; Overcome the PP in the reclaimed materials and caused the problem that melting index rises and mechanical property descends; Thereby obtained the material that suitable tubing is extruded; And improved the mechanical property of material, accomplished that really it is precious that change " is given up ", has also alleviated the pressure to petroleum-based energy when alleviating environmental stress.
The advantage of this patent will describe through specific examples.
Embodiment
Embodiment 1:
By following set of dispense material: reclaimed materials (come from beverage bottle cap, wherein PP content is 5%): Di Cumyl Peroxide 99 (DCP): iso-cyanuric acid triallyl ester (TAIC)=100: 0.25: 0.5.
Reclaimed materials, DCP and TAIC are at room temperature prepared to extrude with high-speed mixer joins twin screw extruder after mixing 10min under the rotating speed of 500rpm charging opening.
Rotating speed with 150rpm is extruded compound, each of forcing machine section temperature setting: first section 140 ℃, and second section 160 ℃, the 3rd section 170 ℃, the 4th section 180 ℃, the 5th section 200 ℃, the 6th section 210 ℃, the 7th section 210 ℃, 200 ℃ of heads.
The performance that adds additional crosslinker front and back material in this instance is relatively seen table 1.
Table 1
Performance Do not contain the additional crosslinker system Add the additional crosslinker system
Elongation at break (%) 464±10 890±15
Tensile strength (MPa) 20±0.5 23.5±0.7
Notched Izod impact strength (KJ/m 2) 25±0.5 38±0.8
Flexural strength (MPa) 18±0.4 23.7±0.5
Modulus in flexure (MPa) 400±9.8 500±12.1
Density (g/m 3) 0.95 0.96
Melting index (g/10min) 1.3 0.7
Embodiment two:
By following set of dispense material: reclaimed materials (come from beverage bottle cap, wherein PP content 5%): DCP: TAIC=100: 0.25: 1.
Reclaimed materials, DCP and TAIC are at room temperature prepared to extrude with high-speed mixer joins twin screw extruder after mixing 10min under the rotating speed of 500rpm charging opening.
Rotating speed with 150rpm is extruded compound, each of forcing machine section temperature setting: first section 140 ℃, and second section 160 ℃, the 3rd section 170 ℃, the 4th section 180 ℃, the 5th section 200 ℃, the 6th section 210 ℃, the 7th section 210 ℃, 200 ℃ of heads.
The performance that adds additional crosslinker front and back material in this instance is relatively seen table 2.
Table 2
Performance Do not contain the additional crosslinker system Add the additional crosslinker system
Elongation at break (%) 464±10 1068±15
Tensile strength (MPa) 20±0.5 24±0.7
Notched Izod impact strength (KJ/m 2) 25±0.5 42±1.2
Flexural strength (MPa) 18±0.4 25±0.6
Modulus in flexure (MPa) 400±9.8 600±11.2
Density (g/m 3) 0.95 0.97
Melting index (g/10min) 1.3 0.5
Embodiment three:
By following set of dispense material: reclaimed materials (come from beverage bottle cap, wherein PP content 5%): Lucidol (BPO): TAIC=100: 0.: 25: 0.5.
Reclaimed materials, BPO and TAIC are at room temperature prepared to extrude with high-speed mixer joins twin screw extruder after mixing 10min under the rotating speed of 500rpm charging opening.
Rotating speed with 150rpm is extruded compound, each of forcing machine section temperature setting: first section 140 ℃, and second section 160 ℃, the 3rd section 170 ℃, the 4th section 180 ℃, the 5th section 200 ℃, the 6th section 210 ℃, the 7th section 210 ℃, 200 ℃ of heads.
The performance that adds additional crosslinker front and back material in this instance is relatively seen table 3.
Table 3
Performance Do not contain the additional crosslinker system Add the additional crosslinker system
Elongation at break (%) 500±11 1000±12.5
Tensile strength (MPa) 21.2±0.5 24.5±0.6
Notched Izod impact strength (KJ/m 2) 27±0.6 40±0.9
Flexural strength (MPa) 19±0.4 24±0.5
Modulus in flexure (MPa) 450±10 550±11.3
Density (g/m 3) 0.96 0.97
Melting index (g/10min) 1.0 0.62
Embodiment four:
By following set of dispense material: reclaimed materials (come from beverage bottle cap, wherein PP content 10%): DCP: triallyl cyanurate (TAC)=100: 0.25: 0.5.
Reclaimed materials, DCP and TAC are at room temperature prepared to extrude with high-speed mixer joins twin screw extruder after mixing 10min under the rotating speed of 500rpm charging opening.
Rotating speed with 150rpm is extruded compound, each of forcing machine section temperature setting: first section 140 ℃, and second section 160 ℃, the 3rd section 170 ℃, the 4th section 180 ℃, the 5th section 200 ℃, the 6th section 210 ℃, the 7th section 210 ℃, 200 ℃ of heads.
The performance that adds additional crosslinker front and back material in this instance is relatively seen table 4.
Table 4
Performance Do not contain the additional crosslinker system Add the additional crosslinker system
Elongation at break (%) 442±10 910±12
Tensile strength (MPa) 18±0.5 23.7±0.6
Notched Izod impact strength (KJ/m 2) 23±0.5 41±0.9
Flexural strength (MPa) 16±0.4 24.3±0.5
Modulus in flexure (MPa) 380±9.6 610±10.2
Density (g/m 3) 0.95 0.97
Melting index (g/10min) 1.4 0.6
From above embodiment, can find out; In the system of peroxide modified recovery bottle cap material, add additional crosslinker; Not only reduce the melting index of system, helped the processing of extruding of tube material, also improved the mechanical property of material; Especially significantly improved the toughness of material, thus the excellent material of obtained performance.

Claims (4)

1. the recovery high density polyethylene(HDPE)/PP composite material of preparation is extruded in a reaction, it is characterized in that described recovery high density polyethylene(HDPE)/PP composite material prepares through following steps:
5～30% polyacrylic high density polyethylene(HDPE)s that contain that (1) will reclaim carry out drying as reclaimed materials; By following ratio of weight and number; Reclaimed materials: linking agent: additional crosslinker=(97.5～99.85): (0.05～0.5): prepare burden (0.1～2), and the adding high-speed mixer of will preparing burden then mixes; The drying of reclaimed materials is selected 80 ℃ of dry 4h down, and the mixed at high speed time is 10min;
(2) material that mixes that step (1) is obtained adds in the charging opening of twin screw extruder;
(3) utilize twin screw extruder to extrude; The temperature of forcing machine is set to 140～210 ℃; Extruded velocity is 120～300rpm, successively through tank cooling, hair dryer dry up, the dicing machine cutting obtains required crosslinked high density polyethylene(HDPE)/PP composite material;
Wherein, high density polyethylene(HDPE): ρ=0.94g/cm 3, M n=21000, M w=228000; Vestolen PP 7052: ρ=0.91g/cm 3, M n=44000, M w=188000,
Said linking agent is to be selected from superoxide, vinylsiloxane, the allyl group silica one or more,
Described additional crosslinker is the allylic additional crosslinker.
2. the recovery high density polyethylene(HDPE)/PP composite material of preparation is extruded in reaction as claimed in claim 1, it is characterized in that, described linking agent adopts Di Cumyl Peroxide 99 or Lucidol.
3. the recovery high density polyethylene(HDPE)/PP composite material of preparation is extruded in reaction as claimed in claim 1, it is characterized in that, described additional crosslinker adopts triallyl cyanurate or iso-cyanuric acid triallyl ester.
4. the recovery high density polyethylene(HDPE)/PP composite material of preparation is extruded in reaction as claimed in claim 1, it is characterized in that, described reclaimed materials is for containing 5% polyacrylic high density polyethylene(HDPE) reclaimed materials.
CN2012100801918A 2012-03-22 2012-03-22 Reclaimed high-density polyethylene/polypropylene composite material prepared through reaction extruding Pending CN102617911A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102936362A (en) * 2012-10-22 2013-02-20 沈阳化工大学 RHDPE particles used in pipe material, and preparation method thereof
CN103709479A (en) * 2013-12-18 2014-04-09 江苏标榜装饰新材料股份有限公司 Aluminum-plastic composite panel with high rigidity and high bending strength and preparation method of aluminum-plastic composite panel
CN108285512A (en) * 2018-02-02 2018-07-17 上海阳越新材料科技有限公司 A kind of toughening enhancing recycle polyethylene/PP composite material and preparation method thereof
CN110776687A (en) * 2019-11-14 2020-02-11 广讯检测（广东）有限公司 PE melt index adjusting master batch and preparation method thereof
CN112280065A (en) * 2020-11-17 2021-01-29 中国葛洲坝集团绿园科技有限公司 Polyethylene reclaimed material, preparation method thereof and solid-wall pipe
CN114621509A (en) * 2021-10-20 2022-06-14 东莞市国亨塑胶科技有限公司 Marine-recovered polyethylene regeneration preparation method

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CN101805472A (en) * 2010-04-20 2010-08-18 湖州环友橡塑材料有限公司 Regeneration high-density polyethylene (HDPE) particle used for tubings and manufacture method thereof
CN102276892A (en) * 2011-05-24 2011-12-14 华东理工大学 Method for preparing polyethylene pipe resin

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CN101121799A (en) * 2006-08-11 2008-02-13 广州市波斯塑胶颜料有限公司 Low-luster polypropylene blending modified material and preparation method thereof
CN101805472A (en) * 2010-04-20 2010-08-18 湖州环友橡塑材料有限公司 Regeneration high-density polyethylene (HDPE) particle used for tubings and manufacture method thereof
CN102276892A (en) * 2011-05-24 2011-12-14 华东理工大学 Method for preparing polyethylene pipe resin

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102936362A (en) * 2012-10-22 2013-02-20 沈阳化工大学 RHDPE particles used in pipe material, and preparation method thereof
CN103709479A (en) * 2013-12-18 2014-04-09 江苏标榜装饰新材料股份有限公司 Aluminum-plastic composite panel with high rigidity and high bending strength and preparation method of aluminum-plastic composite panel
CN103709479B (en) * 2013-12-18 2016-03-09 江苏标榜装饰新材料股份有限公司 Aluminum-plastic composite board of a kind of high rigidity and high bending strength and preparation method thereof
CN108285512A (en) * 2018-02-02 2018-07-17 上海阳越新材料科技有限公司 A kind of toughening enhancing recycle polyethylene/PP composite material and preparation method thereof
CN110776687A (en) * 2019-11-14 2020-02-11 广讯检测（广东）有限公司 PE melt index adjusting master batch and preparation method thereof
CN110776687B (en) * 2019-11-14 2022-05-17 广讯检测（广东）有限公司 PE melt index adjusting master batch and preparation method thereof
CN112280065A (en) * 2020-11-17 2021-01-29 中国葛洲坝集团绿园科技有限公司 Polyethylene reclaimed material, preparation method thereof and solid-wall pipe
CN112280065B (en) * 2020-11-17 2023-03-10 中国葛洲坝集团绿园科技有限公司 Polyethylene reclaimed material, preparation method thereof and solid-wall pipe
CN114621509A (en) * 2021-10-20 2022-06-14 东莞市国亨塑胶科技有限公司 Marine-recovered polyethylene regeneration preparation method
CN114621509B (en) * 2021-10-20 2024-03-12 东莞市国亨塑胶科技有限公司 Polyethylene regeneration preparation method for ocean recovery

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Application publication date: 20120801