CN106633329B - A kind of polyethylene composition and its film - Google Patents

A kind of polyethylene composition and its film Download PDF

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Publication number
CN106633329B
CN106633329B CN201510740850.XA CN201510740850A CN106633329B CN 106633329 B CN106633329 B CN 106633329B CN 201510740850 A CN201510740850 A CN 201510740850A CN 106633329 B CN106633329 B CN 106633329B
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polyethylene composition
film
polyethylene
composition according
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CN106633329A (en
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徐萌
高达利
张师军
徐凯
尹华
邵静波
吕芸
董穆
郭梅芳
施红伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of polyethylene composition and its films.The polyethylene composition contains component A, component B, component C, nucleating agent and Petropols；The component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-14.9g/10min, density pBFor 0.910-0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3.When the polyethylene composition is prepared polyethylene film using Flat film strength, film forming is very good, and obtained film modulus with higher.

Description

A kind of polyethylene composition and its film
Technical field
The present invention relates to a kind of polyethylene composition and its films.
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, with The extrusioning blowing process of the prior art is compared with the polyethylene film product for squeezing out casting technique preparation, and BOPE film has mechanics The advantages such as intensity is high, puncture resistant and shock resistance are good, excellent optical performance, environmental protection and energy saving.Therefore, BOPE film can be wide It is general to be used for 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 biaxial tension processing method of currently used plastic film has Flat film strength and envelope pulling method.Flat membrane stretches Method has been applied in the processing of the thin-film materials such as polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) In, technique is more mature.Compared with envelope pulling method, the stretching ratio of Flat film strength is big, and (cross directional stretch multiplying power is up to 10 times More than), shaping speed fast (highest rolling speed is up to hundreds of ms/min), high production efficiency, and the mechanics of obtained film More preferably, but film forming is influenced significantly by process condition fluctuations for intensity, optical property and the thickness uniformity, film stretch plus Work difficulty is big, has higher requirement for film raw material.Existing Biaxially-oriented polyethylene raw material is only applicable to pipe substantially When steeping pulling method and prepare BOPE film, and these existing polyethylene raw materials being prepared BOPE film using Flat film strength, deposit The defect of rupture is easy to appear in film forming poor (tensile speed and stretching ratio are very low), film, that is, is not suitable for substantially using flat Film stretching method prepares film.Therefore, it in order to make full use of the above-mentioned advantage of Flat film strength, needs to develop a kind of film forming at present The polyethylene raw material for being suitable for Flat film strength and preparing BOPE film that good and film is not easy to occur rupturing.
Although toughness is preferable, its modulus is usually lower in addition, polyethylene film is more soft, and modern film is raw Production. art develops to mass rapidization, especially stretch processes, faster compared with envelope pulling method due to speed of production, If the modulus of film is insufficient, the problem of film surface pleating easily occurs in process of production, and for certain packaging applicationss, Such as self-standing bag, it is also desirable to film itself modulus with higher.
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 film using Flat film strength, and obtained polyethylene is thin The lower defect of the modulus of film, and a kind of new polyethylene composition and the film made of the polyethylene composition are provided.
Specifically, polyethylene composition provided by the invention contains component A, component B, component C, nucleating agent and petroleum tree Rouge；The component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, in the case where temperature is 190 DEG C, load is 2.16kg Melt index MFRAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is total for ethylene/alpha-olefin Poly- linear low density polyethylene, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-14.9g/ 10min, density pBFor 0.910-0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, Melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-150g/10min, density pCFor 0.880- 0.930g/cm3。
Film provided by the invention includes at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The present inventor has found after further investigation, by the above-mentioned component A with particular melt index and density, Polyethylene composition obtained from component B and component C and nucleating agent and Petropols are used cooperatively uses Flat film strength system When standby polyethylene film, has the advantages that stretching ratio is big, rate of film build is high, can satisfy Flat film strength to polyethylene raw material High requirement, and adapt to the economy demand of existing Flat film strength production line, and obtained polyethylene film also has There are the advantages of high-modulus, great prospects for commercial application.
A preferred embodiment of the invention, the mass fraction of the component A described in the polyethylene composition WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10- When 75 parts by weight, the polyethylene composition is in the polyethylene film modulus with higher with preferable film forming and acquisition On the basis of, the film being prepared by the polyethylene composition also has lower mist degree.
According to another preferred method of implementation of the present invention, when the molecular weight distribution of the component A, component B and component C refer to Number is all satisfied Mw/MnWhen≤4.5, the polyethylene composition with preferable film forming and obtain polyethylene film have compared with On the basis of high modulus, the film puncture resistance also with higher that is prepared by the polyethylene composition.
According to another preferred method of implementation of the present invention, when component A, component B and component C in the polyethylene composition Density pA、ρBAnd ρCBetween relationship meet -0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρCWhen≤0.02, the polyethylene Composition is on the basis of the modulus with higher of the polyethylene film with preferable film forming and acquisition, by the polyethylene group The film that conjunction object is prepared also has the advantages that tensile strength and punctured resistance is high and mist degree is low.
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 for being 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.
Polyethylene composition provided by the invention contains component A, component B, component C, nucleating agent and Petropols；Described group Dividing A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, and the melting in the case where temperature is 190 DEG C, load is 2.16kg refers to Number MFRAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is the linear of ethylene/alpha-olefin copolymerization Low density polyethylene (LDPE), the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgBIt is close for 2.1-14.9g/10min Spend ρBFor 0.910-0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, is in temperature 190 DEG C, load be 2.16kg under melt index MFRCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3。
The polyethylene composition provided according to the present invention, it is preferable that the component A is temperature is 190 DEG C, load is Melt index MFR under 2.16kgAFor 0.01-1.5g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MFRBFor 3-10g/10min, melt index of the component C in the case where temperature is 190 DEG C, load is 2.16kg MFRCFor 15-100g/10min.It is highly preferred that melt index of the component A in the case where temperature is 190 DEG C, load is 2.16kg MFRAFor 0.01-1g/10min, melt index MFR of the component B in the case where temperature is 190 DEG C, load is 2.16kgBFor 3-5g/ The melt index MFR of 10min, the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 20-60g/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.
The polyethylene composition provided according to the present invention, it is preferable that the density p of the component AAFor 0.910-0.930g/ cm3, the density p of the component BBFor 0.913-0.928g/cm3, the density p of the component CCFor 0.905-0.928g/cm3.More Preferably, the density p of the component AAFor 0.915-0.926g/cm3, the density p of the component BBFor 0.913-0.924g/ cm3, the density p of the component CCFor 0.910-0.926g/cm3.It is particularly preferred that component A, group in the polyethylene composition The density p of part B and component CA、ρBAnd ρCBetween relationship meet -0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρC≤ 0.02, The polyethylene composition enabled in this way has higher in the polyethylene film with preferable filming performance and acquisition Modulus on the basis of, also there is very high tensile strength and punctured resistance and lower mist degree.
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.
The polyethylene composition provided according to the present invention, in order to enable the polyethylene composition arrived is with good filming On the basis of the polyethylene film modulus with higher that can and obtain, also there is preferable optical property, it is preferable that in institute It states in polyethylene composition, the mass fraction W of the component AAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10-75 parts by weight；It is highly preferred that in the polyethylene composition In, the mass fraction W of the component AAFor 30-80 parts by weight, the mass fraction W of the component BBIt is described for 0.5-8 parts by weight The mass fraction W of component CCFor 20-70 parts by weight.Further, the mass fraction W of the component AAWith the mass fraction of component C WCWith the melt index MFR of component AARelationship preferably satisfy 5.2 × lgMFRA+11.6≥WA/WC≥0.9×lgMFRA+ 2.1, More preferably meet 2.9 × lgMFRA+6.8≥WA/WC≥1.1×lgMFRA+ 2.7, the polyethylene composition is enabled in this way There is bigger stretching ratio and higher rate of extension in flat membrane method film biaxial tension processing.
The polyethylene composition provided according to the present invention, particularly preferably, the polyethylene composition is 190 in temperature DEG C, the melt index under load is 2.16kg be 0.1-20g/10min, most preferably 0.5-10g/10min.It is above-mentioned that will have On the basis of particular melt index and the component A of density, component B and component C and nucleating agent and Petropols are used cooperatively, as general When the melt index of the polyethylene composition entirety is controlled in above-mentioned preferred range, the polyethylene composition that enables to Object has very excellent film forming, tensile strength, punctured resistance and modulus and lower mist degree simultaneously.
The polyethylene composition provided according to the present invention, it is preferable that the molecular weight of the component A, component B and component C point Cloth index is all satisfied Mw/Mn≤ 4.5, more preferably 2.0≤M of satisfactionw/Mn≤4.2.Specifically, in order to obtain with above-mentioned molecular weight Component A, the component B and component C of distribution, the component A, component B and component C are all made of metallocene catalyst polymerisation and obtain.Its In, the type of the metallocene catalyst can be the conventional selection of this field, usually by metallocene compound and organo-aluminium Compound and optional electron donor composition, are specifically known to the skilled person, therefore not to repeat here.Hair of the invention Bright people has found after further investigation, the group with above-mentioned melt index and density that will be obtained using metallocene catalyst polymerisation A, component B and component C and nucleating agent and Petropols is divided to be used cooperatively, obtained polyethylene composition is with good filming On the basis of performance and obtained polyethylene film modulus with higher, also there is very high puncture energy, very Suitable for packaging material.
The present invention is not particularly limited the content of alhpa olefin comonomer in the component A, component B and component C, example Such as, the molar content of alhpa olefin comonomer can be each independently 0.2- in the component A, component B and component C 15mol%, preferably 1.5-10mol%.In the present invention, the molar content of alhpa olefin comonomer refers to by alpha-olefin polymerization shape At structural unit mole account for total monomer structural unit mole ratio.In addition, the component A, component B and component Alhpa olefin in C is each independently C3-C20At least one of alkene.The angle ready availability from raw material, the component A, Alhpa olefin in component B and component C is preferably propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl-1-butylene, 1- Amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 3,3- dimethyl -1- amylene, 3,4- dimethyl -1- amylene, 4,4- diformazan Base-1- amylene, 1- hexene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- ten At least one of two (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, (carbon) alkene of 1- 18 and 1- 20 (carbon) alkene, more Preferably at least one of 1- butylene, 1- hexene and 1- octene.
The present invention is not particularly limited the content of each component in the polyethylene composition, for example, with the component A, the total content of component B and component C are 100 parts by weight meters, and the content of the nucleating agent can be 0.01-0.25 parts by weight, institute The content for stating Petropols can be 10-15 parts by weight；It is highly preferred that being with the total content of the component A, component B and component C 100 parts by weight meters, the content of the nucleating agent are 0.1-0.25 parts by weight, and the content of the Petropols is 10-12 parts by weight.
In polyethylene composition provided by the invention, the crystalline rate of each component has certain difference, the nucleating agent Can play the role of induce polyethylene generate a large amount of crystallites and improve crystalline rate, thus reduce each component crystal size and The inhomogeneities of crystalline rate can play stable pulling membrane process and further increase the work of polyethylene film optical property With, and nucleating agent can also make the structure of film crystalline region part more perfect, to improve the modulus of crystalline region part.
The type of the nucleating agent can be the conventional selection of this field, for example, can for Sorbitol Nucleator and/or Aryl phosphoric acids salt nucleating agent.
The specific example of the Sorbitol Nucleator can include but is not limited to: 1,3:2,4- bis- (benzylidene)-D- Sorbierite, 1,3:2,4- bis- (4- methylbenzene subunit)-D-glucitol, 1,3:2,4- bis- (3,4- dimethylbenzylidene) mountain-D- Pears alcohol, 1,3:2,4- bis- (4- ethyl benzylidene)-D-glucitol, double -1,3:2,4- (4 '-propyl benzal) -1- allyl Sorbierite, double -1,3:2,4- (4 '-ethylbenzylidene) -1- allyl sorbitol, double -1,3:2,4- (4 '-propoxyl group benzal Base) -1- allyl sorbitol, double -1,3:2,4- (4 '-propyl benzal) -1- propyl sorbierite, double -1,3:2,4- (4 '-the third Oxygroup benzal) -1- propyl sorbierite.The Sorbitol Nucleator is preferably (the 3,4- dimethyl benzene methylene of 1,3:2,4- bis- Base)-D-glucitol (can such as be purchased from Milliken Co., the U.S., the trade mark is Millad 3988) and/or double -1,3:2,4- (4 ' - Propyl benzal) -1- propyl sorbierite (as disclosed in CN101484458A, can be purchased from Milliken Co., the U.S., the trade mark be NX8000), particularly preferably double -1,3:2,4- (4 '-propyl benzal) -1- propyl sorbierite.
The specific example of the aryl phosphoric acids salt nucleating agent can include but is not limited to: 2,2 '-methylene-bis- (4,6- Di-tert-butyl-phenyl) sodium phosphate, 2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene-bis- (4, 6- di-tert-butyl-phenyl) lithium phosphate, 2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) lithium phosphate, 2,2 '-ethidines-bis- (4- isopropyl -6- di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene-bis- (4- methyl -6- di-tert-butyl-phenyl) lithium phosphate, 2,2 '-methylene-bis- (4- ethyl -6- di-tert-butyl-phenyl) lithium phosphate, bis- [2,2 '-thiobis (4- methyl -6- di-t-butyls Phenyl) calcium phosphate], bis- [2,2 '-thiobis (4- ethyl -6- di-tert-butyl-phenyl) calcium phosphate], bis- [2,2 '-thiobis (4,6- Di-tert-butyl-phenyl) calcium phosphate], bis- [2,2 '-thiobis (4,6- di-tert-butyl-phenyl) magnesium phosphates], bis- [2,2 '-thiobis (bis- t-octyl phenyl of 4,6-) magnesium phosphate], 2,2 '-butanes-bis- (4,6- 3,5-dimethylphenyl) sodium phosphate, 2,2 '-t-octyls it is sub- It is bis- (4,6- 3,5-dimethylphenyl) sodium phosphates of methyl-, 2,2 '-t-octyl methylene-bis- (4,6- di-tert-butyl-phenyl) sodium phosphate, double [2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyl) calcium phosphate], bis- [2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyl) Magnesium phosphate], bis- [2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyl) barium phosphates], 2,2 '-methylene-bis- (4- methyl-6-tert Butyl phenyl) sodium phosphate, 2,2 '-methylene-bis- (4- ethyl -6- tert-butyl-phenyl) sodium phosphate, it is bis- [4,4 '-dimethyl -6, 6 '-di-t-butyls -2,2 '-xenyl) calcium phosphate], 2,2 '-ethidines-bis- (the m- butyl -6- tert-butyl-phenyl of 4-) sodium phosphate, 2,2 '-methylene-bis- (4,6- 3,5-dimethylphenyl) sodium phosphate, 2,2 '-methylene-bis- (4,6- diethyl phenyl) sodium phosphate, 2, 2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) potassium phosphate, bis- [2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) phosphoric acid Calcium], bis- [2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) magnesium phosphates], bis- [2,2 '-ethidines-bis- (4,6- di-t-butyls Phenyl) barium phosphate], hydroxyl-bis- [2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) aluminum phosphates], three bis- [2,2 '-ethylidenes Bis- (4,6- di-tert-butyl-phenyl) aluminum phosphates of base -], bis- [2,4,8,10- tetra- (1,1 '-the dimethyl ethyl) -6- hydroxyls-of hydroxyl - Eight ring -6- oxygen of 12H- dibenzo [d, g] dioxy phospha] close aluminium.The aryl phosphoric acids salt nucleating agent is preferably 2,2 '-methylenes Bis- (4,6- di-tert-butyl-phenyl) sodium phosphates of base-, hydroxyl-are bis- [2,2 '-ethidines-bis- (4,6- di-tert-butyl-phenyl) aluminum phosphate] With the bis- [eight ring -6- of 2,4,8,10- tetra- (1,1 '-dimethyl ethyl) -6- hydroxyl -12H- dibenzo [d, g] dioxy phospha of hydroxyl - Oxygen] close one of aluminium or a variety of.The aryl phosphoric acids salt nucleating agent can be commercially available, for example, day can be purchased from This rising sun electrification company, the trade mark be ADK NA-11 (2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyl) sodium ascorbyl phosphate) and/or ADK NA-21 (main component are as follows: bis- [2,4,8,10- tetra- (1,1 '-the dimethyl ethyl) -6- hydroxyl -12H- dibenzo of hydroxyl - Eight ring -6- oxygen of [d, g] dioxy phospha] close aluminium) aryl phosphoric acids salt nucleating agent.
Since the molecular weight of Petropols is usually smaller, structure is special, can play the role of stretching lubricant, so that thin Drawing force needed for film stretching is smaller, and drawing process is more stable.In addition, Petropols can not participate in the crystallization of polyethylene, finally It can be present in the amorphous area of polyethylene film, Petropols sheet has very high modulus, therefore energy as rigid annular structure Enough improve the modulus of polyethylene film amorphous area.
In the present invention, the Petropols are preferably Petropols that does not contain a polar group.The Petropols refer to The aggregated obtained resin of the mixtures such as alkene, alkadienes, cycloolefin, styrene derivative and the heterocyclic compound of petroleum distillate Shape substance.Under preferable case, the Petropols are the C in petroleum cracking byproduct5Fraction and/or C9Fraction is through pre-treatment, poly- A kind of thermoplastic resin of the techniques production such as conjunction, distillation, softening point are 100-150 DEG C.Wherein, softening point refers to that substance softens Temperature, that is, Petropols start soften when temperature.Petropols can make its color from yellow after carrying out hydrotreating It becomes colorless to light yellow, therefore preferably C5And/or C9Hydrogenated petroleum resin, most preferably Cyclopeutadiene type resin or with Its resin as the higher alkene of main component.The Petropols can be commercially available, for example, can be purchased from The C of Exxonmobil company5Petropols and/or C9Petropols.
The polyethylene composition provided according to the present invention, it is preferable that the polyethylene composition also contains lubricant, in this way The extrusion processability energy of the polyethylene composition can be improved.The type and dosage of the lubricant all can be this field Conventional selection, for example, the lubricant can be selected from polyethylene glycol (PEG) series lubricant agent, fluoropolymer series lubricant agent, organic Silicon series lubricant agent, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, Fatty acid metal soaps lubricant, alkane and at least one of oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent. Specifically, the PEG series lubricant agent for example can be the PEG molecule that molecular weight is 500-50000, can be by blocking, connecing Branch, crosslinking Treatment, can also pass through other chemical modifications or physical modification.The fluoropolymer series lubricant agent for example can be At least one of polytetrafluoroethylene (PTFE), Kynoar, polyhexafluoropropylene etc., or other are unimodal or multimodal fluorine-containing poly- Close object and crystallization or hemicrystalline fluoropolymer.The organo-silicic oil can be existing various with carbon, silicon atom For molecular backbone, using the oligomer of the organic groups such as methyl, phenyl, alkoxy, vinyl or oligomer as the compound of side chain. The fatty alcohol type emollients can be for example at least one of soft fat alcohol, tallow alcohol, tallow fatty alcohol etc..The rouge Fat acids lubricant for example can be with stearic acid and/or 12- hydroxy stearic acid.The fatty acid ester type emollients for example can be hard At least one of resin acid butyl ester, stearic acid list glycerolipid, cetyl palmitate, tearyl base ester etc..It is described Stearic amide series lubricant agent for example can be stearic amide, oleamide, erucyl amide, n, n- ethylene bis stearic acid amide At least one of (EBS) etc..The fatty acid metal soaps lubricant for example can be lead stearate, calcium stearate, tristearin At least one of sour magnesium, synthesis calcium acetate etc..The alkane and oxidation of alkanes series lubricant agent can be for example atoleine, consolidate At least one of body paraffin, polyethylene wax, polypropylene wax, ethylene oxide wax etc..The micro-and nano-particles series lubricant agent is for example It 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 parts by weight Meter, 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 polyethylene composition can be prepared according to existing various methods, for example, first prepare respectively component A, Component B and component C, the lubrication then contained by the component A, component B, component C, nucleating agent and Petropols and selectively 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.
A preferred embodiment of the invention, the polyethylene composition multiple reactor as shown in Figure 1 simultaneously Be prepared in coupling device, the multiple reactor shunting means include first reactor 1, second reactor 2, third reactor 3, Solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization system 6, wherein the first reactor 1,2 and of second reactor Third reactor 3 is connected in parallel, and the number of solid-liquid (gas) separator 4 is three, anti-with first reactor 1, second respectively Answer device 2 to be connected to third reactor 3, the component A that is prepared by first reactor 1, the component B prepared by second reactor 2 and The component C prepared by third reactor 3 is mutually separated in different solid-liquid (gas) separators 4 respectively, then will be through phase point Component A, component B and component C from after be delivered in homogenization silo 5 in proportion and with nucleating agent, Petropols and other add Add agent to be mixed together uniformly, is sent into melt pelletization system 6 carries out extruding pelletization later.Wherein, the polymerization in each reactor can To be batchwise polymerization, it is also possible to continuous polymerization.When using multiple reactor parallel polymerization, W hereinafterA、WBAnd WCFor each group Divide the yield in unit time in respective reaction device.
Film provided by the invention includes at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The film can have single layer structure, it is possible to have multilayered structure.When the film is multilayered structure, until Few sandwich layer (the usually maximum layer of thickness) is the polyethylene layer formed by the polyethylene composition.For example, the film can With the composite construction with upper epidermis, sandwich layer and layer, and at least described sandwich layer is formed by the polyethylene composition Polyethylene layer.Usually, the thickness of the film can be 10-200 μm, preferably 10-100 μm.In addition, working as the film When composite construction with upper epidermis, sandwich layer and layer, the thickness of the upper epidermis and layer is each independently described The 1-25% of film thickness.
In addition, the film can be monodirectional tension film, or biaxially oriented film, preferably bidirectional stretching are thin Film, the biaxially oriented film being more preferably prepared by flat membrane biaxial tension method.
It is known to the skilled person using the process that flat membrane biaxial tension method prepares biaxially oriented film.Specifically, First above-mentioned polyethylene composition is added in casting apparatus and squeeze out curtain coating slab, it is then that obtained slab is double in film Drawing and forming is carried out into stretcher.During squeezing out curtain coating, slab die head can according to need the knot of the film of acquisition Structure is selected, for example, can use single layer die when needing to obtain the film with single layer structure；When needs are had It, can be multiple using multilayered structure when having film (film with upper epidermis, sandwich layer and layer three-decker) of multilayered structure Head is molded, and at least one layer of (sandwich layer) and the extruder that above-mentioned polyethylene composition is housed in the compound die head of the multilayered structure Hopper is connected to, and at least one layer (sandwich layer) in the film enabled in this way is the poly- second formed by above-mentioned polyethylene composition Alkene 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, The biaxial tension (can carry out film longitudinal (MD) simultaneously and laterally (TD) is stretched) using Synchronos method drawing process, can also (first to carry out film longitudinal stretching using method of fractional steps drawing process, then carry out film cross directional stretch).The Synchronos method stretches Specifically comprises the processes of: the slab carries out the stretching of vertical and horizontal direction after being fully warmed-up, wherein preheating temperature can Think 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.What the method for fractional steps stretched specifically comprises the processes of: 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.
Film provided by the invention has preferable film forming and stretching ratio is big, rate of extension is high.Using flat membrane During pulling method prepares the biaxially oriented film, as described above, stretching ratio >=4 times longitudinal direction (MD) of the film, Laterally stretching ratio >=5 times (TD).Stretching ratio is bigger, then the mechanical strength of film is higher.The transverse direction (TD) of the film is drawn Rate >=50%/s, preferably 60-100%/s are stretched, can guarantee to industrialize continuous production in this way.
Film mechanical strength with higher provided by the invention and preferable optical property.The biaxially oriented film It can meet: longitudinal (MD) tensile strength >=65MPa, preferably >=70MPa；Laterally (TD) tensile strength >=80MPa, preferably ≥90MPa；Longitudinal (MD) modulus >=250MPa, preferably >=300MPa；Laterally (TD) modulus >=300MPa, preferably >= 350MPa.Puncture strength >=2.5N of the biaxially oriented film, preferably >=3.5N.In the present invention, the longitudinal stretching Intensity, transverse tensile strength, longitudinal modulus and transverse modulus are measured according to method specified in GB/T 1040.3-2006. The puncture strength is measured according to method specified in GB/T 10004-2008, wherein film sample with a thickness of 25 ± 5μm。
The production cost of film provided by the invention is low, processing technology is simple, versatility is good, has widened polyethylene film Application field.
The present invention will be described in detail by way of examples below.
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, 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) it melt index (MFR): is measured according to method specified in GB/T 3682-2000, wherein test temperature It is 190 DEG C, load 2.16kg；
(3) it density: is measured according to method specified in GB/T 1033.2-2010 and using density gradient column method；
(4) it film tensile strength and modulus: is measured according to method specified in GB/T 1040.3-2006；
(5) it membrane puncture intensity: is measured according to method specified in GB/T 10004-2008；
(6) it Film Haze: is measured according to method specified in GB/T 2410-2008.
Embodiment 1
The present embodiment is for illustrating polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition:
Polyethylene composition provided in this embodiment is by component A, component B, component C, nucleating agent, Petropols, lubricant It is formed with antioxidant, wherein component A, component B, component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization (LLDPE), and it is all made of identical catalyst system (metallocene catalyst) and polymerization technique preparation, difference is to prepare different The type and molar content of the amounts of hydrogen and alhpa olefin comonomer that enter added by group timesharing are 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 MFR of component AA=1.5g/10min, density pA=0.913g/cm3, molecular weight distributing index Mw/Mn =3.4, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MFR of component BB=2.1g/10min, density pB=0.913g/cm3, molecular weight distributing index Mw/Mn =3.2, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MFR 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 80 weight Part, the mass fraction W of component BBFor 10 parts by weight, the mass fraction W of component CCFor 20 parts by weight, WA/WC=4 (satisfaction 5.2 × lgMFRA+11.6≥WA/WC≥0.9×lgMFRA+ 2.1, also meet 2.9 × lgMFRA+6.8≥WA/WC≥1.1×lgMFRA+ 2.7)；Then nucleating agent, Petropols, lubricant and antioxidant is added, and (specific type and dosage are as shown in table 1, wherein petroleum Resin is the C purchased from Japanese Chu Guang company9Petropols, softening point are 125 DEG C；Lubricant is the production of Switzerland's Clariant Corporation PEG lubricant, molecular weight 10000；Antioxidant is purchased from Ciba, Switzerland, and the trade mark is respectively 1010 and 168), later will mixing Object is added in high speed agitator and is uniformly mixed, then the material mixed is added to the double screw extruder of W&P company manufacture Feeder in, 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 polyethylene composition pellet, detected its melt index MFR=3.6g/10min.
(2) preparation of polyethylene film:
Polyethylene composition pellet made from step (1) is dried, is added to the type of Labtech company, Sweden later Number melting extrusion and be cast in the sandwich layer extruder and upper and lower surface layer extruder of the multilayer extrusion casting machine of LCR400 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 table The weight ratio of the antitack agent and polyethylene composition pellet that are added in layer extruder is 0.02:1, during being cast slab, Curtain coating chilling roll temperature is set as 25 DEG C, polyethylene thickness slab is made, is made of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 100 DEG C, MD Draft temperature is 110 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 100 DEG C, and TD draft temperature is 115 DEG C, and TD is stretched again Rate is 5 times, and film TD rate of extension is 60%/s；Film setting temperature is 120 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and upper epidermis and following table Also contain antitack agent in layer, the thickness of upper epidermis and layer is 0.5 μm.Gained film performance is as shown in table 2.
Embodiment 2
The present embodiment is for illustrating polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition:
Polyethylene composition provided in this embodiment is by component A, component B, component C, nucleating agent, Petropols, lubricant It is formed with antioxidant, wherein component A, component B, component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization (LLDPE), and it is all made of identical catalyst system (metallocene catalyst) and polymerization technique preparation, difference is to prepare different The type and molar content of the amounts of hydrogen and alhpa olefin comonomer that enter added by group timesharing are 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 MFR of component AA=0.01g/10min, density pA=0.930g/cm3, molecular weight distributing index Mw/Mn =3.0, molar content=1.6mol% of alhpa olefin comonomer；
The melt index MFR of component BB=10.0g/10min, density pB=0.930g/cm3, molecular weight distributing index Mw/Mn =2.8, molar content=1.9mol% of alhpa olefin comonomer；
The melt index MFR of component CC=60g/10min, density pC=0.922g/cm3, molecular weight distributing index Mw/Mn= 2.9, molar content=3.8mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 55 weight Part, the mass fraction W of component BBFor 5 parts by weight, the mass fraction W of component CCFor 55 parts by weight, WA/WC=1 (satisfaction 5.2 × lgMFRA+11.6≥WA/WC≥0.9×lgMFRA+ 2.1, also meet 2.9 × lgMFRA+6.8≥WA/WC≥1.1×lgMFRA+ 2.7)；Then nucleating agent, Petropols, lubricant and antioxidant is added, and (specific type and dosage are as shown in table 1, wherein petroleum Resin is the C purchased from Japanese Chu Guang company9Petropols, softening point are 125 DEG C；Lubricant is the production of Switzerland's Clariant Corporation PEG lubricant, molecular weight 6000；Antioxidant is purchased from Ciba, Switzerland, and the trade mark is respectively 1010 and 168), later by mixture It is added in high speed agitator and is uniformly mixed, then the material mixed is added to the double screw extruder of W&P company manufacture In feeder, material enters in twin-screw via feeder, and the temperature of screw rod is maintained between 180-240 DEG C in process, Through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition pellet, detected its melt index MFR= 1.4g/10min。
(2) preparation of polyethylene film:
Polyethylene composition pellet made from step (1) is dried, is added to the type of Labtech company, Sweden later Number melting extrusion and be cast in the sandwich layer extruder and upper and lower surface layer extruder of the multilayer extrusion casting machine of LCR400 Slab, wherein it also needs that inorganic antitack agent is added in the upper and lower surface layer extruder, and be added in the extruder of upper and lower surface layer The weight ratio of antitack agent and polyethylene composition pellet is 0.02:1, during being cast slab, will be cast chilling roll temperature It is set as 85 DEG C, polyethylene thickness slab is made, is made of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 130 DEG C, MD Draft temperature is 126 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 130 DEG C, and TD draft temperature is 128 DEG C, and TD is stretched again Rate is 6 times, and film TD rate of extension is 100%/s；Film setting temperature is 130 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and upper epidermis and following table Also contain antitack agent in layer, the thickness of upper epidermis and layer is 1 μm.Gained film performance is as shown in table 2.
Embodiment 3
The present embodiment is for illustrating polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition:
Polyethylene composition provided in this embodiment polymerize to obtain using multiple reactor shunting means shown in FIG. 1, wherein The polymerization preparation of first reactor 1 component A, the polymerization preparation of second reactor 2 component B, the polymerization preparation component C of third reactor 3, group Dividing A, component B and component C is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, these three components are all made of phase Same catalyst system (metallocene catalyst) and polymerization technique preparation, the hydrogen that difference is added when being to prepare different component Amount, the type of alhpa olefin comonomer and molar content and the yield in unit time of each reactor are different.Specific steps are such as Under:
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to preset polymerization Vinyl monomer and catalyst system are added in polymer reactor by temperature simultaneously later, and temperature is 140 DEG C, pressure is Polyase 13 0 minute under conditions of 2.5MPa respectively obtains component A, component B and component C.Wherein, component A, component B and component C The control of melt index realizes that the control of density passes through the type and addition that adjust alhpa olefin by adjusting the additional amount of hydrogen It measures and realizes.Alhpa olefin used is 1- octene during preparing component A, and preparing alhpa olefin used during component B is 1- fourth Alkene, alhpa olefin used is 1- butylene during preparing component C.
During the preparation process by the yield in unit time W of component A in first reactor 1A, component B in second reactor 2 Yield in unit time WBWith the yield in unit time W of component C in third reactor 3CWeight ratio maintain WA: WB: WC=75:2: 35, wherein WA/WC=2.1 (meet 5.2 × lgMFRA+11.6≥WA/WC≥0.9×lgMFRA+ 2.1, also meet 2.9 × lgMFRA+6.8≥WA/WC≥1.1×lgMFRA+2.7)。
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows:
The melt index MFR of component AA=0.1g/10min, density pA=0.920g/cm3, molecular weight distributing index Mw/Mn =3.1, molar content=2.1mol% of alhpa olefin comonomer；
The melt index MFR of component BB=5.0g/10min, density pB=0.920g/cm3, molecular weight distributing index Mw/Mn =3.5, molar content=5.1mol% of alhpa olefin comonomer；
The melt index MFR of component CC=25g/10min, density pC=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.2, molar content=5.1mol% of alhpa olefin comonomer.
Each component obtained above is respectively delivered to different solid-liquids (gas) separator 4 in yield in unit time ratio It is middle progress mutually separation and and then is transported to stirring homogenization silo 5 in, then according to the ratio be added nucleating agent, Petropols, (specific type and dosage are as shown in table 1, wherein Petropols are the C purchased from Japanese Chu Guang company for lubricant and antioxidant9Stone Oleoresin, softening point are 125 DEG C；Lubricant is the polyethylene wax of Honeywell Inc., U.S. production；Antioxidant is purchased from Switzerland's vapour Bagong department, the trade mark are respectively 1010 and 168) carry out mixing homogenizing, add mixture to the twin-screw of W&P company manufacture later In the feeder of extruder, material enters in twin-screw via feeder, and the temperature of screw rod is maintained at 170-230 in process Between DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition pellet, detected its melting and referred to Number MFR=0.9g/10min.
(2) preparation of polyethylene film:
Polyethylene composition pellet made from step (1) is dried, is added to the type of Labtech company, Sweden later It, will curtain coating urgency during be cast slab number to carry out melting extrusion and being cast slab in the multilayer extrusion casting machine of LCR400 Chilling roller temperature is set as 35 DEG C, and polyethylene thickness slab is made, which is single layer structure.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 116 DEG C, MD Draft temperature is 118 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 120 DEG C, and TD draft temperature is 120 DEG C, and TD is stretched again Rate is 5 times, and film TD rate of extension is 100%/s；Film setting temperature is 122 DEG C, obtains the single layer that average thickness is 25 μm Film.Gained film performance is as shown in table 2.
Embodiment 4
The present embodiment is for illustrating polyethylene composition and its film provided by the invention.
Polyethylene composition and polyethylene film are prepared according to the method for embodiment 1, unlike, the preparation of component A The dosage of each substance is different in the process, so that the density p of component A, component B and component CA、ρBAnd ρCBetween relationship be unsatisfactory for- 0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρC≤ 0.02, obtain the film that average thickness is 25 μm, wherein upper epidermis is under The thickness on surface layer is 0.5 μm.In the preparation process of the component A, the performance of obtained component A is as follows: the melting of component A Index M FRA=1.5g/10min, density pA=0.928g/cm3, molecular weight distributing index Mw/Mn=3.0, alhpa olefin comonomer Molar content=1.9mol%.The specific formula of the polyethylene composition is shown in Table 1, and the performance of gained film is as shown in table 2.
Comparative example 1
This comparative example is used to illustrate the polyethylene raw material and its film of reference.
(1) polyethylene raw material:
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 MFR=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 1, unlike, by the polyethylene composition pellet with identical The polyethylene raw material of this comparative example step (1) of parts by weight substitutes, and is repeatedly attempted the case where stretching rupture of membranes, no farad occur It is stretched into film.In addition, repeatedly being attempted still to occur after the TD rate of extension in polyethylene film preparation process is down to 50%/s The case where stretching rupture of membranes, can not stretch film forming.
Comparative example 2
This comparative example is used to illustrate the polyethylene raw material and its film of reference.
(1) preparation of polyethylene composition:
By the polyethylene raw material of comparative example 1 and nucleating agent, Petropols, lubricant, (specific type and dosage are such as antioxidant Shown in table 1, wherein the dosage of polyethylene raw material is 100 parts by weight；Petropols are the C purchased from Japanese Chu Guang company9Petroleum tree Rouge, softening point are 125 DEG C；Lubricant is the polyethylene wax of Honeywell Inc., U.S. production；Antioxidant is purchased from Switzerland's vapour Bagong Department, the trade mark, which is respectively 1010 and 168) is added in high speed agitator, to be uniformly mixed, then the material mixed is added to W&P public affairs It takes charge of in the feeder of the double screw extruder of manufacture, material enters in twin-screw via feeder, the temperature of screw rod in process Degree be maintained between 170-230 DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition grain Material.
(2) preparation of polyethylene film:
The polyethylene film of this comparative example uses the upper blowing method film blowing device extrusion and blow molding of DR.COLLIN company, Germany It obtains, the specific method is as follows: the polyethylene composition pellet that above-mentioned steps (1) is chosen being added to upper blowing method film blowing device and is squeezed out In the hopper of machine, raw material after the abundant fusion plastification of extruder, by head annular die extrusion melt membrane tube is made, after pass through Compressed air inflation (blow-up ratio is 2.5 times), and polyethylene film is made after vane is cooling, wherein film is that average thickness is 25 μm of single layer structure.The performance of gained film is as shown in table 2.
Comparative example 3
This comparative example is used to illustrate the polyethylene composition and its film of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides is made of component 1, component 2, lubricant and antioxidant, wherein component 1 With component 2 it is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and is all made of identical catalyst system The preparation of (metallocene catalyst) and polymerization technique, the amounts of hydrogen and alhpa olefin that difference is added when being to prepare different component are total The type and molar content of polycondensation monomer are 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 1 and component 2.Its In, the control of the melt index of component 1 and component 2 is realized by adjusting the additional amount of hydrogen, and the control of density is by adjusting α The type and additional amount of alkene and realize.Alhpa olefin used is 1- hexene during preparing component 1, during preparing component 2 Alhpa olefin used is 1- butylene.
Through detecting, the performance of component 1 and component 2 prepared by the above method is as follows:
The melt index MFR of component 11=5.0g/10min, density p1=0.913g/cm3, molecular weight distributing index Mw/Mn =3.2, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MFR of component 22=15g/10min, density p2=0.905g/cm3, molecular weight distributing index Mw/Mn= 3.5, molar content=9.8mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed according to the ratio, wherein the mass fraction W of component 11For 80 weight Part, the mass fraction W of component 22For 20 parts by weight, W1/W2=4；Then lubricant and antioxidant (specific type and dosage is added As shown in table 1, wherein total dosage of component 1 and component 2 is 100 parts by weight；Lubricant is the production of Switzerland's Clariant Corporation PEG lubricant, molecular weight 10000；Antioxidant is purchased from Ciba, Switzerland, and the trade mark is respectively 1010 and 168), later will mixing Object is added in high speed agitator and is uniformly mixed, then the material mixed is added to the double screw extruder of W&P company manufacture Feeder in, 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 polyethylene composition pellet, detected its melt index MFR=6.2g/10min.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 1, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.The performance of gained film is as shown in table 2.
Comparative example 4
This comparative example is used to illustrate the polyethylene composition and its film of reference.
(1) preparation of polyethylene composition:
Polyethylene composition is prepared according to the method for comparative example 3, unlike, while lubricant and antioxidant is added Being also added into nucleating agent and Petropols, (specific type and dosage are as shown in table 1, wherein component 1 and total dosage of component 2 are 100 parts by weight；Petropols are the C purchased from Japanese Chu Guang company9Petropols, softening point are 125 DEG C), obtain polyethylene group Object pellet is closed, its melt index MFR=7.4g/10min is detected.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 1, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.The performance of gained film is as shown in table 2.
Table 1
Table 2
It can be concluded that, polyethylene composition provided by the invention is used to prepare in embodiment 1-3 two-way from the result in table 2 PE film is stretched, has the advantages that film forming multiplying power is big, rate of extension is fast and modulus is high compared with the film of the prior art, it is prepared The performance of film is able to satisfy longitudinal direction (MD) tensile strength >=70MPa, laterally (TD) tensile strength >=90MPa, longitudinal (MD) mould Amount >=300MPa, lateral (TD) modulus >=350MPa, puncture strength >=3.0N.Comparison from embodiment 1 and embodiment 4 can Out, when the density p of component A, component B and component C in the polyethylene compositionA、ρBAnd ρCBetween relationship meet -0.04≤ ρA-ρB≤ 0.02 and -0.04≤ρA-ρCWhen≤0.02, the polyethylene composition is with preferable film forming and higher modulus On the basis of, the film tensile strength also with higher and punctured resistances that be prepared by the polyethylene composition and compared with Low mist degree.
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 (33)

1. a kind of polyethylene composition, which is characterized in that the polyethylene composition contains component A, component B, component C, nucleation Agent and Petropols；The component A is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, is 190 DEG C, load in temperature For the melt index MFR under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is second Alkene/alhpa olefin copolymerization linear low density polyethylene, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-14.9g/10min, density pBFor 0.910-0.930g/cm3；The component C is the linea low density of ethylene/alpha-olefin copolymerization Polyethylene, the melt index MFR in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3,
Wherein, in the polyethylene composition component A, component B and component C density pA、ρBAnd ρCBetween relationship meet- 0.04≤ρA-ρB≤ 0.02, and -0.04≤ρA-ρC≤ 0.02,
In terms of being 100 parts by weight by the total content of the component A, component B and component C, the content of the nucleating agent is 0.01-0.25 Parts by weight, the content of the Petropols are 10-15 parts by weight.
2. polyethylene composition according to claim 1, wherein the component A is temperature is 190 DEG C, load is Melt index MFR under 2.16kgAFor 0.01-1.5g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MFRBFor 3-10g/10min, melt index of the component C in the case where temperature is 190 DEG C, load is 2.16kg MFRCFor 15-100g/10min.
3. polyethylene composition according to claim 1, wherein the component A is temperature is 190 DEG C, load is Melt index MFR 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 MFRBFor 3-5g/10min, melt index MFR of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 20-60g/10min。
4. polyethylene composition according to claim 1, wherein the density p of the component AAFor 0.910-0.930g/ cm3, the density p of the component BBFor 0.913-0.928g/cm3, the density p of the component CCFor 0.905-0.928g/cm3。
5. polyethylene composition according to claim 4, wherein the density p of the component AAFor 0.915-0.926g/ cm3, the density p of the component BBFor 0.913-0.924g/cm3, the density p of the component CCFor 0.910-0.926g/cm3。
6. polyethylene composition described in any one of -5 according to claim 1, wherein in the polyethylene composition, The mass fraction W of the component AAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, described group Divide the mass fraction W of CCFor 10-75 parts by weight.
7. polyethylene composition according to claim 6, wherein in the polyethylene composition, the matter of the component A Measure number WAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction W of the component CC For 20-70 parts by weight.
8. polyethylene composition according to claim 6, wherein the mass fraction W of the component AAWith the quality of component C Number WCWith the melt index MFR of component AARelationship meet 5.2 × lgMFRA+11.6≥WA/WC≥0.9×lgMFRA+2.1。
9. polyethylene composition according to claim 8, wherein the mass fraction W of the component AAWith the quality of component C Number WCWith the melt index MFR of component AARelationship meet 2.9 × lgMFRA+6.8≥WA/WC≥1.1×lgMFRA+2.7。
10. polyethylene composition described in any one of -5 and 8 according to claim 1, wherein the polyethylene composition exists Melt index under temperature is 190 DEG C, load is 2.16kg is 0.1-20g/10min.
11. polyethylene composition according to claim 10, wherein the polyethylene composition is 190 DEG C, carries in temperature Melt index under lotus is 2.16kg is 0.5-10g/10min.
12. polyethylene composition described in any one of -5 according to claim 1, wherein the component A, component B and component The molecular weight distributing index of C is all satisfied Mw/Mn≤4.5。
13. polyethylene composition according to claim 12, wherein the molecular weight of the component A, component B and component C point Cloth index is all satisfied 2.0≤Mw/Mn≤4.2。
14. polyethylene composition according to claim 13, wherein the component A, component B and component C are all made of luxuriant gold Metal catalyst polymerize to obtain.
15. polyethylene composition described in any one of -5 according to claim 1, wherein the component A, component B and component The molar content of alhpa olefin comonomer is each independently 0.2-15mol% in C.
16. polyethylene composition according to claim 15, wherein alhpa olefin is total in the component A, component B and component C The molar content of polycondensation monomer is each independently 1.5-10mol%.
17. polyethylene composition according to claim 15, wherein the alhpa olefin in the component A, component B and component C It is each independently C3-C20At least one of alkene.
18. polyethylene composition according to claim 17, wherein the alhpa olefin in the component A, component B and component C It is each independently propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 1- amylene, 3- Methyl-1-pentene, 4- methyl-1-pentene Alkene, 3,3- dimethyl-1- amylene, 3,4- dimethyl-1- amylene, 4,4- dimethyl-1- amylene, 1- hexene, 4- methyl-1-oneself Alkene, 5- methyl-1-hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- dodecylene, tetradecene, 16 carbon of 1- At least one of alkene, 1- octadecene and 1- eicosylene.
19. polyethylene composition according to claim 18, wherein the alhpa olefin in the component A, component B and component C It is each independently at least one of 1- butylene, 1- hexene and 1- octene.
20. polyethylene composition according to claim 1 or 2, wherein the nucleating agent be Sorbitol Nucleator and/ Or aryl phosphoric acids salt nucleating agent.
21. polyethylene composition according to claim 1 or 2, wherein the Petropols are C5And/or C9Plus hydrogen stone Oleoresin.
22. polyethylene composition according to claim 21, wherein the softening point of the Petropols is 100-150 DEG C.
23. polyethylene composition according to claim 22, wherein the Petropols are Cyclopeutadiene type resins.
24. polyethylene composition according to claim 1 or 2, wherein the polyethylene composition also contains lubricant.
25. polyethylene composition according to claim 24, wherein with the total weight of the component A, component B and component C For 100 parts by weight meters, the content of the lubricant is 0.05-5 parts by weight.
26. polyethylene composition according to claim 25, wherein the lubricant be selected from polyethylene glycol series lubricant agent, Fluoropolymer series lubricant agent, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester profit Lubrication prescription, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and the micro-nano grain of rice At least one of subclass lubricant.
27. a kind of film, the film includes at least one layer of polyethylene composition as described in any one of claim 1-26 The polyethylene layer that object is formed.
28. film according to claim 27, wherein the film has the composite junction of upper epidermis, sandwich layer and layer Structure, and at least described sandwich layer is the polyethylene layer formed by the polyethylene composition.
29. film according to claim 27, wherein when the film has the compound of upper epidermis, sandwich layer and layer When structure, the thickness of the upper epidermis and layer is each independently the 1-25% of the film thickness.
30. film according to claim 27, wherein the film is that two-way drawing is prepared by flat membrane biaxial tension method Stretch film.
31. film according to claim 30, wherein preparing the biaxially oriented film using flat membrane biaxial tension method During, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5 times；It is described two-way being prepared using flat membrane biaxial tension method During oriented film, cross directional stretch rate >=50%/s.
32. the film according to any one of claim 27-31, wherein the film with a thickness of 10-200 μm.
33. film according to claim 32, wherein the film with a thickness of 10-100 μm.
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