CN105623059A - Polyethylene composition and thin film thereof - Google Patents
Polyethylene composition and thin film thereof Download PDFInfo
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- CN105623059A CN105623059A CN201410583605.8A CN201410583605A CN105623059A CN 105623059 A CN105623059 A CN 105623059A CN 201410583605 A CN201410583605 A CN 201410583605A CN 105623059 A CN105623059 A CN 105623059A
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Abstract
The invention provides a polyethylene composition and a thin film thereof. The polyethylene composition contains a component A and a component C and optionally contains a component B; the component A is ethylene/alpha olefin copolymerized linear low-density polyethylene, the melt index MIA is 0.01-2 g/10 min at the temperature of 190 DEG C and the load of 2.16 kg, and the density [rho]A is 0.880-0.936 g/cm<3>; the component B is ethylene/alpha olefin copolymerized linear low-density polyethylene, the melt index MIB is 2.1-14.9 g/10 min at the temperature of 190 DEG C and the load of 2.16 kg, and the density [rho]B is 0.910-0.930 g/cm<3>; the component C is ethylene/alpha olefin copolymerized linear low-density polyethylene, the melt index MIC is 15-150 g/10 min at the temperature of 190 DEG C and the load of 2.16 kg, and the density [rho]C is 0.880-0.930 g/cm<3>. When the polyethylene thin film is prepared from the polyethylene composition by a flat film stretching method, the stretching ratio is large, the film forming speed is high, and the film forming property is quite good.
Description
Technical field
The present invention relates to a kind of polyethylene composition and thin film thereof.
Background technology
Biaxially-oriented polyethylene (BiaxiallyOrientedPolyethylene, BOPE) thin film is the thin-film material through stretch processes molding of polyethylene (PE) resin with special molecular structure. In the molding process of BOPE thin film, after thin film drawn processes, PE macromolecular chain and crystalline texture occur height-oriented, thus significantly improving the hot strength of thin film, reduce tension fracture elongation rate, and make that the mist degree of thin film is lower, glossiness is higher and transparent better. Additionally, compared with polyethylene film goods prepared by the extrusioning blowing process of prior art and extrusion casting technique, BOPE thin film has the advantages such as mechanical strength height, puncture resistant and shock resistance good, excellent optical performance, environmental protection and energy saving. Therefore, BOPE thin film can be widely used in the aspects such as packaging bag, heavily packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane, medical and sanitary products, plastic film for agricultural use.
The biaxial tension processing method of the plastic sheeting adopted at present has Flat film strength and envelope pulling method. Flat film strength has been applied in the processing of the thin-film materials such as polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET), and technique is comparatively ripe. Compared with envelope pulling method, the stretching ratio of Flat film strength big (cross directional stretch multiplying power is up to more than 10 times), shaping speed fast (the highest rolling speed is up to hundreds of ms/min), production efficiency are high, and the mechanical strength of the thin film obtained, optical property and thickness evenness are all more preferably, but film forming is affected significantly by process condition fluctuations, film stretching difficulty of processing is big, has higher requirement for film raw material. Existing Biaxially-oriented polyethylene raw material is substantially all only applicable to envelope pulling method and prepares BOPE thin film, and when adopting Flat film strength to prepare BOPE thin film these polyethylene raw material existing, there is film property difference (draw speed and stretching ratio are very low), easily there is the defect broken in film, that is, substantially it is not suitable for adopting Flat film strength to prepare thin film. Therefore, in order to make full use of the above-mentioned advantage of Flat film strength, need a kind of good film-forming property of exploitation at present badly and film is not easy occur that the Flat film strength that is applicable to broken prepares the polyethylene raw material of BOPE thin film.
Summary of the invention
The invention aims to overcome and existing polyethylene raw material is adopted that Flat film strength exists film property difference when preparing polyethylene film, film is easily broken, namely it is not suitable for the defect adopting Flat film strength to prepare thin film, and a kind of new polyethylene composition and the thin film being made up of this polyethylene composition are provided.
Specifically, polyethylene composition provided by the invention contains the component B that component A, component C and selectivity contain; Described component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-2g/10min, density is 0.880-0.936g/cm3; Described component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 2.1-14.9g/10min, density is 0.910-0.930g/cm3; Described component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 15-150g/10min, density is 0.880-0.930g/cm3��
Thin film provided by the invention at least includes one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The present inventor finds after further investigation, by above-mentioned have particular melt index and the component A of density, component B and component C with the use of and when the polyethylene composition that obtains adopts Flat film strength to prepare polyethylene film, there is the advantage that stretching ratio is big, rate of film build is high, disclosure satisfy that the Flat film strength high requirement to polyethylene raw material, and adapt to the economy demand of existing Flat film strength production line, great prospects for commercial application.
A preferred embodiment of the invention, as the mass fraction W of component A described in described polyethylene compositionAFor 25-90 weight portion, the mass fraction W of described component BBFor 0.1-10 weight portion, the mass fraction W of described component CCDuring for 10-75 weight portion, this polyethylene composition has on the basis of better film property, this polyethylene composition the thin film prepared also has relatively low mist degree.
Another kind of preferred implementation according to the present invention, when the molecular weight distributing index of described component A, component B and component C is satisfied by Mw/MnWhen��4.5, this polyethylene composition has on the basis of better film property, this polyethylene composition the thin film prepared also has higher intensity and puncture resistance.
Another kind of preferred implementation according to the present invention, when the density p of component A, component B and component C in described polyethylene compositionA����BAnd ��CBetween relation meet-0.04�ܦ�A-��B�� 0.02, and-0.04�ܦ�A-��CWhen��0.02, this polyethylene composition has on the basis of better film property, this polyethylene composition the thin film prepared also has the advantage that hot strength and punctured resistance are high and mist degree is low.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is the structural representation of the multiple reactor shunting means for preparing polyethylene composition.
Description of reference numerals
1-the first reactor; 2-the second reactor; 3-the 3rd reactor; 4-solid-liquid (gas) separator; 5-homogenization silo; 6-melt pelletization system.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
Polyethylene composition provided by the invention contains the component B that component A, component C and selectivity contain; Described component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3; Described component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 2.1-14.9g/10min, density pBFor 0.910-0.930g/cm3; Described component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3��
According to polyethylene composition provided by the invention, it is preferable that described component A temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-1.5g/10min, described component B temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 3-10g/10min, described component C temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 15-100g/10min. It is highly preferred that described component A temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-1g/10min, described component B temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 3-5g/10min, described component C temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 20-60g/10min.
In the present invention, described melt index is all measured according to the method for regulation in GB/T3682-2000, and wherein, it is 190 DEG C that test condition includes temperature, and load is 2.16kg.
According to polyethylene composition provided by the invention, it is preferable that the density p of described component AAFor 0.910-0.930g/cm3, the density p of described component BBFor 0.913-0.928g/cm3, the density p of described component CCFor 0.905-0.928g/cm3. It is highly preferred that the density p of described component AAFor 0.915-0.926g/cm3, the density p of described component BBFor 0.913-0.924g/cm3, the density p of described component CCFor 0.910-0.926g/cm3. It is particularly preferred that the density p of component A, component B and component C in described polyethylene compositionA����BAnd ��CBetween relation meet-0.04�ܦ�A-��B�� 0.02, and-0.04�ܦ�A-��C�� 0.02, the polyethylene composition so enabled to has on the basis of good filming performance, also has very high hot strength and punctured resistance and relatively low mist degree.
Described component A, component B and component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization, wherein, linear structure refers to and contains only short-chain branch structure in strand, and do not contain long branched chain structure and cross-linked structure, it is determined by polymerization single polymerization monomer and polymerization process condition, being specially as well known to those skilled in the art, therefore not to repeat here.
According to polyethylene composition provided by the invention to polyethylene composition having on the basis of good filming performance, also there is good optical property, it is preferable that in described polyethylene composition, the mass fraction W of described component AAFor 25-90 weight portion, the mass fraction W of described component BBFor 0.1-10 weight portion, the mass fraction W of described component CCFor 10-75 weight portion; It is highly preferred that in described polyethylene composition, the mass fraction W of described component AAFor 30-80 weight portion, the mass fraction W of described component BBFor 0.5-8 weight portion, the mass fraction W of described component CCFor 20-70 weight portion. Further, the mass fraction W of described component AAMass fraction W with component CCMelt index MI with component AARelation preferably meet 5.2 �� lgMIA+11.6��WA/WC��0.9��lgMIA+ 2.1, more preferably meet 2.9 �� lgMIA+6.8��WA/WC��1.1��lgMIA+ 2.7, so enable to described polyethylene composition and there is the rate of extension of bigger stretching ratio and Geng Gao in flat embrane method thin film biaxial tension is processed.
According to polyethylene composition provided by the invention, it is particularly preferred to ground, described polyethylene composition temperature be 190 DEG C, load be the melt index under 2.16kg be 0.1-20g/10min, it is most preferred that for 0.5-10g/10min. By have above-mentioned particular melt index and the component A of density, component B and component C with the use of basis on, melt index overall for described polyethylene composition is controlled in above-mentioned preferred scope, it is possible to make the polyethylene composition obtained have very excellent film property, hot strength and punctured resistance and relatively low mist degree simultaneously.
The content of described component B is not particularly limited by the present invention, with the gross weight of described polyethylene composition for benchmark, and the mass percentage content M of described component BBPreferably��35 weight %, more preferably MB�� 25 weight %.
According to polyethylene composition provided by the invention, it is preferable that the molecular weight distributing index of described component A, component B and component C is satisfied by Mw/Mn�� 4.5, more preferably meet 2.0��Mw/Mn�� 4.2. Specifically, having the component A of above-mentioned molecular weight distribution, component B and component C to obtain, described component A, component B and component C all adopt metallocene catalyst polymerisation to obtain. Wherein, the kind of described metallocene catalyst can be the conventional selection of this area, and it is generally made up of metallocene compound and organo-aluminum compound and optional electron donor, is specially as well known to those skilled in the art, and therefore not to repeat here. The present inventor finds after further investigation, by adopt metallocene catalyst polymerisation obtain have above-mentioned melt index and the component A of density, component B and component C with the use of, the thin film obtained has on the basis of good filming performance, also there is very high anti-puncture performance, be highly suitable for packaging material.
The content of alhpa olefin comonomer in described component A, component B and component C is not particularly limited by the present invention, such as, in described component A, component B and component C, the molar content of alhpa olefin comonomer can be each independently 0.2-15mol%, it is preferred to 1.5-10mol%. In the present invention, the molar content of alhpa olefin comonomer refers to that the mole of the construction unit formed by alpha-olefin polymerization accounts for the ratio of the mole of total monomer construction unit. Additionally, the alhpa olefin in described component A, component B and component C is each independently C3-C20At least one in alkene. from the angle that raw material is ready availability, described component A, alhpa olefin in component B and component C is preferably propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, 4-methyl isophthalic acid-butylene, 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 isophthalic acid-hexene, 5-methyl isophthalic acid-hexene, 1-heptene, 2-heptene, 1-octene, 1-decene, 1-12 (carbon) alkene, 1-14 (carbon) alkene, 1-16 (carbon) alkene, at least one in 1-18 (carbon) alkene and 1-20 (carbon) alkene, it is more preferably 1-butylene, at least one in 1-hexene and 1-octene.
According to polyethylene composition provided by the invention, it is preferable that described polyethylene composition, possibly together with lubricant, so can improve the extrusion processing characteristics of described polyethylene composition. The kind of described lubricant and consumption can be all the conventional selection of this area, such as, described lubricant can be selected from least one in Polyethylene Glycol (PEG) series lubricant agent, fluoropolymer series lubricant agent, silicone based lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent. Specifically, described PEG series lubricant agent such as can for the PEG molecule that molecular weight is 500-50000, and it can pass through end-blocking, grafting, crosslinking Treatment, it is also possible to through other chemical modifications or physical modification. Described fluoropolymer series lubricant agent can be such as at least one in politef, Kynoar, polyhexafluoropropylene etc., it is also possible to the fluoropolymer of or multimodal unimodal for other and crystallization or hemicrystalline fluoropolymer. Described organo-silicic oil can be existing various with carbon, silicon atom for molecular backbone, the compound being side chain with the oligomer of the organic groups such as methyl, phenyl, alkoxyl, vinyl or oligomer. Described fatty alcohol type emollients can be such as at least one in soft fat alcohol, hard fatty alcohol, tallow fatty alcohol etc. Described fatty acid lubricant such as can stearic acid and/or 12-hydroxy stearic acid. Described fatty acid ester type emollients can be such as at least one in butyl stearate, stearic acid list glyceride, cetyl palmitate, stearyl base ester etc. Described stearic amide series lubricant agent can be such as at least one in stearic amide, oleamide, erucyl amide, n, n-ethylene bis stearic acid amide (EBS) etc. Described fatty acid metal soaps lubricant can be such as at least one in lead stearate, calcium stearate, magnesium stearate, synthesis calcium acetate etc. Described alkane and oxidation of alkanes series lubricant agent can be such as at least one in liquid paraffin, hard paraffin, Tissuemat E, polypropylene wax, ethylene oxide wax etc. Described micro-and nano-particles series lubricant agent can be such as powdered rubber and/or aerosil particles. Additionally, with the gross weight of described component A, component B and component C for 100 parts by weight, the content of described lubricant can be 0.05-5 weight portion, it is preferred to 0.5-3 weight portion.
In addition, described polyethylene composition can also contain existing various other auxiliary agents normally used in polyvinyl resin, polyethylene film, and the stretching film property of polyethylene composition provided by the invention, mechanical property and optical property will not be had adverse effect on by other auxiliary agents described. Other auxiliary agents described include but not limited to: at least one in antioxidant, slipping agent, antistatic additive, antitack agent etc. Additionally, the consumption of other auxiliary agents described can be all the conventional selection of this area, these those skilled in the art all being known, therefore not to repeat here.
Described polyethylene composition can prepare according to existing various methods, such as, first prepare component A, component B and component C respectively, then the lubricant described component A, component B and component C and selectivity contained and other auxiliary agents carry out mechanical mixture according to proportioning in mechanical mixing equipment, are subsequently adding in melt blending equipment and carry out melt blending. Wherein, described mechanical mixing equipment can be such as homogenizer, kneader etc. Described melt blending equipment can be such as double screw extruder, single screw extrusion machine, mill, banbury etc.
A preferred embodiment of the invention, described polyethylene composition prepares in multiple reactor shunting means as shown in Figure 1, described multiple reactor shunting means includes the first reactor 1, second reactor 2, 3rd reactor 3, solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization system 6, wherein, described first reactor 1, second reactor 2 and the 3rd reactor 3 are connected in parallel, the number of described solid-liquid (gas) separator 4 is three, respectively with the first reactor 1, second reactor 2 connects with the 3rd reactor 3, the component A prepared by the first reactor 1, the component B prepared by the second reactor 2 and component C prepared by the 3rd reactor 3 is separated respectively in different solid-liquid (gas) separators 4, then by the component A after being separated, component B and component C is delivered in homogenization silo 5 in proportion and is mixed together uniformly with other additives, send in melt pelletization system 6 afterwards and carry out extruding pelletization. wherein, the polymerization in each reactor can be batchwise polymerization, it is also possible to be continuous polymerization. when adopting multiple reactor parallel polymerization, W hereinafterA��WBAnd WCFor each component yield in unit time in respective reaction device.
Thin film provided by the invention at least includes one layer of polyethylene layer formed by above-mentioned polyethylene composition.
Described thin film can have single layer structure, it is possible to have multiple structure. When described thin film is multiple structure, at least main stor(e)y (being generally the layer that thickness is maximum) is the polyethylene layer formed by described polyethylene composition. Such as, described thin film can have the composite construction of upper epidermis, sandwich layer and layer, and at least described sandwich layer is the polyethylene layer formed by described polyethylene composition. As a rule, the thickness of described thin film can be 10-200 ��m, it is preferred to 10-100 ��m. Additionally, when described thin film has the composite construction of upper epidermis, sandwich layer and layer, the thickness of described upper epidermis and layer is each independently the 1-25% of described film thickness.
Additionally, described thin film can be monodirectional tension film, it is also possible to for biaxially oriented film, it is preferred to biaxially oriented film, more preferably the biaxially oriented film prepared by flat film biaxial tension method.
The process that flat film biaxial tension method prepares biaxially oriented film is adopted to be known to the skilled person. Specifically, first above-mentioned polyethylene composition is joined and casting apparatus carries out extrusion curtain coating slab, then the slab obtained is carried out drawing and forming in thin film biaxial tension equipment. In the process of extrusion curtain coating, the structure of the film that slab die head can obtain as required selects, for instance, when needing to obtain the thin film with single layer structure, it is possible to adopt single layer die; When needing to obtain thin film (there is the thin film of upper epidermis, sandwich layer and layer three-decker) with multiple structure, multiple structure compound die head can be adopted, and at least one of which (sandwich layer) connects with the extruder hopper equipped with above-mentioned polyethylene composition in described multiple structure compound die head, at least one of which (sandwich layer) in the thin film so enabled to is the polyethylene layer formed by above-mentioned polyethylene composition. In extrusion, extrusion temperature can be 160-260 DEG C, and the temperature of curtain coating chilling roller can be 15-85 DEG C. In addition, described biaxial tension can adopt Synchronos method drawing process (namely simultaneously carrying out thin film longitudinally (MD) and laterally (TD) stretching), method of fractional steps drawing process (namely first carry out thin film longitudinal stretching, then carry out thin film cross directional stretch) can also be adopted. Described Synchronos method stretches specifically comprises the processes of: described slab is after being fully warmed-up, carry out the stretching of vertical and horizontal direction simultaneously, wherein, preheating temperature can be 75-165 DEG C, draft temperature can be 75-160 DEG C, longitudinally (MD) stretching ratio >=4 times, laterally (TD) stretching ratio >=5 times, cross directional stretch speed >=50%/s. The described method of fractional steps stretches specifically comprises the processes of: described slab is after being fully warmed-up, first carry out longitudinal stretching, carry out cross directional stretch afterwards, wherein, preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155 DEG C, longitudinally (MD) stretching ratio >=4 times, laterally (TD) stretching ratio >=5 times, cross directional stretch speed >=50%/s. Additionally, setting treatment can not be carried out after film stretching molding, it is also possible to be annealed setting treatment. When being annealed setting treatment, thin film setting treatment temperature can be 80-165 DEG C. Finally, thin film can also carry out surface corona process, cutting edge and rolling and process, and finally gives thin film of the present invention.
Thin film provided by the invention has good film property and stretching ratio is big, rate of extension is high. Flat film strength is being adopted to prepare in the process of described biaxially oriented film, as it has been described above, the longitudinal direction of described thin film (MD) stretching ratio >=4 times, laterally (TD) stretching ratio >=5 times. Stretching ratio is more big, then the mechanical strength of thin film is more high. Transverse direction (TD) rate of extension >=50%/s of described thin film, it is preferred to 60-100%/s, so ensure that industrialization produces continuously.
Thin film provided by the invention has higher mechanical strength and good optical property. Described biaxially oriented film performance can meet: longitudinally (MD) hot strength >=55MPa, it is preferred to >=60MPa; Laterally (TD) hot strength >=65MPa, it is preferred to >=70MPa. Puncture strength >=the 2.5N of described biaxially oriented film, it is preferred to >=3.5N. Tension fracture elongation rate��350% of described biaxially oriented film, it is preferred to��300%. In the present invention, described longitudinal tensile strength and transverse tensile strength are measured according to the method for regulation in GB/T1040.3-2006. Described puncture strength is measured according to the method for regulation in GB/T10004-2008, and wherein, the thickness of film sample is 25 �� 5 ��m. Described tension fracture elongation rate is measured according to the method for regulation in GB/T1040.3-2006.
The production cost of thin film provided by the invention is low, processing technique is simple, versatility is good, has widened the application of polyethylene film.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples:
Thin film biaxial tension equipment is purchased from Br �� ckner company of Germany, and model is KaroIV.
Described polyethylene composition and film performance are tested in accordance with the following methods:
(1) molecular weight distributing index (Mw/Mn): adopt the PL-GPC220 type chromatograph of gel permeation of PolymerLaboratories company of Britain to be measured in conjunction with IR5 type infrared detector, chromatographic column is Plgel10 ��m of MIXED-B post of 3 series connection, solvent and mobile phase are 1,2,4-trichloro-benzenes, column temperature is 150 DEG C, and flow velocity is 1.0mL/min, adopts the EasiCalPS-1 Narrow distribution polystyrene standard specimen of PL company to carry out universal calibration;
(2) melt index (MI): be measured according to the method for regulation in GB/T3682-2000, wherein, test temperature is 190 DEG C, and load is 2.16kg;
(3) density: according in GB/T1033.2-2010 regulation method and adopt density gradient column method to be measured.
Embodiment 1
The present embodiment is used for polyethylene composition provided by the invention and thin film thereof are described.
(1) preparation of polyethylene composition:
The polyethylene composition that the present embodiment provides is made up of component A, component B and component C, these three component is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and all adopt identical catalyst system (metallocene catalyst) and polymerization technique to prepare, it is distinctive in that the kind of amounts of hydrogen affiliated when preparing different component and alhpa olefin comonomer and molar content are different. Specifically comprise the following steps that
By ethylene, alhpa olefin, hydrogen and nitrogen, (ethylene, alhpa olefin, hydrogen and nitrogen are polymer grade, use after elimination water, oxygen, lower same) join in gas fluidized bed reactor, (described metallocene catalyst system is the carried metallocene catalyst prepared by CN102453124A embodiment 1 to be subsequently adding metallocene catalyst system, lower same), afterwards temperature be 84-88 DEG C, pressure be 1.8-2.0MPa when polymerization, respectively obtain component A, component B and component C. Wherein, the control of the melt index of component A, component B and component C realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component A, alhpa olefin used is 1-hexene, and in the process of preparation component B, alhpa olefin used is 1-hexene, and in the process of preparation component C, alhpa olefin used is 1-butylene.
After testing, said method the performance of the component A, component B and the component C that prepare is as follows:
The melt index MI of component AA=1.5g/10min, density pA=0.913g/cm3, molecular weight distributing index Mw/Mn=3.4, the molar content=7.5mol% of alhpa olefin comonomer;
The melt index MI of component BB=2.1g/10min, density pB=0.913g/cm3, molecular weight distributing index Mw/Mn=3.2, the molar content=7.5mol% 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, the molar content=9.1mol% of alhpa olefin comonomer.
Undertaken weighing and mixing by proportioning by above-mentioned prepared each component, wherein the mass fraction W of component AAIt is 80 weight portions, the mass fraction W of component BBIt is 10 weight portions, the mass fraction W of component CCIt is 20 weight portions, WA/WC=4 (meet 5.2 �� lgMIA+11.6��WA/WC��0.9��lgMIA+ 2.1, also meet 2.9 �� lgMIA+6.8��WA/WC��1.1��lgMIA+ 2.7), (described lubricant is the PEG lubricant that Switzerland's Clariant Corporation produces to be subsequently adding lubricant, molecular weight 10000, and with said components A, the quality sum of component B and component C is 100 parts by weight, the addition of lubricant is 0.1 weight portion), feed the mixture into mix homogeneously in high speed agitator afterwards, again the material mixed is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 160-210 DEG C, uniform through screw rod melting mixing, extrusion, pelletize is also dried, obtain polyethylene composition pellet, its melt index MI=2.4g/10min after testing.
(2) preparation of polyethylene film:
The polyethylene composition pellet that above-mentioned steps (1) prepares is dried, join afterwards the multilayer extrusion casting machine that model is LCR400 of Labtech company of Sweden sandwich layer extruder and on, layer extruder carries out melt extrude and curtain coating slab, wherein, on described, layer extruder also needs add inorganic antitack agent (silicon dioxide, lower same), and on, the antitack agent added in layer extruder and the weight ratio of polyethylene composition pellet are 0.02:1, in curtain coating slab process, curtain coating chilling roll temperature is set as 25 DEG C, make polyethylene thickness slab, it is by upper epidermis, sandwich layer and layer are constituted.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of thin film biaxial tension equipment, adopt the two-way step drawing technological forming that after first longitudinal (MD) stretching, laterally (TD) stretches, each step process condition is as follows: it is 100 DEG C that MD preheats temperature, MD draft temperature is 110 DEG C, and MD stretching ratio is 4 times; It is 100 DEG C that TD preheats temperature, and TD draft temperature is 115 DEG C, and TD stretching ratio is 5 times, and thin film TD rate of extension is 60%/s; Thin film setting temperature is 120 DEG C, obtaining the thin film that average thickness is 25 ��m, it is made up of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and thickness possibly together with antitack agent, upper epidermis and layer is 0.5 ��m in upper epidermis and layer.
Embodiment 2
The present embodiment is used for polyethylene composition provided by the invention and thin film thereof are described.
(1) preparation of polyethylene composition:
The polyethylene composition that the present embodiment provides is made up of component A, component B and component C, these three component is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and all adopt identical catalyst system (metallocene catalyst) and polymerization technique to prepare, it is distinctive in that the kind of amounts of hydrogen affiliated when preparing different component and alhpa olefin comonomer and molar content are different. Specifically comprise the following steps that
Ethylene, alhpa olefin, hydrogen and nitrogen are joined in gas fluidized bed reactor, are subsequently adding metallocene catalyst system, afterwards temperature be 84-88 DEG C, pressure be 1.8-2.0MPa when polymerization, respectively obtain component A, component B and component C. Wherein, the control of the melt index of component A, component B and component C realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component A, alhpa olefin used is 1-butylene, and in the process of preparation component B, alhpa olefin used is 1-butylene, and in the process of preparation component C, alhpa olefin used is 1-hexene.
After testing, said method the performance of the component A, component B and the component C that prepare is as follows:
The melt index MI of component AA=0.01g/10min, density pA=0.930g/cm3, molecular weight distributing index Mw/Mn=3.0, the molar content=1.6mol% of alhpa olefin comonomer;
The melt index MI of component BB=10.0g/10min, density pB=0.930g/cm3, molecular weight distributing index Mw/Mn=2.8, the molar content=1.9mol% of alhpa olefin comonomer;
The melt index MI of component CC=60g/10min, density pC=0.922g/cm3, molecular weight distributing index Mw/Mn=2.9, the molar content=3.8mol% of alhpa olefin comonomer.
Undertaken weighing and mixing by proportioning by above-mentioned prepared each component, wherein the mass fraction W of component AAIt is 55 weight portions, the mass fraction W of component BBIt is 5 weight portions, the mass fraction W of component CCIt is 55 weight portions, WA/WC=1 (meets 5.2 �� lgMIA+11.6��WA/WC��0.9��lgMIA+ 2.1, also meet 2.9 �� lgMIA+6.8��WA/WC��1.1��lgMIA+ 2.7), (described lubricant is the PEG lubricant that Switzerland's Clariant Corporation produces to be subsequently adding lubricant, molecular weight 6000, and with said components A, the quality sum of component B and component C is 100 parts by weight, the addition of lubricant is 3 weight portions), feed the mixture into mix homogeneously in high speed agitator afterwards, again the material mixed is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 180-240 DEG C, uniform through screw rod melting mixing, extrusion, pelletize is also dried, obtain polyethylene composition pellet, its melt index MI=0.9g/10min after testing.
(2) preparation of polyethylene film:
The polyethylene composition pellet that above-mentioned steps (1) prepares is dried, join afterwards the multilayer extrusion casting machine that model is LCR400 of Labtech company of Sweden sandwich layer extruder and on, layer extruder carries out melt extrude and curtain coating slab, wherein, on described, layer extruder also needs add inorganic antitack agent, and on, the antitack agent added in layer extruder and the weight ratio of polyethylene composition pellet are 0.02:1, in curtain coating slab process, curtain coating chilling roll temperature is set as 85 DEG C, make polyethylene thickness slab, it is by upper epidermis, sandwich layer and layer are constituted.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of thin film biaxial tension equipment, adopt the two-way step drawing technological forming that after first longitudinal (MD) stretching, laterally (TD) stretches, each step process condition is as follows: it is 130 DEG C that MD preheats temperature, MD draft temperature is 126 DEG C, and MD stretching ratio is 4 times; It is 130 DEG C that TD preheats temperature, and TD draft temperature is 128 DEG C, and TD stretching ratio is 6 times, and thin film TD rate of extension is 100%/s; Thin film setting temperature is 130 DEG C, obtaining the thin film that average thickness is 25 ��m, it is made up of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and thickness possibly together with antitack agent, upper epidermis and layer is 1 ��m in upper epidermis and layer.
Embodiment 3
The present embodiment is used for polyethylene composition provided by the invention and thin film thereof are described.
(1) preparation of polyethylene composition:
The polyethylene composition that the present embodiment provides adopts the multiple reactor shunting means polymerization shown in Fig. 1 to obtain, wherein the first reactor 1 polymerization preparation component A, second reactor 2 polymerization preparation component B, 3rd reactor 3 polymerization preparation component C, component A, component B and component C is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, these three component all adopts identical catalyst system (metallocene catalyst) and polymerization technique to prepare, it is distinctive in that amounts of hydrogen affiliated when preparing different component, the yield in unit time of the kind of alhpa olefin comonomer and molar content and each reactor is different. specifically comprise the following steps that
Alhpa olefin, normal hexane and hydrogen are joined in polymer reactor, and polymer reactor is heated to default polymerization temperature, afterwards vinyl monomer and catalyst system are added simultaneously in polymer reactor, and temperature be 140 DEG C, pressure be 2.5MPa when polyase 13 0 minute, respectively obtain component A, component B and component C. Wherein, the control of the melt index of component A, component B and component C realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component A, alhpa olefin used is 1-octene, and in the process of preparation component B, alhpa olefin used is 1-butylene, and in the process of preparation component C, alhpa olefin used is 1-butylene.
By the yield in unit time W of component A in the first reactor 1 in preparation processA, the yield in unit time W of component B in the second reactor 2BWith the yield in unit time W of component C in the 3rd reactor 3CWeight ratio maintain WA: WB: WC=75:2:35, wherein WA/WC=2.1 (meet 5.2 �� lgMIA+11.6��WA/WC��0.9��lgMIA+ 2.1, also meet 2.9 �� lgMIA+6.8��WA/WC��1.1��lgMIA+2.7)��
After testing, said method the performance of the component A, component B and the component C that prepare is as follows:
The melt index MI of component AA=0.1g/10min, density pA=0.920g/cm3, molecular weight distributing index Mw/Mn=3.1, the molar content=2.1mol% of alhpa olefin comonomer;
The melt index MI of component BB=5.0g/10min, density pB=0.920g/cm3, molecular weight distributing index Mw/Mn=3.5, the molar content=5.1mol% of alhpa olefin comonomer;
The melt index MI of component CC=25g/10min, density pC=0.920g/cm3, molecular weight distributing index Mw/Mn=3.2, the molar content=5.1mol% of alhpa olefin comonomer.
Above-mentioned prepared each component is respectively delivered in different solid-liquid (gas) separators 4 in yield in unit time ratio and carries out being separated and and then being transported to, in the homogenization silo 5 stirred, then adding lubricant by proportioning and carry out mixing homogenizing. Wherein, lubricant is the Tissuemat E that Honeywell Inc. of the U.S. produces, and with the quality sum of said components A, component B and component C for 100 parts by weight, the addition of lubricant is 1 weight portion. Afterwards the mixture of homogenized feed bin 5 homogenizing is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 170-230 DEG C, through screw rod melting mixing uniformly, extrusion, pelletize drying, obtain polyethylene composition pellet, after testing its melt index MI=0.6g/10min.
(2) preparation of polyethylene film:
The polyethylene composition pellet that above-mentioned steps (1) prepares is dried, join afterwards and the multilayer extrusion casting machine that model is LCR400 of Labtech company of Sweden carries out melt extruding and curtain coating slab, in curtain coating slab process, curtain coating chilling roll temperature is set as 35 DEG C, making polyethylene thickness slab, this slab is single layer structure.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of thin film biaxial tension equipment, adopt the two-way step drawing technological forming that after first longitudinal (MD) stretching, laterally (TD) stretches, each step process condition is as follows: it is 116 DEG C that MD preheats temperature, MD draft temperature is 118 DEG C, and MD stretching ratio is 4 times; It is 120 DEG C that TD preheats temperature, and TD draft temperature is 120 DEG C, and TD stretching ratio is 5 times, and thin film TD rate of extension is 100%/s; Thin film setting temperature is 122 DEG C, obtains the single thin film that average thickness is 25 ��m.
Embodiment 4
The present embodiment is used for polyethylene composition provided by the invention and thin film thereof are described.
Polyethylene composition and polyethylene film is prepared according to the method for embodiment 1, the difference is that, the component C of the component B identical weight part in described polyethylene composition substitutes, namely, described polyethylene composition contains only component A and component C, obtaining the thin film that average thickness is 25 ��m, wherein, the thickness of upper epidermis and layer is 0.5 ��m.
Embodiment 5
The present embodiment is used for polyethylene composition provided by the invention and thin film thereof are described.
Polyethylene composition and polyethylene film is prepared according to the method for embodiment 1, the difference is that, in the preparation process of component A, the consumption of each material is different so that the density p of component A, component B and component CA����BAnd ��CBetween relation be unsatisfactory for-0.04�ܦ�A-��B�� 0.02 and-0.04�ܦ�A-��C�� 0.02, obtain the thin film that average thickness is 25 ��m, wherein, the thickness of upper epidermis and layer is 0.5 ��m. In the preparation process of described component A, the performance of the component A obtained is as follows: the melt index MI of component AA=1.5g/10min, density pA=0.928g/cm3, molecular weight distributing index Mw/Mn=3.0, the molar content=1.9mol% of alhpa olefin comonomer.
Comparative example 1
This comparative example is for illustrating polyethylene raw material and the thin film thereof of reference.
(1) polyethylene raw material:
Polyethylene raw material used by this comparative example is the film-grade linear low density polyethylene that DOW chemical company of the U.S. produces, and trade mark ELITE5400G, catalyst is metallocene catalyst, melt index MI=1.0g/10min, density p=0.916g/cm3, molecular weight distributing index Mw/Mn=3.2.
(2) preparation of polyethylene film:
Polyethylene film is prepared according to the method for embodiment 3, the difference is that, the polyethylene raw material of this comparative example step (1) of described polyethylene composition pellet identical weight part is substituted, through repeatedly attempting all occurring stretching the situation of rupture of membranes, it is impossible to stretch film forming. Additionally, after the TD rate of extension in polyethylene film preparation process is down to 50%/s, through repeatedly attempting still occurring stretching the situation of rupture of membranes, it is impossible to stretch film forming.
Comparative example 2
This comparative example is for illustrating polyethylene raw material and the thin film thereof of reference.
(1) polyethylene raw material:
Polyethylene raw material used by this comparative example is identical with comparative example 1.
(2) preparation of polyethylene film:
The polyethylene film of this comparative example adopts the upper blowing method film blowing device extrusion and blow molding of DR.COLLIN company of Germany to obtain, concrete grammar is as follows: the polyethylene raw material that above-mentioned steps (1) is chosen joined in the hopper of upper blowing method film blowing device extruder, after the abundant fusion plastification of the extruded machine of raw material, extruded by the annular die of head and make melt membrane tube, compressed air inflation (blow-up ratio is 2.5 times) afterwards, and make polyethylene film after vane cools down, wherein thin film is average thickness is the single layer structure of 25 ��m.
Comparative example 3
This comparative example is for illustrating polyethylene composition and the thin film thereof of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides is made up of component 1 and component 2, both components are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and all adopt identical catalyst system (metallocene catalyst) and polymerization technique to prepare, it is distinctive in that the kind of amounts of hydrogen affiliated when preparing different component and alhpa olefin comonomer and molar content are different. Specifically comprise the following steps that
Ethylene, alhpa olefin, hydrogen and nitrogen are joined in gas fluidized bed reactor, are subsequently adding metallocene catalyst system, afterwards temperature be 84-88 DEG C, pressure be 1.8-2.0MPa when polymerization, respectively obtain component 1 and component 2. Wherein, the control of the melt index of component 1 and component 2 realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component 1, alhpa olefin used is 1-hexene, and in the process of preparation component 2, alhpa olefin used is 1-butylene.
After testing, said method the component 1 prepared and the performance of component 2 are as follows:
The melt index MI of component 11=5.0g/10min, density p1=0.913g/cm3, molecular weight distributing index Mw/Mn=3.2, the molar content=7.5mol% of alhpa olefin comonomer;
The melt index MI of component 22=15g/10min, density p2=0.905g/cm3, molecular weight distributing index Mw/Mn=3.5, the molar content=9.8mol% of alhpa olefin comonomer.
Undertaken weighing and mixing by proportioning by above-mentioned prepared each component, wherein the mass fraction W of component 11It is 80 weight portions, the mass fraction W of component 22It is 20 weight portions, W1/W2=4, (described lubricant is the PEG lubricant that Switzerland's Clariant Corporation produces to be subsequently adding lubricant, molecular weight 10000, and with the quality sum of said components 1 and component 2 for 100 parts by weight, the addition of lubricant is 0.1 weight portion), feed the mixture into mix homogeneously in high speed agitator afterwards, again the material mixed is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 160-210 DEG C, uniform through screw rod melting mixing, extrusion, pelletize is also dried, obtain polyethylene composition pellet, its melt index MI=6.2g/10min after testing.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 1, result shows, through repeatedly attempting, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) �� 2 times (MD), the highest stretching ratio of thin film TD is only 10%/s, i.e. stretching ratio and rate of extension are all too low, stretching film property is poor, does not possess practicality.
Comparative example 4
This comparative example is for illustrating polyethylene composition and the thin film thereof of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides is made up of component 1 and component 2, both components are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and all adopt identical catalyst system (metallocene catalyst) and polymerization technique to prepare, it is distinctive in that the kind of amounts of hydrogen affiliated when preparing different component and alhpa olefin comonomer and molar content are different. Specifically comprise the following steps that
Ethylene, alhpa olefin, hydrogen and nitrogen are joined in gas fluidized bed reactor, are subsequently adding metallocene catalyst system, afterwards temperature be 84-88 DEG C, pressure be 1.8-2.0MPa when polymerization, respectively obtain component 1 and component 2. Wherein, the control of the melt index of component 1 and component 2 realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component 1, alhpa olefin used is 1-butylene, and in the process of preparation component 2, alhpa olefin used is 1-hexene.
After testing, said method the component 1 prepared and the performance of component 2 are as follows:
The melt index MI of component 11=0.01g/10min, density p1=0.930g/cm3, molecular weight distributing index Mw/Mn=2.8, the molar content=1.8mol% of alhpa olefin comonomer;
The melt index MI of component 22=5.0g/10min, density p2=0.922g/cm3, molecular weight distributing index Mw/Mn=2.7, the molar content=4.1mol% of alhpa olefin comonomer.
Undertaken weighing and mixing by proportioning by above-mentioned prepared each component, wherein the mass fraction W of component 11It is 55 weight portions, the mass fraction W of component 22It is 55 weight portions, W1/W2=1, (described lubricant is the PEG lubricant that Switzerland's Clariant Corporation produces to be subsequently adding lubricant, molecular weight is 6000, and with the quality sum of said components 1 and component 2 for 100 parts by weight, the addition of lubricant is 3 weight portions), feed the mixture into mix homogeneously in high speed agitator afterwards, again the material mixed is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 180-240 DEG C, uniform through screw rod melting mixing, extrusion, pelletize is also dried, obtain polyethylene composition pellet, its melt index MI=0.22g/10min after testing.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 2, result shows, through repeatedly attempting, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) �� 2 times (MD), the highest stretching ratio of thin film TD is only 10%/s, i.e. stretching ratio and rate of extension are all too low, stretching film property is poor, does not possess practicality.
Comparative example 5
This comparative example is for illustrating polyethylene composition and the thin film thereof of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides adopts the polymerization of multiple reactor shunting means to obtain, wherein first reactor polymerization preparation component the 1, second reactor polymerization preparation component 2, component 1 and the linear low density polyethylene (LLDPE) that component 2 is ethylene/alpha-olefin copolymerization, both components all adopt identical catalyst system (metallocene catalyst) and polymerization technique to prepare, and are distinctive in that the yield in unit time of amounts of hydrogen affiliated when preparing different component, the kind of alhpa olefin comonomer and molar content and each reactor is different. Specifically comprise the following steps that
Alhpa olefin, normal hexane and hydrogen are joined in polymer reactor, and polymer reactor is heated to default polymerization temperature, afterwards vinyl monomer and catalyst system are added simultaneously in polymer reactor, and temperature be 140 DEG C, pressure be 2.5MPa when polyase 13 0 minute, respectively obtain component 1 and component 2. Wherein, the control of the melt index of component 1 and component 2 realizes by regulating the addition of hydrogen, and the control of density is realized by kind and the addition of adjustment alhpa olefin. In the process of preparation component 1, alhpa olefin used is 1-octene, and in the process of preparation component 2, alhpa olefin used is 1-butylene.
By the yield in unit time W of component 1 in the first reactor in preparation process1With the yield in unit time W of component 2 in the second reactor2Weight ratio maintain W1: W2=20:80.
After testing, said method the component 1 prepared and the performance of component 2 are as follows:
The melt index MI of component 11=0.1g/10min, density p1=0.920g/cm3, molecular weight distributing index Mw/Mn=3.1, the molar content=2.1mol% of alhpa olefin comonomer;
The melt index MI of component 22=25g/10min, density p2=0.920g/cm3, molecular weight distributing index Mw/Mn=3.5, the molar content=5.1mol% of alhpa olefin comonomer.
Above-mentioned prepared each component is transported in solid-liquid (gas) separator in yield in unit time ratio and carries out being separated and and then being transported to, in the homogenization silo stirred, then adding lubricant by proportioning and carry out mixing homogenizing. Wherein, lubricant is the Tissuemat E that Honeywell Inc. of the U.S. produces, and with the quality sum of said components 1 and component 2 for 100 parts by weight, the addition of lubricant is 1 weight portion. Afterwards the mixture of homogenized feed bin homogenizing is joined in the feeder of the double screw extruder that W&P company manufactures, material enters in twin screw via feeder, in the course of processing, the temperature of screw rod is maintained between 170-230 DEG C, through screw rod melting mixing uniformly, extrusion, pelletize drying, obtain polyethylene composition pellet, after testing its melt index MI=8.2g/10min.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 3, result shows, through repeatedly attempting, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) �� 2 times (MD), the highest stretching ratio of thin film TD is only 10%/s, i.e. stretching ratio and rate of extension are all too low, stretching film property is poor, does not possess practicality.
Test case
Test case is for illustrating polyethylene film and the test of reference polyethylene film performance.
(1) Film Haze: being measured according to the method for regulation in GB/T2410-2008, wherein, film sample thickness is 25 �� 5 ��m, and acquired results is as shown in table 1;
(2) film stretching intensity, modulus and tension fracture elongation rate: being measured according to the method for regulation in GB/T1040.3-2006, acquired results is as shown in table 1;
(3) membrane puncture intensity: being measured according to the method for regulation in GB/T10004-2008, wherein, film sample thickness is 25 �� 5 ��m, and acquired results is as shown in table 1.
Table 1
Result from table 1 can draw, embodiment 1-3 adopt polyethylene composition provided by the invention prepare biaxial tension PE thin film, have compared with the thin film of prior art that film forming multiplying power is big, rate of extension is fast, mechanical strength is high, the advantage of good in optical property, the performance of prepared thin film all can meet longitudinally (MD) hot strength >=55MPa, laterally (TD) hot strength >=65MPa, puncture strength >=2.5N, tension fracture elongation rate��350%. From the contrast of embodiment 1 and embodiment 5 it can be seen that work as the density p of component A, component B and component C described polyethylene compositionA����BAnd ��CBetween relation meet-0.04�ܦ�A-��B�� 0.02, and-0.04�ܦ�A-��CWhen��0.02, this polyethylene composition has on the basis of better film property, this polyethylene composition the thin film prepared also has higher hot strength and punctured resistance and relatively low mist degree. Can be seen that from the contrast of embodiment 1 with comparative example 1-2, adopt commercial polyethylene raw material prepared by prior art cannot stretch film forming, thus be not suitable for adopting Flat film strength to be processed, and compared with the inflation film of prior art, adopt the mechanical strength of the thin film of Flat film strength machine-shaping and puncture strength is higher and Film Haze is relatively low. Additionally, from the contrast of embodiment 1-3 and comparative example 3-5 it can be seen that adopt polyethylene composition provided by the invention as the raw material preparing thin film, there is better filming performance, more prospects for commercial application.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode. In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a polyethylene composition, it is characterised in that described polyethylene composition contains the component B that component A, component C and selectivity contain; Described component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3; Described component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 2.1-14.9g/10min, density pBFor 0.910-0.930g/cm3; Described component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3��
2. polyethylene composition according to claim 1, wherein, described component A temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-1.5g/10min, described component B temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 3-10g/10min, described component C temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 15-100g/10min; Preferably, described component A temperature be 190 DEG C, load be the melt index MI under 2.16kgAFor 0.01-1g/10min, described component B temperature be 190 DEG C, load be the melt index MI under 2.16kgBFor 3-5g/10min, described component C temperature be 190 DEG C, load be the melt index MI under 2.16kgCFor 20-60g/10min.
3. polyethylene composition according to claim 1, wherein, the density p of described component AAFor 0.910-0.930g/cm3, the density p of described component BBFor 0.913-0.928g/cm3, the density p of described component CCFor 0.905-0.928g/cm3; Preferably, the density p of described component AAFor 0.915-0.926g/cm3, the density p of described component BBFor 0.913-0.924g/cm3, the density p of described component CCFor 0.910-0.926g/cm3��
4. polyethylene composition according to claim 3, wherein, the density p of component A, component B and component C in described polyethylene compositionA����BAnd ��CBetween relation meet-0.04�ܦ�A-��B�� 0.02, and-0.04�ܦ�A-��C��0.02��
5. the polyethylene composition according to any one in claim 1-4, wherein, in described polyethylene composition, the mass fraction W of described component AAFor 25-90 weight portion, the mass fraction W of described component BBFor 0.1-10 weight portion, the mass fraction W of described component CCFor 10-75 weight portion; Preferably, in described polyethylene composition, the mass fraction W of described component AAFor 30-80 weight portion, the mass fraction W of described component BBFor 0.5-8 weight portion, the mass fraction W of described component CCFor 20-70 weight portion.
6. polyethylene composition according to claim 5, wherein, the mass fraction W of described component AAMass fraction W with component CCMelt index MI with component AARelation meet 5.2 �� lgMIA+11.6��WA/WC��0.9��lgMIA+ 2.1, it is preferable that meet 2.9 �� lgMIA+6.8��WA/WC��1.1��lgMIA+2.7��
7. polyethylene composition according to claim 6, wherein, with the gross weight of described polyethylene composition for benchmark, the mass percentage content M of described component BB�� 35 weight %, it is preferable that MB�� 25 weight %.
8. according to claim 1-4, polyethylene composition described in any one in 6 and 7, wherein, described polyethylene composition temperature be 190 DEG C, load be the melt index under 2.16kg be 0.1-20g/10min, it is preferred to 0.5-10g/10min.
9. the polyethylene composition according to any one in claim 1-4, wherein, the molecular weight distributing index of described component A, component B and component C is satisfied by Mw/Mn�� 4.5, it is preferable that meet 2.0��Mw/Mn��4.2��
10. polyethylene composition according to claim 9, wherein, described component A, component B and component C all adopt metallocene catalyst polymerisation to obtain.
11. the polyethylene composition according to any one in claim 1-4, wherein, in described component A, component B and component C, the molar content of alhpa olefin comonomer is each independently 0.2-15mol%, it is preferred to 1.5-10mol%.
12. polyethylene composition according to claim 11, wherein, the alhpa olefin in described component A, component B and component C is each independently C3-C20At least one in alkene, it is preferably propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, 4-methyl isophthalic acid-butylene, 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 isophthalic acid-hexene, 5-methyl isophthalic acid-hexene, 1-heptene, 2-heptene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, at least one in 1-vaccenic acid and 1-eicosylene, it is more preferably 1-butylene, at least one in 1-hexene and 1-octene.
13. the polyethylene composition according to any one in claim 1-4, wherein, described polyethylene composition is possibly together with lubricant; Preferably, with the gross weight of described component A, component B and component C for 100 parts by weight, the content of described lubricant is 0.05-5 weight portion; It is highly preferred that at least one that described lubricant is in Polyethylene Glycol series lubricant agent, fluoropolymer series lubricant agent, silicone based lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent.
14. a thin film, described thin film at least includes the polyethylene layer that one layer of polyethylene composition described in any one in claim 1-13 is formed.
15. thin film according to claim 14, wherein, described thin film has the composite construction of upper epidermis, sandwich layer and layer, and at least described sandwich layer is the polyethylene layer formed by described polyethylene composition; Preferably, when described thin film has the composite construction of upper epidermis, sandwich layer and layer, the thickness of described upper epidermis and layer is each independently the 1-25% of described film thickness.
16. thin film according to claim 14, wherein, described thin film is for be prepared biaxially oriented film by flat film biaxial tension method; Preferably, flat film biaxial tension method is being adopted to prepare in the process of described biaxially oriented film, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5 times; Flat film biaxial tension method is being adopted to prepare in the process of described biaxially oriented film, cross directional stretch speed >=50%/s.
17. the thin film according to any one in claim 14-16, wherein, the thickness of described thin film is 10-200 ��m, it is preferred to 10-100 ��m.
18. thin film according to claim 16, wherein, the longitudinal tensile strength >=55MPa of described biaxially oriented film, transverse tensile strength >=65MPa; Puncture strength >=the 2.5N of described biaxially oriented film; Tension fracture elongation rate��350% of described biaxially oriented film.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583605.8A CN105623059B (en) | 2014-10-27 | 2014-10-27 | A kind of polyethylene composition and its film |
| BR102015027108-5A BR102015027108B1 (en) | 2014-10-27 | 2015-10-26 | polyethylene composition and film |
| KR1020150149448A KR102400379B1 (en) | 2014-10-27 | 2015-10-27 | A polyethylen composition and a film formed therefrom |
| JP2015211332A JP6615572B2 (en) | 2014-10-27 | 2015-10-27 | Polyethylene compositions and films formed therefrom |
| US14/924,302 US9988505B2 (en) | 2014-10-27 | 2015-10-27 | Polyethylene compositions and films formed therefrom |
| EP15191626.9A EP3015502B1 (en) | 2014-10-27 | 2015-10-27 | A polyethylene composition and a film formed therefrom |
| ES15191626.9T ES2619196T3 (en) | 2014-10-27 | 2015-10-27 | Composition of polyethylene and film formed from it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583605.8A CN105623059B (en) | 2014-10-27 | 2014-10-27 | A kind of polyethylene composition and its film |
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| CN106633329A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethylene composition and film thereof |
| CN109720060A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Polyvinyl alcohol polyethylene laminated film and preparation method thereof |
| CN111662498A (en) * | 2019-03-08 | 2020-09-15 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN116239831A (en) * | 2021-12-08 | 2023-06-09 | 中国石油天然气股份有限公司 | Polyethylene composition and preparation method thereof, polyethylene film and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633329A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethylene composition and film thereof |
| CN109720060A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Polyvinyl alcohol polyethylene laminated film and preparation method thereof |
| CN109720060B (en) * | 2017-10-30 | 2021-02-05 | 中国石油化工股份有限公司 | Polyvinyl alcohol/polyethylene composite film and preparation method thereof |
| CN111662498A (en) * | 2019-03-08 | 2020-09-15 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN111662498B (en) * | 2019-03-08 | 2023-01-24 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN116239831A (en) * | 2021-12-08 | 2023-06-09 | 中国石油天然气股份有限公司 | Polyethylene composition and preparation method thereof, polyethylene film and preparation method thereof |
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