CN106279483B - A kind of electromagnetic shielding polyethylene film and preparation method thereof - Google Patents
A kind of electromagnetic shielding polyethylene film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to electromagnetic wave shield film fields, disclose a kind of electromagnetic shielding polyethylene film and preparation method thereof of high intensity, wherein, the electromagnetic shielding polyethylene film with a thickness of 20-200 μm, preferably 20-130 μm, electromagnet shield effect is >=20dB, preferably >=30dB, longitudinal tensile strength >=20MPa, preferably >=25MPa；Transverse tensile strength >=25MPa, preferably >=30MPa.Electromagnetic shielding polyethylene film provided by the present invention and the electromagnetic shielding polyethylene film being prepared by preparation method of the invention; electromagnetic shielding protection can be effectively performed; and processing technology is simple, versatility is good, has widened the application field of polyethylene film.
Description
Technical field
The present invention relates to electromagnetic wave shield film fields, and in particular, to a kind of electromagnetic shielding polyethylene film of high intensity
And preparation method thereof.
Background technique
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have special point
Polyethylene (PE) resin of minor structure is through the molding thin-film material of stretch processes.In the molding process of BOPE film
In, after the processing of film drawn, PE macromolecular chain and crystalline texture generation are height-oriented, to significantly improve the stretching of film
Intensity reduces tension fracture elongation rate, and makes that the mist degree of film is lower, glossiness is higher and transparent more preferable.In addition,
BOPE film is than the extrusioning blowing process of the prior art and the polyethylene film of extrusion casting technique production in terms of physical property
It has greatly improved, there is mechanical strength high, puncture resistant and shock resistance is good, excellent optical performance, heat sealability and moisture resistance
The advantages such as good, energy conservation and environmental protection, especially in the case where thickness reduces 50%, key performance remains to reach other polyethylene films
Performance.Therefore, BOPE film can be widely used in packaging bag, again packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane,
Medical and sanitary products, plastic film for agricultural use etc..
The processing method for being presently available for production bidirectional stretching plastic film has Flat film strength and envelope pulling method.Flat membrane
Pulling method has been applied in adding for the thin-film materials such as polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET)
In work, technique is more mature.Compared with envelope pulling method, the technique of Flat film strength is more mature, has stretching ratio big (horizontal
To stretching ratio up to 10 times or more), shaping speed fast (highest rolling speed is up to hundreds of ms/min), high production efficiency, and
And mechanical strength, optical property and the thickness uniformity of obtained the film advantages such as more preferably, but film forming is by technique item
Part influence of fluctuations is significant, and film stretch process difficulty is big, has higher requirement for film raw material.Existing biaxial tension is poly-
Ethylene raw is only applicable to envelope pulling method preparation BOPE film substantially, and these existing polyethylene raw materials are used flat membrane
When pulling method prepares BOPE film, film forming poor (tensile speed and stretching ratio are very low), film are easy to appear the defect of rupture, base
Originally be not suitable for the polyethylene film for preparing film, and obtaining using Flat film strength mechanical property and optical property compared with
Difference.Therefore flat membrane stretching polyethylene film has higher requirement for polyethylene raw material.
With the high speed development of electronics and information industry, the electronic product for generating Electromagnetic Interference sharply increases, and electromagnetic wave is dry
It disturbs and has become a kind of public hazards；Accurate electronic equipment and component are also easy to be damaged by Electromagnetic Interference simultaneously.Electromagnetism
Shielding material is earned widespread respect and is applied as a kind of effective means of anti-electromagnetism.Currently, polymer matrix electromagnetic shielding material
It is once completed with processing and forming, the more low advantage of price, is an important development direction of electromagnetic shielding material.Electromagnetic shielding
Film mainly uses PP, PET etc., and polyethylene is current production rate maximum, most widely used plastics variety, is widely used in thin
Film, cable etc..Electromagnetic shielding polyethylene film is prepared by addition conductive metal filler, has and processes simple, performance
The advantages that good, electroconductive stuffing mainly has at least one of conductive metal particles and conductive metallic fiber.
Therefore, need to develop a kind of electromagnetic shielding polyethylene film and preparation method thereof of high intensity at present.
Summary of the invention
The purpose of the invention is to overcome existing polyethylene raw material preparing polyethylene film using Flat film strength
When there are film formings that poor, film is easily broken, that is, be not suitable for preparing the defect of film using Flat film strength, and provide a kind of new
Polyethylene composition and the electromagnetic wave shield film made of the polyethylene composition.
To achieve the goals above, the present invention provides a kind of electromagnetic shielding polyethylene film, wherein the electromagnetic shielding is poly-
Vinyl film includes polyethylene composition, conductive filler and coupling agent, the electromagnetic shielding polyethylene film with a thickness of 20-
200 μm, preferably 20-130 μm, electromagnet shield effect are >=20dB, preferably >=30dB, and longitudinal tensile strength >=20MPa is excellent
It is selected as >=25MPa；Transverse tensile strength >=25MPa, preferably >=30MPa.
Electromagnetic shielding polyethylene film provided by the invention has stretching ratio height, tensile strength big and shield effectiveness
Good advantage, it is great to have prospects for commercial application.
A preferred embodiment of the invention, when the electromagnetic shielding polyethylene film includes polyethylene composition
Object, conductive filler and coupling agent, and the polyethylene composition contains component A, component B and component C；The component A be ethylene/
The linear low density polyethylene of alhpa olefin copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor
0.01-2.5g/10min, density pAFor 0.905-0.920g/cm3；The component B is the linea low density of ethylene/alpha-olefin copolymerization
Polyethylene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 0.01-2.5g/10min, density pBFor
0.921-0.936g/cm3；The component C be ethylene/alpha-olefin copolymerization linear low density polyethylene, temperature be 190 DEG C,
Load is the melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.905-0.928g/cm3；The component A,
The molecular weight distributing index of component B and component C are all satisfied Mw/MnWhen≤4.5, by the polyethylene composition, conductive filler and coupling
Dosage form at film not only there is preferable stretching ratio and tensile strength, but also it also has extraordinary shield effectiveness, non-
The often electromagnetic shielding polyethylene film suitable for the preparation of flat membrane biaxial tension method.
The present invention also provides the preparation methods of electromagnetic shielding polyethylene film, wherein this approach includes the following steps：
(1) polyethylene composition, the conductive filler and the coupling agent are subjected to machine in mechanical mixing equipment
Tool mixing, is then added in melt blending equipment and carries out melt blending；Or
First by addition to the conductive filler all components carry out melt blending after, then again with the conductive filler into
Row melt blending；
(2) electromagnetic shielding polyethylene slab is prepared using flat membrane biaxial tension method；And
(3) the obtained electromagnetic shielding polyethylene slab is subjected to drawing and forming in film biaxial tension equipment.
Electromagnetic shielding polyethylene film provided by the present invention and the electromagnetism being prepared by preparation method of the invention
Polyethylene film is shielded, electromagnetic shielding protection can be effectively performed, and processing technology is simple, versatility is good, has widened poly- second
The application field of alkene film.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structural schematic diagram to be used to prepare the multiple reactor shunting means of polyethylene composition.
Description of symbols
1- first reactor；2- second reactor；3- third reactor；4- solid-liquid (gas) separator；5- homogenization silo；
6- melt pelletization system.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Electromagnetic shielding polyethylene film provided by the invention, the electromagnetic shielding polyethylene film includes polyethylene composition
Object, conductive filler and coupling agent, the electromagnetic shielding polyethylene film with a thickness of 20-200 μm, preferably 20-130 μm, electricity
Magnetic screen efficiency is >=20dB, preferably >=30dB, longitudinal tensile strength >=20MPa, preferably >=25MPa；Cross directional stretch is strong
Degree >=25MPa, preferably >=30MPa.
In the present invention, the longitudinal tensile strength and transverse tensile strength are according to specified in GB/T 1040.3-2006
Method is measured.The shield effectiveness is tested according to SJ20524 standard with flange coaxial test equipment, and electromagnetic wave bands are
50MHz is to 1GHz frequency range.
Provided electromagnetic shielding polyethylene film according to the present invention, wherein the electromagnetic shielding polyethylene film can be with
For monodirectional tension film, or biaxially oriented film, preferably bidirectional oriented film, more preferably by flat membrane biaxial tension
The biaxially oriented film that method is prepared.
The polyethylene composition can be prepared according to existing various methods, for example, first prepare respectively component A,
Component B and component C, then by the component A, component B, component C, conductive filler, coupling agent and the selective lubrication that contains
Agent and other auxiliary agents carry out mechanical mixture in mechanical mixing equipment according to the proportion, are then added in melt blending equipment and are melted
Melt blending.Wherein, the mechanical mixing equipment can be for example high-speed mixer, kneader etc..The melt blending equipment example
It such as can be double screw extruder, single screw extrusion machine, open mill, mixer.
It is known to the skilled person using the process that flat membrane biaxial tension method prepares biaxially oriented film.Specifically,
Above-mentioned polyethylene composition is added in casting apparatus and squeeze out curtain coating slab, it is then that obtained slab is two-way in film
Drawing and forming is carried out in stretcher.During squeezing out curtain coating, slab die head can according to need the structure of the film of acquisition
It is selected, for example, single layer die can be used when needing to obtain the film with single layer structure；When needs are had
It, can be compound using multilayered structure when film (film with upper epidermis, sandwich layer and layer three-decker) of multilayered structure
Die head, and at least one layer of (sandwich layer) and the extruder material that above-mentioned polyethylene composition is housed in the compound die head of the multilayered structure
Bucket is connected to, and at least one layer (sandwich layer) in the film enabled in this way is the polyethylene formed by above-mentioned polyethylene composition
Layer.In extrusion process, extrusion temperature can be 160-260 DEG C, and the temperature for being cast chilling roller can be 15-85 DEG C.In addition, institute
Stating biaxial tension can be using Synchronos method drawing process (i.e. while carrying out film longitudinal (MD) and transverse direction (TD) stretches), can also be with
Using method of fractional steps drawing process (film longitudinal stretching is first carried out, then carries out film cross directional stretch).What the Synchronos method stretched
Concrete technology is：The slab carries out the stretching of vertical and horizontal direction after being fully warmed-up, wherein preheating temperature can be with
It is 75-165 DEG C, draft temperature can be 75-160 DEG C, longitudinal stretching ratio >=4 times (MD), laterally stretching ratio >=5 (TD)
Times, cross directional stretch rate >=50%/s.The concrete technology that the method for fractional steps stretches is：The slab is advanced after being fully warmed-up
Row longitudinal stretching carries out cross directional stretch later, wherein preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155
DEG C, longitudinal stretching ratio >=4 times (MD), lateral stretching ratio >=5 times (TD), cross directional stretch rate >=50%/s.In addition, film
It can be handled without setting after drawing and forming, annealing setting processing can also be carried out.When carrying out annealing setting processing, film
The treatment temperature that shapes can be 80-165 DEG C.Finally, film can also carry out surface corona processing, cutting edge and winding processing, most
Film of the present invention is obtained eventually.
Provided electromagnetic shielding polyethylene film stretching ratio is big according to the present invention, and rate of extension is high.Using flat membrane
During biaxial tension method prepares the electromagnetic shielding polyethylene film, longitudinal stretching ratio >=4 times (MD), laterally (TD) is drawn
Stretch multiplying power >=5 times；Stretching ratio is bigger, then the mechanical strength of film is higher；Preferably, it is prepared using flat membrane biaxial tension method
During the electromagnetic shielding polyethylene film, lateral (TD) rate of extension >=50%/s, preferably 60-100%/s, in this way
It can guarantee to industrialize continuous production.
Provided electromagnetic shielding polyethylene film according to the present invention, the component A are the linear of ethylene/alpha-olefin copolymerization
Low density polyethylene (LDPE), the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAIt is close for 0.01-2.5g/10min
Spend ρAFor 0.905-0.920g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, is in temperature
190 DEG C, load be 2.16kg under melt index MIBFor 0.01-2.5g/10min, density pBFor 0.921-0.936g/cm3；Institute
The linear low density polyethylene that component C is ethylene/alpha-olefin copolymerization is stated, it is molten in the case where temperature is 190 DEG C, load is 2.16kg
Melt index M ICFor 10-80g/10min, density pCFor 0.905-0.928g/cm3；The molecule of the component A, component B and component C
Amount profile exponent is all satisfied Mw/Mn≤ 4.5, preferably it is all satisfied 2≤Mw/Mn≤4.2。
Provided electromagnetic shielding polyethylene film according to the present invention, in above-mentioned polyethylene composition, it is preferable that described
Melt index MI of the component A in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-1g/10min, the component B is in temperature
Melt index MI under being 2.16kg for 190 DEG C, loadBFor 0.01-1.5g/10min, the component C temperature be 190 DEG C,
Load is the melt index MI under 2.16kgCFor 15-60g/10min；
In the present invention, the melt index is measured according to method specified in GB/T3682-2000, wherein
Test condition includes that temperature is 190 DEG C, load 2.16kg.
Provided electromagnetic shielding polyethylene film according to the present invention, it is preferable that the density p of the component AAFor 0.910-
0.918g/cm3, the density p of the component BBFor 0.926-0.930g/cm3, the density p of the component CCFor 0.910-
0.926g/cm3。
In the present invention, the density according to method specified in GB/T 1033.2-2010 and uses density gradient column
Method is measured.
The component A, component B and component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization, wherein linear
Structure refers in strand only containing short-chain branch structure, and does not contain long branched chain structure and cross-linked structure, by polymerized monomer and
Polymerization process condition is determined, is specifically known to the skilled person, and therefore not to repeat here.
Provided electromagnetic shielding polyethylene film according to the present invention, in order to enable the polyethylene composition arrived is with good
On the basis of good filming performance, also there is preferable optical property, it is preferable that in the polyethylene composition, the component A
Mass fraction WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 5-75 parts by weight, the mass parts of the component C
Number WCFor 10-75 parts by weight；It is highly preferred that in the polyethylene composition, the mass fraction W of the component AAFor 30-80 weight
Measure part, the mass fraction W of the component BBFor 5-45 parts by weight, the mass fraction W of the component CCFor 20-70 parts by weight.Into one
Step ground, the mass fraction W of the component AAWith the mass fraction W of component CCWith the melt index MI of component AARelationship it is preferably full
Foot meets 5.2 × lgMIA+11.6≥(WA+WB)/WC≥0.9×lgMIA+ 2.1, it is preferable that the mass fraction W of the component AA
With the mass fraction W of component CCWith the melt index MI of component AARelationship meet 2.9 × lgMIA+6.8≥(WA+WB)/WC≥
1.1×lgMIA+ 2.7, enable to the polyethylene composition to have in flat membrane method film biaxial tension processing so bigger
Stretching ratio and higher rate of extension.
Provided electromagnetic shielding polyethylene film according to the present invention, particularly preferably, the polyethylene composition is in temperature
Melt index under degree is 190 DEG C, load is 2.16kg is 0.1-20g/10min, most preferably 0.5-10g/10min.It is inciting somebody to action
On the basis of component A, component B and component C with above-mentioned particular melt index and density are used cooperatively, by the polyethylene group
The melt index control of object entirety is closed in above-mentioned preferred range, the polyethylene composition that enables to while being had very
Excellent film forming, tensile strength and punctured resistance and lower mist degree.
Provided electromagnetic shielding polyethylene film according to the present invention, it is preferable that the component A, component B and component C's
Molecular weight distributing index is all satisfied Mw/Mn≤ 4.5, more preferably 2.0≤M of satisfactionw/Mn≤4.2.Specifically, in order to obtain with upper
Component A, the component B and component C, the component A, component B and component C for stating molecular weight distribution are all made of metallocene catalyst polymerisation
It obtains.Wherein, the type of the metallocene catalyst can be the conventional selection of this field, usually by metallocene compound and
Organo-aluminum compound and optional electron donor composition, are specifically known to the skilled person, therefore not to repeat here.This hair
Bright inventor has found there is above-mentioned melt index and close for what is obtained using metallocene catalyst polymerisation after further investigation
Component A, component B and the component C of degree are used cooperatively, and obtained film also has non-on the basis of with good filming performance
Often high puncture energy, is highly suitable for packaging material.
Provided electromagnetic shielding polyethylene film according to the present invention, the present invention is in the component A, component B and component C
The content of alhpa olefin comonomer is not particularly limited, for example, alhpa olefin comonomer in the component A, component B and component C
Molar content can be each independently 0.2-15mol%, preferably 2-10mol%.In the present invention, alhpa olefin copolymerization is single
The molar content of body refers to that the mole of the structural unit formed by alpha-olefin polymerization accounts for the ratio of the mole of total monomer structural unit
Example.In addition, the alhpa olefin in the component A, component B and component C is each independently C3-C20At least one of alkene.From original
Expect that ready availability angle is set out, the alhpa olefin in the component A, component B and component C is preferably propylene, 1- butylene, 2- butylene, 3-
Methyl-1-butylene, 4- methyl-1-butylene, 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 3,3- dimethyl-1- penta
Alkene, 3,4- dimethyl-1- amylene, 4,4- dimethyl-1- amylene, 1- hexene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1-
Heptene, 2- heptene, 1- octene, 1- decene, 1- 12 (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, 1- 18 (carbon) alkene
At least one of with 1- 20 (carbon) alkene, more preferably at least one of 1- butylene, 1- hexene and 1- octene.
Provided electromagnetic shielding polyethylene film according to the present invention, the conductive filler can be selected from conductive metal particles
Class and/or conductive metallic fiber class, and on the basis of the total weight of the component A, the component B of 100 parts by weight and component C, institute
The content for stating conductive filler can be 12-30 parts by weight, preferably 12-16 parts by weight；Wherein, conductive metal particles and metal are fine
Dimension can be one of silver, aluminium, copper, iron, nickel and stainless steel or a variety of.
Provided electromagnetic shielding polyethylene film, the coupling agent can improve the polyethylene composition according to the present invention
Compatibility between object and conductive filler, type, usage and dosage all can be this field conventional selection, for example, described
Coupling agent can be selected from titante coupling agent, and the titante coupling agent can be selected from monoalkoxy type titanate esters, single alkane
One of base pyrophosphoric acid ester type titanate esters, corrdination type titanate esters and chelating titanate are a variety of；Preferably, the titanate esters
Class coupling agent is selected from butyl titanate and/or tetraisopropyl titanate；And with the component A, component B and the component C of 100 parts by weight
Total weight on the basis of, the content of the coupling agent can be 1-6 parts by weight, preferably 4-6 parts by weight.
Provided electromagnetic shielding polyethylene film, the polyethylene composition can also contain selective according to the present invention
Lubricant；The lubricant can improve the extrusion processability energy of the polyethylene composition, and type and dosage can be with
For the conventional selection of this field, for example, the lubricant can be selected from polyethylene glycol (PEG) series lubricant agent, fluoropolymers
Lubricant, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic acid acyl
In amine lubricant, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent
At least one.For example, the lubricant can be selected from polyethylene glycol (PEG) series lubricant agent, fluoropolymer series lubricant agent, have
Machine silicon series lubricant agent, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide class lubrication
At least one in agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent
Kind.Specifically, the PEG series lubricant agent for example can be the PEG molecule that molecular weight is 500-50000, can by sealing end,
Grafting, crosslinking Treatment, can also pass through other chemical modifications or physical modification.The fluoropolymer series lubricant agent for example can be with
For at least one of polytetrafluoroethylene (PTFE), Kynoar, polyhexafluoropropylene etc., or other are unimodal or multimodal fluorine-containing
Polymer and crystallization or hemicrystalline fluoropolymer.The organo-silicic oil can be existing various former with carbon, silicon
Son is molecular backbone, using the oligomer of the organic groups such as methyl, phenyl, alkoxy, vinyl or oligomer as the chemical combination of side chain
Object.The fatty alcohol type emollients can be for example at least one of soft fat alcohol, tallow alcohol, tallow fatty alcohol etc..Institute
Stating fatty acid lubricant for example can be with stearic acid and/or 12- hydroxy stearic acid.The fatty acid ester type emollients for example can be with
For at least one of butyl stearate, stearic acid list glycerolipid, cetyl palmitate, tearyl base ester etc..
The stearic amide series lubricant agent for example can be stearic amide, oleamide, erucyl amide, N, the double stearic acid of N- ethylene
At least one of amide (EBS) etc..The fatty acid metal soaps lubricant for example can for lead stearate, calcium stearate,
At least one of magnesium stearate, synthesis calcium acetate etc..The alkane and oxidation of alkanes series lubricant agent for example can be liquid stone
At least one of wax, solid paraffin, polyethylene wax, polypropylene wax, ethylene oxide wax etc..The micro-and nano-particles series lubricant agent
It such as can be powdered rubber and/or aerosil particles.In addition, with the total weight of the component A, component B and component C for 100 weights
Part meter is measured, the content of the lubricant can be 0.05-5 parts by weight, preferably 0.5-3 parts by weight.
In addition, can also contain in the polyethylene composition existing various in polyvinyl resin, polyethylene film
Other usually used auxiliary agents, and other described auxiliary agents will not stretching film forming to polyethylene composition provided by the invention,
Mechanical property and optical property have adverse effect on.Other described auxiliary agents include but is not limited to：Antioxidant, slipping agent, resist it is quiet
At least one of electric agent, antitack agent etc..In addition, the dosage of other auxiliary agents all can be this field conventional selection, it is right
This those skilled in the art can know that therefore not to repeat here.
The present invention also provides a kind of preparation methods of electromagnetic shielding polyethylene film, wherein this method includes following step
Suddenly：
(1) polyethylene composition, the conductive filler and the coupling agent are subjected to machine in mechanical mixing equipment
Tool mixing, is then added in melt blending equipment and carries out melt blending；Or
First by addition to the conductive filler all components carry out melt blending after, then again with the conductive filler into
Row melt blending；
(2) electromagnetic shielding polyethylene slab is prepared using flat membrane biaxial tension method；And
(3) the obtained electromagnetic shielding polyethylene slab is subjected to drawing and forming in film biaxial tension equipment.
The preparation method of provided electromagnetic shielding polyethylene film according to the present invention, wherein the mechanical mixing equipment
It such as can be high-speed mixer, kneader etc..The melt blending equipment can for example squeeze for double screw extruder, single screw rod
Machine, open mill, mixer etc. out.
The polyethylene composition is prepared in multiple reactor shunting means as shown in Figure 1, the multiple reactor
Shunting means includes first reactor 1, second reactor 2, third reactor 3, solid-liquid (gas) separator 4,5 and of homogenization silo
Melt pelletization system 6, wherein the first reactor 1, second reactor 2 and third reactor 3 are connected in parallel, the solid-liquid
(gas) separator 4 is connected to first reactor 1, second reactor 2 and third reactor 3 respectively, is prepared by first reactor 1
Component A, the component B prepared by second reactor 2, and the component C prepared by third reactor 3 is in solid-liquid (gas) separator 4
It is middle mutually to be separated, then by component A, component B and the component C after mutually separating be delivered in homogenization silo 5 in proportion and with
Conductive filler and the lubricant selectively contained and other additives are mixed together uniformly, are sent into melt pelletization system 6 later
Middle carry out extruding pelletization.Wherein, the polymerization in each reactor can be batchwise polymerization, be also possible to continuous polymerization.When using more
When reactor parallel polymerization, W hereinafterA、WBAnd WCFor yield in unit time of each component in respective reaction device.
Specifically, a kind of preferred embodiment according to the present invention, a kind of provided electromagnetic shielding polyethylene film
Preparation method, process are as follows：
(1) contain according to existing various methods by the component A, component B, component C and conductive filler and preferably
Lubricant and other auxiliary agents carry out mechanical mixture in mechanical mixing equipment according to the proportion, be then added in melt blending equipment into
Row melt blending.In addition, can also be first by all components in addition to conductive filler and after auxiliary agent carries out melt blending, then fill out with conduction
Material carries out melt blending.Wherein, the mechanical mixing equipment can be for example high-speed mixer, kneader etc..The melting is altogether
Mixing device can be for example double screw extruder, single screw extrusion machine, open mill, mixer etc..
(2) electromagnetic shielding polyethylene slab is prepared using flat membrane biaxial tension method.Specifically, the conduction first step obtained
Filler/polyethylene blend, which is added in casting apparatus, squeeze out curtain coating slab, and in extrusion process, extrusion temperature can be
160-260 DEG C, the temperature for being cast chilling roller can be 15-85 DEG C.
(3) obtained slab is subjected to drawing and forming in film biaxial tension equipment.The biaxial tension can use
Synchronos method drawing process (carries out film longitudinal (MD) simultaneously and laterally (TD) is stretched), can also use method of fractional steps drawing process
(first carry out film longitudinal stretching, then carry out film cross directional stretch).The concrete technology that the Synchronos method stretches is：The slab
After being fully warmed-up, while carrying out the stretching of vertical and horizontal direction, wherein preheating temperature can be 75-165 DEG C, draft temperature
It can be 75-160 DEG C, longitudinal stretching ratio >=3 times (MD), lateral stretching ratio >=4 times (TD), cross directional stretch rate >=
50%/s.The concrete technology that the method for fractional steps stretches is：The slab first carries out longitudinal stretching after being fully warmed-up, it is laggard
Row cross directional stretch, wherein preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155 DEG C, and longitudinal (MD) is stretched again
Rate >=4 times, lateral stretching ratio >=5 times (TD), cross directional stretch rate >=50%/s.In addition, can not after film drawing and forming
Setting processing is carried out, annealing setting processing can also be carried out.When carrying out annealing setting processing, film shapes treatment temperature can be with
It is 80-165 DEG C.Finally, film can also carry out surface corona processing, cutting edge and winding processing, finally obtain of the present invention
Antistatic film.
Electromagnetic shielding polyethylene film provided by the present invention and the electromagnetism being prepared by preparation method of the invention
Polyethylene film is shielded, electromagnetic shielding protection can be effectively performed, and processing technology is simple, versatility is good, has widened poly- second
The application field of alkene film.
In the following Examples and Comparative Examples：
Film biaxial tension equipment is purchased from Germany Br ü ckner company, model Karo IV.
The polyethylene composition and film performance are tested in accordance with the following methods：
(1) molecular weight distributing index (Mw/Mn)：Using the PL-GPC 220 of Polymer Laboratories company of Britain
Type gel permeation chromatograph combination IR5 type infrared detector is measured, and chromatographic column is 3 series connection Plgel, 10 μm of MIXED-B
Column, solvent and mobile phase are 1,2,4- trichloro-benzenes, and column temperature is 150 DEG C, flow velocity 1.0mL/min, using the EasiCal of PL company
PS-1 Narrow distribution polystyrene standard specimen carries out universal calibration；
(2) melt index (MI)：It is measured according to method specified in GB/T 3682-2000, wherein test temperature
It is 190 DEG C, load 2.16kg；
(3) density：It is measured according to method specified in GB/T 1033.2-2010 and using density gradient column method；
(4) longitudinal tensile strength and transverse tensile strength：It is surveyed according to method specified in GB/T 1040.3-2006
It is fixed；
(5) shield effectiveness：According to SJ20524 standard, tested with flange coaxial test equipment, electromagnetic wave bands 50MHz
To 1GHz frequency range.
Embodiment 1
The present embodiment is for illustrating electromagnetic shielding polyethylene film provided by the invention and preparation method thereof.
I, the preparation of polyethylene composition：
Polyethylene composition 1 provided in this embodiment is made of component A, component B and component C, these three components are second
Alkene/alhpa olefin copolymerization linear low density polyethylene (LLDPE), and it is all made of identical catalyst system (metallocene catalyst)
Prepared with polymerization technique, the type of amounts of hydrogen and alhpa olefin comonomer that difference is added when being to prepare different component and
Molar content is different.Specific step is as follows：
By ethylene, alhpa olefin, hydrogen and nitrogen, (ethylene, alhpa olefin, hydrogen and nitrogen are polymer grade, after removing water, oxygen
Use, similarly hereinafter) it is added in gas fluidized bed reactor, the metallocene catalyst system (metallocene catalyst is then added
System is the carried metallocene catalyst being prepared by CN102453124A embodiment 1, similarly hereinafter), it is later 84- in temperature
88 DEG C, pressure be 1.8-2.0MPa under conditions of polymerize, respectively obtain component A, component B and component C.Wherein, component A, component B
Control with the melt index of component C realizes that the control of density passes through the kind for adjusting alhpa olefin by adjusting the additional amount of hydrogen
Class and additional amount and realize.Alhpa olefin used is 1- hexene during preparing component A, prepares α alkene used during component B
Hydrocarbon is 1- hexene, and alhpa olefin used is 1- butylene during preparing component C.
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows：
The melt index MI of component AA=1.2g/10min, density pA=0.910g/cm3, molecular weight distributing index Mw/Mn=
3.36, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MI of component BB=2.1g/10min, density pB=0.923g/cm3, molecular weight distributing index Mw/Mn=
3.3, molar content=5.5mol% of alhpa olefin comonomer；
The melt index MI of component CC=15g/10min, density pC=0.905g/cm3, molecular weight distributing index Mw/Mn=
3.5, molar content=9.1mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 70 weight
Part, the mass fraction W of component BBFor 20 parts by weight, the mass fraction W of component CCFor 20 parts by weight, (WA+WB)/WC=4.5 (meet
5.2×lgMIA+11.6≥(WA+WB)/WC≥0.9×lgMIA+ 2.1, also meet 2.9 × lgMIA+6.8≥(WA+WB)/WC≥
1.1×lgMIA+2.7)；It adds mixture in high speed agitator and is uniformly mixed later, then the material mixed is added to
In the feeder of the double screw extruder of W&P company manufacture, material enters in twin-screw via feeder, screw rod in process
Temperature be maintained between 160-210 DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition
Pellet is detected its melt index MI=2.1g/10min.
The preparation of II, electromagnetic shielding polyethylene film：
Polyethylene composition 1；Fe powder, 1000 mesh；Coupling agent, butyl titanate.
(1) polyethylene composition 1 is 100 parts by weight meters, and Fe powder is 25 parts by weight, and coupling agent is 5 parts by weight.It will mix later
Conjunction object, which is added in high speed agitator, to be uniformly mixed, then the material mixed is added to the twin-screw extrusion of W&P company manufacture
In the feeder of machine, material enters in twin-screw via feeder, in process the temperature of screw rod be maintained at 160-210 DEG C it
Between, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain mixture pellet.
(2) mixture pellet made from above-mentioned steps (1) is dried, is added to Labtech company of Sweden later
Melting extrusion cocurrent is carried out in the sandwich layer extruder of the multilayer extrusion casting machine of model LCR400 and upper and lower surface layer extruder
Prolong slab, wherein also need to be added inorganic antitack agent (silica, similarly hereinafter) in the upper and lower surface layer extruder, and upper and lower
The weight ratio of the antitack agent and mixture pellet that are added in the extruder of surface layer is 0.02:1, during being cast slab, it will flow
Prolong chilling roll temperature and be set as 25 DEG C, electromagnetic shielding polyethylene thickness slab is made, is made of upper epidermis, sandwich layer and layer.
(3) above-mentioned electromagnetic shielding polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is used
The two-way step drawing technological forming that laterally (TD) is stretched after first longitudinal (MD) is stretched, each step process condition are as follows：MD preheating temperature
Degree is 105 DEG C, and MD draft temperature is 110 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 105 DEG C, and TD draft temperature is 115
DEG C, TD stretching ratio is 5 times, and film TD rate of extension is 60%/s；Film setting temperature is 120 DEG C, by upper epidermis, sandwich layer
It is constituted with layer, each layer raw material is the electromagnetic shielding polyethylene of the present embodiment, and also containing anti-in upper epidermis and layer
Stick.
The performance of gained electromagnetic shielding polyethylene film is as shown in table 1.
Embodiment 2
The present embodiment is for illustrating electromagnetic shielding polyethylene film provided by the invention and preparation method thereof.
I, the preparation of polyethylene composition：
Polyethylene composition 2 provided in this embodiment is made of component A, component B and component C, these three components are second
Alkene/alhpa olefin copolymerization linear low density polyethylene (LLDPE), and it is all made of identical catalyst system (metallocene catalyst)
Prepared with polymerization technique, the type of amounts of hydrogen and alhpa olefin comonomer that difference is added when being to prepare different component and
Molar content is different.Specific step is as follows：
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, metallocene catalyst is then added
System polymerize under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa later, respectively obtains component A, component B and group
Divide C.Wherein, the control of the melt index of component A, component B and component C is realized by adjusting the additional amount of hydrogen, density
Control is realized by the type and additional amount for adjusting alhpa olefin.Alhpa olefin used is 1- butylene, preparation during preparing component A
Alhpa olefin used is 1- butylene during component B, and preparing alhpa olefin used during component C is 1- hexene.
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows：
The melt index MI of component AA=0.02g/10min, density pA=0.915g/cm3, molecular weight distributing index Mw/Mn
=2.96, molar content=7.6mol% of alhpa olefin comonomer；
The melt index MI of component BB=1.0g/10min, density pB=0.926g/cm3, molecular weight distributing index Mw/Mn=
3.0, molar content=4.9mol% of alhpa olefin comonomer；
The melt index MI of component CC=60g/10min, density pC=0.920g/cm3, molecular weight distributing index Mw/Mn=
2.85, molar content=5.8mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 45 weight
Part, the mass fraction W of component BBFor 10 parts by weight, the mass fraction W of component CCFor 60 parts by weight；(WA+WB)/WC=0.9 (meets
5.2×lgMIA+11.6≥(WA+WB)/WC≥0.9×lgMIA+ 2.1, also meet 2.9 × lgMIA+6.8≥(WA+WB)/WC≥
1.1×lgMIA+2.7)；It adds mixture in high speed agitator and is uniformly mixed later, then the material mixed is added to
In the feeder of the double screw extruder of W&P company manufacture, material enters in twin-screw via feeder, screw rod in process
Temperature be maintained between 180-240 DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition
Pellet is detected its melt index MI=1.8g/10min.
The preparation of II, electromagnetic shielding polyethylene film：
Polyethylene composition 2；Stainless steel fibre, 6.5 μm of Φ, draw ratio 370；Coupling agent, tetraisopropyl titanate.
Polyethylene composition 2 is 100 parts by weight meters, and the additional amount of stainless steel fibre is 12 parts by weight, the addition of coupling agent
Amount is 3 parts by weight.
Preparation method is carried out by embodiment 1, and unlike step (1) in embodiment 1, stainless steel fibre is squeezed from twin-screw
The side loading mouth of machine is added out.The performance of gained electromagnetic shielding polyethylene film is as shown in table 1.
Embodiment 3
The present embodiment is for illustrating electromagnetic shielding polyethylene film provided by the invention and preparation method thereof.
Electromagnetic shielding polyethylene film is prepared according to the method for embodiment 1, unlike, group in the polyethylene composition
B is divided to be substituted with the component C of identical weight part, i.e., the described polyethylene composition only contains combination A and combination C.
The performance of gained electromagnetic shielding polyethylene film is as shown in table 1.
Embodiment 4
The present embodiment is for illustrating electromagnetic shielding polyethylene film provided by the invention and preparation method thereof.
Electromagnetic shielding polyethylene film is prepared according to the method for embodiment 1, unlike, drawing process is synchronous bidirectional drawing
It stretches, the stretching ratio of MD and TD are 4 times, rate of extension 60%/s.
The performance of gained electromagnetic shielding polyethylene film is as shown in table 1.
Comparative example 1
Polyethylene raw material used in this comparative example is the film-grade linear low density polyethylene of U.S. DOW chemical company production
Alkene, trade mark ELITE 5400G, catalyst are metallocene catalyst, melt index MI=1.0g/10min, density p=0.916g/
cm3, molecular weight distributing index Mw/Mn=3.2.
Fe powder/polyethylene film is prepared according to the method for embodiment 1, unlike, the polyethylene composition is with identical
The polyethylene raw material of this comparative example of parts by weight substitutes.It is repeatedly attempted the case where stretching rupture of membranes occur, film forming can not be stretched.
Comparative example 2
This comparative example prepares film according to the method for embodiment 1, unlike, conductive filler Fe powder is not added.
The performance of gained polyethylene film is as shown in table 1.
Table 1
It can be concluded that, filled out in embodiment 1-4 using polyethylene composition provided by the invention, conduction from the result in table 1
Electromagnetic shielding polyethylene (PE) film of material and coupling agent preparation biaxial tension, has stretching times compared with the film of the prior art
The advantage that rate is big, shield effectiveness is good.Electromagnetic shielding polyethylene film provided by the present invention and by preparation method of the invention
Electromagnetic shielding protection can be effectively performed in the electromagnetic shielding polyethylene film being prepared, and processing technology is simple, versatility
It is good, widen the application field of polyethylene film.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (23)
1. a kind of electromagnetic shielding polyethylene film, which is characterized in that the electromagnetic shielding polyethylene film includes polyethylene composition
Object, conductive filler and coupling agent, the electromagnetic shielding polyethylene film with a thickness of 20-200 μm, electromagnet shield effect is >=
20dB, longitudinal tensile strength >=20MPa, transverse tensile strength >=25MPa；
Wherein, the polyethylene composition contains component A, component B and component C；
The component A be ethylene/alpha-olefin copolymerization linear low density polyethylene, temperature be 190 DEG C, load 2.16kg
Under melt index MIAFor 0.01-2.5g/10min, density pAFor 0.905-0.92g/cm3；
The component B be ethylene/alpha-olefin copolymerization linear low density polyethylene, temperature be 190 DEG C, load 2.16kg
Under melt index MIBFor 0.01-2.5g/10min, density pBFor 0.921-0.936g/cm3；
The component C be ethylene/alpha-olefin copolymerization linear low density polyethylene, temperature be 190 DEG C, load 2.16kg
Under melt index MICFor 10-80g/10min, density pCFor 0.905-0.928g/cm3；
The molecular weight distributing index of described component A, B and C are all satisfied Mw/Mn≤4.5。
2. electromagnetic shielding polyethylene film according to claim 1, wherein the thickness of the electromagnetic shielding polyethylene film
It is 20-130 μm, electromagnet shield effect is >=30dB, longitudinal tensile strength >=25MPa；Transverse tensile strength >=30MPa.
3. electromagnetic shielding polyethylene film according to claim 2, wherein the electromagnetic shielding polyethylene film is using flat
Film biaxial tension method is prepared.
4. electromagnetic shielding polyethylene film according to claim 3, wherein using described in the preparation of flat membrane biaxial tension method
During electromagnetic shielding polyethylene film, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5 times.
5. electromagnetic shielding polyethylene film according to claim 4, wherein using described in the preparation of flat membrane biaxial tension method
During electromagnetic shielding polyethylene film, cross directional stretch rate >=50%/s.
6. electromagnetic shielding polyethylene film according to claim 1, wherein the component A is 190 DEG C, load in temperature
For the melt index MI under 2.16kgAFor 0.01-1g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg
Melt index MIBFor 0.01-1.5g/10min, melting of the component C in the case where temperature is 190 DEG C, load is 2.16kg refers to
Number MICFor 15-60g/10min.
7. electromagnetic shielding polyethylene film according to claim 1, wherein the density p of the component AAFor 0.91-
0.918g/cm3, the density p of the component BBFor 0.926-0.93g/cm3, the density p of the component CCFor 0.91-0.926g/
cm3。
8. electromagnetic shielding polyethylene film according to claim 1, wherein in the polyethylene composition, described group
Divide the mass fraction W of AAFor 25-90 parts by weight, the mass fraction W of the component BBFor 5-75 parts by weight, the quality of the component C
Number WCFor 10-75 parts by weight.
9. electromagnetic shielding polyethylene film according to claim 8, wherein in the polyethylene composition, described group
Divide the mass fraction W of AAFor 30-80 parts by weight, the mass fraction W of the component BBFor 5-45 parts by weight, the quality of the component C
Number WCFor 20-70 parts by weight.
10. electromagnetic shielding polyethylene film according to claim 1, wherein the mass fraction W of the component AAWith component C
Mass fraction WCWith the melt index MI of component AARelationship meet 5.2 × lgMIA+11.6≥(WA+WB)/WC≥0.9×
lgMIA+2.1。
11. electromagnetic shielding polyethylene film according to claim 10, wherein the mass fraction W of the component AAAnd component
The mass fraction W of CCWith the melt index MI of component AARelationship meet 2.9 × lgMIA+6.8≥(WA+WB)/WC≥1.1×
lgMIA+2.7。
12. electromagnetic shielding polyethylene film according to claim 9, wherein the polyethylene composition is 190 in temperature
DEG C, the melt index under load is 2.16kg be 0.1-20g/10min.
13. electromagnetic shielding polyethylene film according to claim 12, wherein the polyethylene composition is in temperature
190 DEG C, the melt index under load is 2.16kg be 0.5-10g/10min.
14. electromagnetic shielding polyethylene film described in any one of -13 according to claim 1, wherein the component A, component
The molecular weight distributing index of B and component C are all satisfied 2≤Mw/Mn≤4.2。
15. electromagnetic shielding polyethylene film according to claim 14, wherein the component A, component B and component C are adopted
It is obtained with metallocene catalyst polymerisation.
16. electromagnetic shielding polyethylene film according to claim 1, wherein α alkene in the component A, component B and component C
The molar content of hydrocarbon comonomer is each independently 0.2-15mol%.
17. electromagnetic shielding polyethylene film according to claim 16, wherein α in the component A, component B and component C
The molar content of olefin comonomer is each independently 2-10mol%.
18. electromagnetic shielding polyethylene film according to claim 1, wherein the conductive filler is selected from conductive metal grain
Subclass and/or conductive metallic fiber class, the coupling agent be selected from titanate coupling agent, and with the component A of 100 parts by weight,
On the basis of the total weight of component B and component C, the content of the conductive filler is 12-30 parts by weight, and the content of the coupling agent is
1-6 parts by weight.
19. electromagnetic shielding polyethylene film according to claim 18, wherein the content of the conductive filler is 12-16
Parts by weight, the content of the coupling agent are 4-6 parts by weight.
20. electromagnetic shielding polyethylene film according to claim 1, wherein the α in the component A, component B and component C
Alkene is each independently C3-C20At least one of alkene.
21. electromagnetic shielding polyethylene film according to claim 20, wherein in the component A, component B and component C
Alhpa olefin be propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 3,
3- dimethyl-1- amylene, 3,4- dimethyl-1- amylene, 4,4- dimethyl-1- amylene, 1- hexene, 4- methyl-1-hexene, 5- first
Base -1- hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- dodecylene, tetradecene, cetene, 1- 18
At least one of carbene and 1- eicosylene.
22. electromagnetic shielding polyethylene film according to claim 21, wherein in the component A, component B and component C
Alhpa olefin is at least one of 1- butylene, 1- hexene and 1- octene.
23. the preparation method of electromagnetic shielding polyethylene film described in any one of claim 1-22, wherein this method packet
Include following steps：
(1) polyethylene composition, the conductive filler and the coupling agent are carried out in mechanical mixing equipment mechanical mixed
It closes, is then added in melt blending equipment and carries out melt blending；Or
After all components in addition to the conductive filler are first carried out melt blending, then melted again with the conductive filler
Melt blending；
(2) electromagnetic shielding polyethylene slab is prepared using flat membrane biaxial tension method；And
(3) the obtained electromagnetic shielding polyethylene slab is subjected to drawing and forming in film biaxial tension equipment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362390A (en) * | 2008-09-28 | 2009-02-11 | 北京理工大学 | Wide band electromagnetic wave-shielded polyethylene compound film containing carbonyl iron powder and preparation method thereof |
| CN102066466A (en) * | 2008-05-16 | 2011-05-18 | 埃克森美孚石油公司 | Biaxially oriented LLDPE blends |
| CN102604194A (en) * | 2012-02-11 | 2012-07-25 | 常州市嘉鹏塑料制品有限公司 | Transparent electromagnetic shielding film |
| CN102850678A (en) * | 2012-09-20 | 2013-01-02 | 吴江市天源塑胶有限公司 | High-strength conductive plastic |
| CN104558792A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Polyethylene composition and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010018685A (en) * | 2008-07-09 | 2010-01-28 | Mitsubishi Plastics Inc | Electroconductive resin film |
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2015
- 2015-06-12 CN CN201510323677.3A patent/CN106279483B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066466A (en) * | 2008-05-16 | 2011-05-18 | 埃克森美孚石油公司 | Biaxially oriented LLDPE blends |
| CN101362390A (en) * | 2008-09-28 | 2009-02-11 | 北京理工大学 | Wide band electromagnetic wave-shielded polyethylene compound film containing carbonyl iron powder and preparation method thereof |
| CN102604194A (en) * | 2012-02-11 | 2012-07-25 | 常州市嘉鹏塑料制品有限公司 | Transparent electromagnetic shielding film |
| CN102850678A (en) * | 2012-09-20 | 2013-01-02 | 吴江市天源塑胶有限公司 | High-strength conductive plastic |
| CN104558792A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Polyethylene composition and preparation method thereof |
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