CN102643476B - Polyethylene mixing material for easily-stripped electrolytic cathode plate sealing strip and preparation method thereof - Google Patents

Polyethylene mixing material for easily-stripped electrolytic cathode plate sealing strip and preparation method thereof Download PDF

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Publication number
CN102643476B
CN102643476B CN201210139339.0A CN201210139339A CN102643476B CN 102643476 B CN102643476 B CN 102643476B CN 201210139339 A CN201210139339 A CN 201210139339A CN 102643476 B CN102643476 B CN 102643476B
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China
Prior art keywords
negative plate
mixing material
sealed strip
polyethylene
plate sealed
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Expired - Fee Related
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CN201210139339.0A
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CN102643476A (en
Inventor
滕谋勇
邓爱霞
赵笛
葛祥才
谢倩
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Liaocheng University
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Liaocheng University
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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
    • B29C48/03—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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • 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
    • B29C2948/92904—Die; Nozzle zone

Abstract

The invention provides a polyethylene mixing material for an easily-stripped electrolytic cathode plate sealing strip and a preparation method thereof, which belong to the technical field of plastic processing and application and the technical field of wet electrolysis of metal including copper and the like. The polyethylene mixing material for producing the electrolytic cathode plate sealing strip comprises, by weight: 100 parts of polyethylene resin, 0.1-20 parts of linear low-density polyethylene resin, 0.1-10 parts of functional polymers, 0.1-1 part of antioxygen, 0.05-1 part of metal deactivator, 0.1-5 parts of flow modifiers and appropriate parts of colorants. The sealing strip prepared by the mixing material has the advantage of being easy to strip.

Description

Easily peel off polyethylene mixing material and preparation method thereof for electrolytic negative plate sealed strip
Technical field
The present invention relates to a kind of polyethylene mixing material and preparation method for electrolytic negative plate sealed strip that easily peel off, have the advantages that adhesive property is good and easily peel off, belong to the wet method electrolysis technical field of the metals such as plastics processing and application technology and copper.
Background technology
At present, suitability for industrialized production high purity copper, manganese, zinc mainly adopt the method for electrolysis.Wherein, important production parts are negative plate, by electrode, introduce negative charge, and bivalent cupric ion or mn ion, zine ion reduce and form copper, manganese, zinc on negative plate, then by the unit of delaminating, cathode copper are peeled, and form highly purified metal.Negative plate mainly adopts stainless steel or titanium to make, and for reaching the object of insulation, shape of product rule, on the both sides of negative plate, need to add one deck insulated enclosure bar.
The production method of sealed strip has two kinds: 1) by forcing machine, polyethylene melting directly extruded and is attached on negative plate, and then cooling; 2) first produce insulated enclosure bar, be then set on negative plate.By first method, produce insulated enclosure bar, there is the shortcoming poor with metal polar plate viscosifying power in the polythene material that manufacturer is used at present, simultaneously due to electrolyte temperature in electrolyzer higher (electrolytic copper temperature is generally at 65 ℃), material is subject to thermo-oxidative ageing, in addition in electrolytic solution, exist and contain transition metal, degradation process is accelerated, and the sealed strip life-span of producing is in this way generally about 3 months.After insulated enclosure bar is aging, cause the electrolytic copper of producing to occur deformity, the problem such as knob, end face be uneven as occurred, affects production marketing.While reusing, first sealed strip is peeled from negative plate, then to the polishing of sealed strip place, again melt extrude moulding, this has increased labour intensity greatly, and production efficiency is not high yet.The sealed strip of producing by second method can be with reference to Granted publication CN 201169646Y(application number 200820096325.4) structure of " the sealed insulation contained side bar of electrolytic negative plate ", the sealed strip of this structure is comprised of sealed insulation bar contained side and tensioning rod, under the effect of tensioning rod, sealed edge is clamped to negative plate.Yet because macromolecular material has creep properties, especially when middle electrolyte temperature is higher, be more prone to occur creep, make the insulated enclosure bar of said structure occur not clamping phenomenon, have to coat seal gum in the junction of sealed strip and negative plate, this has not only increased cost, simultaneously due to seal gum and the bounding force of sealed strip own not strong, also easily make electrolytic solution penetrate on the negative plate of sealed strip sealing place, make metallic reducing at sealed strip place, while peeling off, under the effect of mechanical force, sealed strip is accelerated to be destroyed.
As can be seen here, more there is the defect that toughness is low, be difficult for peeling off in existing sealed strip.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of electrolytic negative plate sealed strip with easily peeling off polyethylene composition, by extrusion by melting, produce sealed strip, use High molecular weight polyethylene resin, be aided with linear low density polyethylene resin simultaneously and improve its toughness, add functional polymer to increase the bounding force that constituent has solved constituent and negative plate, add metal passivator that its life-span is increased substantially, add flow ability modifying agent to improve the processing characteristics of constituent.
The scheme solving the problems of the technologies described above is: easily peel off electrolytic negative plate sealed strip polyethylene mixing material, unit meter contains 100 parts of polyvinyl resins by weight, linear low density polyethylene resin 0.1-20 part, functional polymer 0.1-10 part, metal passivator 0.05-1 part, flow ability modifying agent 0.1-5 part, amount of colorant.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: unit meter contains 100 parts of polyvinyl resins by weight, linear low density polyethylene resin 5-15 part, functional polymer 2-6 part, metal passivator 0.06-0.08 part, flow ability modifying agent 1-3 part, amount of colorant.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: described polyvinyl resin is multipolymer, and comonomer is alpha-olefin, its density>=0.940g/cm 3, melt flow rate (MFR)≤1.0g/10min.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: described linear low density polyethylene resin is multipolymer, and comonomer is alpha-olefin, its density≤0.926g/cm 3, melt flow rate (MFR)≤2.0g/10min.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: described functional polymer is ethylene copolymer or poly material modified (preferred, the comonomer of described ethylene copolymer is vinylformic acid; Preferably, described poly material modified be polycthylene grafted material; Preferably, the compound that described graft materials monomer is vinylformic acid, maleic anhydride, glycidyl methacrylate, vinylbenzene or described monomer).
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: described metal passivator is acid amides or hydrazide kind compound.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: the mixture that described flow ability modifying agent is inside and outside lubricant agent, the mixture of one or more that described inside and outside lubricant agent is following material: polyethylene wax, paraffin, Poly Propylene Wax, oxidized polyethlene wax, brown coal ester type waxes, calcium stearate, Zinic stearas, silicone lubricant and fluorinated lubricant.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: described tinting material is carbon black or its masterbatch.
The described electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off, preferred scheme is: the mass concentration of described black masterbatch is 5%-50%.
The present invention also provides the described preparation method of polyethylene mixing material for electrolytic negative plate sealed strip that easily peels off, and by following operation, is undertaken:
A) by weight, by polyvinyl resin, linear low density polyethylene resin, functional polymer,, metal passivator, lubricant, tinting material be even in stirrer for mixing, squeezes into feed bin;
B), by twin screw or single Screw Extrusion granulation for the compound in feed bin, processing parameter is selected as follows:
Body temperature: 170-220 ℃, 190-220 ℃, 200-225 ℃, 210-230 ℃, 210-230 ℃, 210-230 ℃, head temperature: 210-220 ℃;
Engine speed: 30-60 rev/min, feeding rotating speed: 160-180 rev/min;
C) the pellet paper and plastics compound bag packing being cut into.
The present invention is by use High molecular weight polyethylene resin to be aided with the toughness of linear low density polyethylene resin constituent simultaneously, can meet the requirement to sealed strip toughness when mechanically peel of the industries such as electrolytic copper, add functional polymer greatly to increase the bounding force of constituent and negative plate, sealing effectiveness strengthens greatly, overcome the phenomenon of electrolytic solution infiltration sealing place, add metal passivator that transition metal ion is significantly reduced the catalyzed degradation effect of constituent, its life-span can be increased to more than 2 years, the tinting material carbon black adding or its masterbatch, there is the effect of anti-photoaging, can improve storage and the work-ing life of sealed strip.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described.
The material that the present invention adopts has: polyvinyl resin, linear low density polyethylene resin, functional polymer, metal passivator, flow ability modifying agent, amount of colorant.
Described polyvinyl resin is copolymerized macromolecule amount high density polyethylene(HDPE), and property indices requirement is: comonomer is alpha-olefin, its density>=0.940g/cm 3, melt flow rate (MFR)≤1.0g/10min.
Described linear low density polyethylene resin is multipolymer, and comonomer is alpha-olefin, its density≤0.926g/cm 3, melt flow rate (MFR)≤2.0g/10min.The object that adds type low density polyethylene resin is further to improve the toughness of constituent.
Described functional polymer ethylene copolymer or poly material modified, the comonomer of ethylene copolymer is vinylformic acid, poly material modified be polycthylene grafted material, grafted monomer is the compound of vinylformic acid, maleic anhydride, glycidyl methacrylate, vinylbenzene or above-mentioned monomer.It utilizes the polarity of functional polymer to improve the bonding force of constituent and negative plate as the used time, improves sealing effectiveness.
Described metal passivator is acid amides or hydrazide kind compound, metal passivator add can with electrolytic solution in transition metal ion especially cupric ion, iron ion form inner complex, reduce the catalyzed degradation of transition metal ion to constituent, thereby improve its life-span.
The inside and outside lubricant agent adding can improve the mobility of constituent, the electric current of forcing machine while reducing extrusion moulding, and the sealed strip smooth surface of simultaneously producing, is conducive to peeling off of electrolytic metal.
The tinting material carbon black adding or its masterbatch, be the screener of UV-light, the free radical that can be produced by uviolizing, storage and the work-ing life of improving sealed strip.
Below the embodiment of several different proportionings of the present invention:
Note: EAA is ethene and acrylic copolymer, and LLDPE-g-MAH is LLDPE grafted maleic anhydride, and LLDPE-g-AA (St) is LLDPE graft acrylic acid vinylbenzene.
The present invention prepares and easily peels off electrolytic negative plate sealed strip and by the method for polyethylene mixing material be:
A) by weight, polyvinyl resin, linear low density polyethylene resin, functional polymer, metal passivator, lubricant, tinting material is even in stirrer for mixing, squeeze into feed bin;
B), by twin screw or single Screw Extrusion granulation for the compound in feed bin, processing parameter is selected as follows:
Body temperature: 170-220 ℃, 190-220 ℃, 200-225 ℃, 210-230 ℃, 210-230 ℃, 210-230 ℃, head temperature: 210-220 ℃;
Engine speed: 30-60 rev/min, feeding rotating speed: 160-180 rev/min;
C) the pellet paper and plastics compound bag packing being cut into.
The performance representative value of the mixing material that the present invention obtains is in Table 1.
Table 1 is easily peeled off the performance performance representative value of polyethylene mixing material for electrolytic negative plate sealed strip
Sequence number Project Performance
1 Tensile strength (MPa) ≥25
2 Elongation at break (%) ≥350
3 Oxidation induction time (min, 200 ℃) ≥120
4 20 ℃ of volume specific resistances (Ω cm) ≥1.5×10 13
5 Dielectric strength (MV/m, 20 ℃) ≥25.6
6 Embrittlement temperature (℃) ＜－70
7 Stripping strength (N/cm) with pole plate ≥40
8 Frictional coefficient with copper ≤0.1
As can be seen from the above table, good technique effect of the present invention is embodied in:
1, in mixing material, added functional polymer, the sealed strip that extrusion moulding obtains and the stripping strength of pole plate are high, good sealing effect;
2, in mixing material, added metal passivator, the life-span of material extends greatly, can reach more than 2 years;
3, toughness of material is good, can stand the impact of mechanical force when peeling off, not broken;
4, in mixing material, add flow ability modifying agent can improve Drawing abillity, the sealed strip smooth surface of simultaneously processing, the cathode copper of production, manganese, zinc easily get off from sur-face peeling.
Mixing material of the present invention can adopt single screw rod to carry out the production of insulated enclosure bar, and processing temperature is: fuselage 180-220 ℃, head 210-230 ℃.Above processing condition can be adjusted as the case may be, and generally, top temperature is not generally over 240 ℃.
It should be pointed out that above embodiment is the more representational example of the present invention, obvious technical scheme of the present invention is not limited to above-described embodiment.Can also there be a lot of distortion.Those of ordinary skill in the art, from then on, with disclosed can mention or it is associated in invention, all should think the claimed scope of this patent.

Claims (7)

1. easily peel off electrolytic negative plate sealed strip polyethylene mixing material, it is characterized by: unit meter contains 100 parts of polyvinyl resins by weight, linear low density polyethylene resin 0.1-20 part, functional polymer 0.1-10 part, metal passivator 0.05-1 part, flow ability modifying agent 0.1-5 part, amount of colorant; Described polyvinyl resin is multipolymer, and comonomer is alpha-olefin, its density>=0.940g/cm 3, melt flow rate (MFR)≤1.0g/10min; Described functional polymer is ethylene copolymer or poly material modified, the comonomer of described ethylene copolymer is vinylformic acid, described poly material modified be polycthylene grafted material, described graft materials monomer is the compound of vinylformic acid, glycidyl methacrylate, vinylbenzene or described monomer; Described metal passivator is acid amides or hydrazide kind compound; Described flow ability modifying agent is the mixture of inside and outside lubricant agent, the mixture of one or more that described inside and outside lubricant agent is following material: Poly Propylene Wax, oxidized polyethlene wax, brown coal ester type waxes, calcium stearate, Zinic stearas, silicone lubricant and fluorinated lubricant.
2. the electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off according to claim 1, is characterized by: linear low density polyethylene resin 5-15 part, functional polymer 2-6 part, metal passivator 0.06-0.08 part, flow ability modifying agent 1-3 part.
3. the electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off according to claim 1 and 2, is characterized by: described linear low density polyethylene resin is multipolymer, and comonomer is alpha-olefin, its density≤0.926g/cm 3, melt flow rate (MFR)≤2.0g/10min.
4. the electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off according to claim 1 and 2, is characterized by: described tinting material is carbon black or its masterbatch.
5. the electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off according to claim 4, is characterized by: the mass concentration of described black masterbatch is 5%-50%.
6. the electrolytic negative plate sealed strip polyethylene mixing material of easily peeling off according to claim 5, is characterized by: mass concentration is 20%-30%.
7. according to easily peeling off the preparation method of electrolytic negative plate sealed strip with polyethylene mixing material described in claim 1 or 2, it is characterized by: by following operation, undertaken: a) by weight, polyvinyl resin, linear low density polyethylene resin, functional polymer, metal passivator, lubricant, tinting material is even in stirrer for mixing, squeeze into feed bin; B), by twin screw or single Screw Extrusion granulation for the compound in feed bin, processing parameter is selected as follows: body temperature: 170-220 ℃, 190-220 ℃, 200-225 ℃, 210-230 ℃, 210-230 ℃, 210-230 ℃, head temperature: 210-220 ℃; Engine speed: 30-60 rev/min, feeding rotating speed: 160-180 rev/min; C) the pellet paper and plastics compound bag packing being cut into.
CN201210139339.0A 2012-05-08 2012-05-08 Polyethylene mixing material for easily-stripped electrolytic cathode plate sealing strip and preparation method thereof Expired - Fee Related CN102643476B (en)

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CN114539663A (en) * 2022-04-18 2022-05-27 尚纬股份有限公司 Ethylene cable, strippable semiconductive insulation shielding material and preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1407009A (en) * 2001-08-24 2003-04-02 夏平 Antistatic polyolefine film
CN1464005A (en) * 2002-06-11 2003-12-31 上海高分子功能材料研究所 Silicon alkyl cross bonding polyethylene fire-retardancy insulating plastics
CN102241850A (en) * 2011-06-22 2011-11-16 青岛润兴塑料新材料有限公司 Polyethylene modified plastic with high performance and double resistance and manufacture method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1407009A (en) * 2001-08-24 2003-04-02 夏平 Antistatic polyolefine film
CN1464005A (en) * 2002-06-11 2003-12-31 上海高分子功能材料研究所 Silicon alkyl cross bonding polyethylene fire-retardancy insulating plastics
CN102241850A (en) * 2011-06-22 2011-11-16 青岛润兴塑料新材料有限公司 Polyethylene modified plastic with high performance and double resistance and manufacture method thereof

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