WO2020139119A1 - Polymère pour la production à grande vitesse d'un film bi-orienté, film et article fabriqué à partir de celui-ci - Google Patents

Polymère pour la production à grande vitesse d'un film bi-orienté, film et article fabriqué à partir de celui-ci Download PDF

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Publication number
WO2020139119A1
WO2020139119A1 PCT/RU2018/000904 RU2018000904W WO2020139119A1 WO 2020139119 A1 WO2020139119 A1 WO 2020139119A1 RU 2018000904 W RU2018000904 W RU 2018000904W WO 2020139119 A1 WO2020139119 A1 WO 2020139119A1
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Prior art keywords
polypropylene
film
molecular weight
mol
fraction
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PCT/RU2018/000904
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English (en)
Inventor
Kristina Andreevna SAMAROVA
Ludmila Borisovna SHABALINA
Irina Gennadievna RYZHIKOVA
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Public Joint Stock Company “SIBUR Holding”
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Priority to JP2021538031A priority Critical patent/JP7213989B2/ja
Priority to EA202191584A priority patent/EA202191584A1/ru
Priority to CZ2021355A priority patent/CZ2021355A3/cs
Priority to PCT/RU2018/000904 priority patent/WO2020139119A1/fr
Publication of WO2020139119A1 publication Critical patent/WO2020139119A1/fr

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    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/10—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 of paper or cardboard
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2519/00—Labels, badges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present invention relates to polypropylene for the preparation of films, in particular biaxially oriented polypropylene (BOPP) films. Structural characteristics of the claimed polypropylene allow to increase the processing speed in the process of preparing BOPP films up to 450 m/min or higher without plate-out formation and the use of gliding additives (for example, metal stearates), which are known to facilitate the process of film production.
  • the invention also relates to BOPP films, at least one layer of which contains polypropylene. Films according to the invention are suitable for producing packaging, including packaging for food products, adhesive tapes, labels, etc.
  • polypropylene films are a popular material for the manufacture of high-quality flexible packaging.
  • biaxially oriented polypropylene (BOPP) films are used for the manufacture of food and non-food products packaging, for individual or multiple-unit packaging, wherein the packaging can be made transparent or metallized, matte, colored (depending on the filler color).
  • BOPP films are used to make labels, adhesive tapes, etc.
  • the major component of BOPP films is isotactic polypropylene with a degree of isotacticity of 87-89% (isotacticity is determined by the content of isotactic pentads [mmmm] by C 13 NMR analysis).
  • isotacticity is determined by the content of isotactic pentads [mmmm] by C 13 NMR analysis.
  • the presence of a certain number of defects in the structure of isotactic macromolecules contributes to a higher orientation ability of the polymer.
  • the higher orientation ability of polypropylene allows increasing the speed of processing and increasing the volume of film production.
  • At least one layer of such film contains polypropylene having a melt flow rate from 0.5 to 15 g/10 min and xylene cold soluble fraction value of less than 3.5 wt.%; the degree of crystallinity determined by X-ray diffraction ranging from 0.5 to 0.85 and xylene and heptane insoluble fractions content of more than 94% by weight.
  • the film additionally contains at least a second layer containing a heterophasic statistical copolymer (impact copolymer), where the heterophasic statistical copolymer has a melt flow rate of from 0.5 to 15.0 g/10 min and a melting point of from 120 to 170°C.
  • the film is characterized by high tensile strength, impact strength, and puncture resistance due to low content of the xylene cold soluble (XCS) fraction.
  • the disadvantage of the solution proposed in EP21431 16 is the slow processing speed of polypropylene due to the low content of xylene cold soluble (XCS) fraction.
  • a method of producing a BOPP film where the core layer of the film contains either polypropylene with atacticity of at least 10% or a polymer composition which comprises a mixture of an isotactic polymer with a degree of atacticity of less than 5% and atactic polypropylene, syndiotactic polypropylene, ethylene-propylene copolymers, propylene terpolymer, polybutene or linear low density polyethylene.
  • the use of propylene polymer or polymer composition with a degree of atacticity of 10% or more allows obtaining a BOPP film with high tear resistance.
  • isotactic polypropylene There are no other requirements to the characteristics of isotactic polypropylene. Consequently, the content of fractions having certain molecular weights and fractions having a certain solubility in xylene and heptane is not considered as a criterion for determining suitability of the polypropylene for use in film processing.
  • An object of the present invention is to determine the combination of structural characteristics of polypropylene that allows to increase the efficiency of the process of biaxial orientation of polypropylene to obtain a BOPP film.
  • the technical result of the present invention resides in the increase in the productivity of the process of obtaining BOPP films by using the polypropylene in the film composition, the structural characteristics of the polypropylene making it possible to process the film at the speed of at least 450 m/min.
  • the technical result also includes a lack of plate-out formation on the die in the process of film preparation, which thereby reduces equipment downtime.
  • An additional technical result resides in the possibility of obtaining a wide range of films: transparent, matte, filled, general purpose, etc. as well as the possibility of applying layer coatings, for example, a metallized layer, printing, etc.
  • the object of the present invention is solved and the technical result is achieved by introducing a polypropylene into the film, which polypropylene has the following characteristics:
  • the amount of the xylene cold soluble (XCS) fraction in the polymer falls within the range from 4.0 to 6.0 wt.%, wherein the proportion of the fraction with a molecular weight in the range of 50,000 g/mol and greater is at least 40 wt.%, while the proportion of the fraction with a molecular weight in the range from 1,500 to 50,000 g/mol, is not more than 40 wt.%
  • the amount of the heptane soluble (HS) fraction in the polymer falls within the range from 2.5 to 3.5 wt.%, wherein the proportion of the fraction with a molecular weight of 50,000 g/mol and greater is at least 60 wt.%, while the proportion of the fraction with a molecular weight in the range of from 1,500 to 50,000 g/mol, is not more than 40 wt.%.
  • xylene- soluble and heptane- soluble fractions characterized by certain values of molecular weights allows to increase the speed of the process for preparing biaxially oriented films by improving the polypropylene orientation. While not wishing to be bound by any particular theory, the inventors believe that in order to reduce the adverse effect of increased plate-out formation on the forming die and to retain the orientation ability of the polypropylene, said polypropylene must contain a certain amount of XS and HS fractions having a certain content of low molecular weight (from 1,500 to 50,000 g/mol) and high molecular weight (from 50,000 g/mol and above) components.
  • Fig 1 illustrates a BOPP film prepared from the polypropylene according to the invention.
  • Fig 2 illustrates the BOPP film prepared in Example 3.
  • Fig 3 illustrates the BOPP film prepared in Example 4.
  • Fig 4 illustrates the BOPP film prepared in Example 5.
  • XCS xylene cold soluble
  • HS heptane soluble
  • a distinctive feature of the claimed polypropylene to be used in the manufacture of BOPP films is the molecular weight of XCS fraction being mainly in the range of from 1,500 to 50,000 g/mol, whereas the proportion of XCS fraction with a molecular weight of more than 50,000 g/mol does not exceed 40 wt.%, preferably does not exceed 30 wt.%, more preferably does not exceed 20 wt.%.
  • the proportion of HS fraction with a molecular weight of 50,000 g/mol and greater is at least 60 wt.%, preferably at least 65 wt.%, most preferably at least 70 wt.%, and the proportion of HS fraction with a molecular weight ranging from 1,500 to 50,000 g/mol is not more than 40 wt.%, preferably not more than 25 wt.%, most preferably not more than 15 wt.%.
  • the molecular weight distribution of the polypropylene is of from 4 to 7, more preferably is in the range from 5 to 7.
  • the content of the isotacticity pentad of polypropylene [mmmm] is of from 87 to 89%.
  • the present invention provides a polymer for the preparation of BOPP films at high processing speed (at least 450 m/min), which can be obtained using supported Ziegler-Natta titanium-magnesium catalysts of the general formula MgCb/TiCU/Di/Di/TEA, where titanium tetrahalides are supported on magnesium halides, D1 is an internal electron donor, D2 is an external electron donor, triethylaluminum (TEA) is a co-catalyst.
  • MgCb/TiCU/Di/Di/TEA titanium tetrahalides are supported on magnesium halides
  • D1 is an internal electron donor
  • D2 is an external electron donor
  • triethylaluminum (TEA) is a co-catalyst.
  • any compound known from the prior art as a donor of the Ziegler-Natta catalyst is used, wherein the compound comprises at least one of the following functional groups: alcohol, amino, amide or ester group.
  • specific examples of internal donors include, but are not limited to: methanol, ethanol, isopropanol and butanol, diethylamine, diisopropylamine and triethylamine, formamide and acetamide, C1-C20 benzoic acid alkyl esters, Ci-Cs alkyl esters of aliphatic monocarboxylic acids, 1,8- naphthyl diesters, malonates, succinates and glutarates.
  • fourth-generation Ziegler-Natta catalysts comprising phthalate compounds as donors
  • internal electron donors represented by fluorene compounds.
  • the organosilicon compound represented by the following formula R n Si(OR)4- n can be used, where R is a hydrocarbon radical, OR is an alkoxy group, R is a hydrocarbon group, and n is an integer 0 ⁇ n ⁇ 4.
  • organosilicon compounds represented by this formula include the following: diisopropyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, dicyclohexyl dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2 - methylcyclopentyl trimethoxysilane, cyclopentiltrietoksisilan, n- propyltrimethoxysilane, dicyclopenty
  • the characteristics of polypropylene depend both on the nature and on the amount of external electron donor used in the catalyst system.
  • the external donor is added at a molar ratio of co-catalyst (Co) to external donor (ED) [Co/ED ratio] in the range of from 2 to 180.
  • catalysts and methods for preparation thereof are catalysts and methods for preparation thereof disclosed in EP2221320, EP2638080, EP2951215 documents.
  • the polypropylene of the present invention can be obtained by gas phase or suspension polymerization of propylene in the presence of the above catalysts.
  • the components of the catalytic system can be brought into contact with each other before adding them to the polymerization reactor.
  • an alkyl-Al compound can be used, for example, triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexylamine aluminum, tri-n-octyl aluminum.
  • Polymerization using a Ziegler-Natta catalyst is generally carried out at a temperature in the range of 50-80°C, preferably in the range of 65-75°C and an operating pressure in the range from 0.1 to 5.0 MPa, preferably in the range of from 0.5 to 3.5 MPa.
  • the melt flow index (MFl230 ° c / 2.i6 kg ) of the used polymers determined according to ASTM D 1238 should be at least 3 g/10 min.
  • polypropylene can be prepared according to the processes described, for example, in the documents US8178633, EP2726517, etc.
  • the polypropylene contains stabilizers, which comprise at least a mixture of antioxidants and acid absorbers.
  • Any antioxidants known from the prior art can be used as antioxidants, preferably a mixture of phosphite and phenol antioxidants is used.
  • As an acid absorber any acid absorber known from prior art other than the metal stearate class compounds can be used.
  • other known additives can be additionally used to allow polypropylene to retain its properties during processing and operation.
  • the amount of stabilizers added to the polypropylene is from 1 to 3 kg per ton of polypropylene, preferably from 1.2 to 2.5 kg per ton of polypropylene, more preferably from 1.2 to 1.5 kg per ton of polypropylene.
  • the polypropylene according to the invention is substantially free from calcium stearate.
  • Calcium stearate transforms into stearic acid when interacting with acids, which readily migrates to the surface making it impossible to produce a metallized film.
  • substantially free means a content of less than 0.010% by weight, preferably less than 0.005 wt.%, most preferably less than 0.001 wt.%.
  • the specified polypropylene can be used both as a primary and as an additional component of any film layer of any formulations known from the prior art.
  • the exact structure of the film (the number and order of layers) and the content of the layers depend on the requirements for the film and articles made from the film.
  • the film may contain other polyolefins as well as functional polymers.
  • Copolymers and terpolymers of a-olefins are used as polyolefins, specifically, copolymers of propylene and ethylene, propylene and butene, terpolymers of propylene, ethylene and butene, etc.
  • copolymers of ethylene with vinyl alcohol polyvinylidene chloride, copolymers of vinylidene chloride, polyesters, polyamides (to impart gas and/or aroma-proof properties to the film), interpolymers of ethylene and a- olefin (for adhesive-free paper-to-film lamination), maleic anhydride homopolypropylene (adhesive layer in coextrusion films), etc.
  • the film is intended for the preparation of wrapping paper, as the base for adhesive tapes, etc. and is a multi-layer polypropylene film, each layer of which consists of polypropylene that has the above characteristics as well as of antistatic substances and/or anti-caking substances and/or antioxidant.
  • the antiblocking agents are silicon dioxide (S1O2), polymethyl methacrylate (PMMA), and the like, and the antioxidant is a phenolic antioxidant.
  • the film is intended for adhesive- free film-to-paper lamination and includes at least the following: a core layer containing polypropylene having the above characteristics, and a functional layer comprising: ethylene-butene copolymer, ethylene-octene copolymer, ethylene-butene-octene terpolymer, ethylene-butene copolymer modified with grafted maleic anhydride, ethylene-octene copolymer modified with grafted maleic anhydride, ethylene-butene- octene terpolymer, modified by grafted maleic anhydride or mixtures thereof, or mixtures formed from any of the above copolymer and/or terpolymer, modified copolymers and/or terpolymers, and blends with hydrogenated petroleum resin.
  • a core layer containing polypropylene having the above characteristics and a functional layer comprising: ethylene-butene copolymer, ethylene-octene copolymer,
  • the film has barrier properties and contains at least the following layers: one layer of propylene polymer that has the above characteristics, and a layer of gas barrier material represented by polyamide, a copolymer of ethylene and vinyl alcohol, etc.
  • a layer of modified polyolefin, for example, a layer of propylene polymer modified with maleic anhydride may optionally be used to improve the adhesion between the layer of propylene polymer meeting the above characteristics and the layer of gas barrier material.
  • additives can be included in the formulation in effective amounts, i.e. in quantities that provide the desired functional properties or improve the parameters and/or functionality of the finished film.
  • examples of additives include, but are not limited to the following: additives that offer anti-block, anti-static and slip effects as well as antioxidants and neutralizers, technological additives, nucleating agents, additives that reduce the effect of UV radiation, and UV-absorbers, dyes, fillers, thickeners, modifiers based on hydrocarbon resins, etc.
  • the total thickness of the films varies over wide ranges depending on the intended purpose of use.
  • the film has a total thickness of from 2 to 100 pm, preferably from 5 to 50 pm, more preferably from 10 to 30 pm.
  • the film of the present invention is obtained by coextrusion of polypropylene with other polymers followed by biaxial orientation.
  • the orientation value of the film in the Machine Direction is from 4.5 to 5.5, in the Transverse Direction - up to 10.
  • film surface activation/modification to make it suitable for printing for example, by plasma treatment, corona treatment, and flame treating
  • the treated film is used to make the final article such as packaging, metallized packaging, label, bag, adhesive tape and other articles using the BOPP films according to the invention.
  • Specific examples include, but are not limited to: making a label as specified in EP2197669, WO2017077184 documents, making a bag as disclosed in particular in US9108391 document, preparing food packaging as indicated, for example, in WO2016205381 document, producing a metallized film as described in EP0925912 document.
  • melt flow index was determined in accordance with ASTM D1238
  • the mass fraction of the soluble fraction in boiling heptane/isotactic fraction was determined according to National State Standard 26996-86.
  • MWD molecular weight distribution
  • GPC Gel Permeation Chromatography
  • the microstructure, the degree of isotacticity, and the pentad ratio of polypropylene samples were determined by the method of high resolution nuclear magnetic resonance spectroscopy on carbon nuclei ( 13 C NMR) on Bruker Avance III 400 MHz NMR spectrometer.
  • 13 C NMR nuclear magnetic resonance spectroscopy on carbon nuclei
  • a sample weighing 250 mg was dissolved in 2.5 ml of trichlorobenzene with heating to 140°C.
  • the number of scans on 13 C nuclei is 16,000.
  • the experiment temperature was 140°C.
  • Propylene polymer having MFI 3.0 g/10 min (at 230°C and 2.16 kg) was obtained by gas-phase technology at a temperature of 65-75°C and a working pressure of 2.2 MPa.
  • a catalyst prepared in a similar way as in example 6 of EP0361493 was used as a catalyst, except that diisobutyl dimethoxysilane was used as an external electron donor.
  • the BOPP film was a five-layer film, with each layer thereof consisting of the above polypropylene and antioxidants, such as the hindered phenolic antioxidant, pentaerythritol tetraoxy (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010), and phosphorus-containing antioxidant, tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168), and also hydrotalcite as an acid absorber, in the amount of 1.35 kg of stabilizers per ton of polypropylene.
  • antioxidants such as the hindered phenolic antioxidant, pentaerythritol tetraoxy (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010), and phosphorus-containing antioxidant, tris (2,4-di-tert-butylphenyl
  • the film was prepared by continuous extrusion of polypropylene with a stepwise orientation, heat setting and cooling of the film slab: molten materials plasticized in each of the extruders (five extruders corresponding to the number of layers); were combined in a die (head) and flowed confluent from a slot die onto a cooling drum (shaft) in the form of a slab, then the slab was cooled down by passing through a water bath. Next, the film slab was reheated to 100-115°C on heating cylinders and stretched up to 6 times its original length in the machine direction on the rollers. The film stretched in the machine direction went into an oven, where it was heated once again by air up to 170-180°C and stretched up in the transverse direction 10 times its original width. The total film thickness was 20 pm, while the outer layers were 0.9 pm thick, the intermediate layers were 2.5 pm, the core layer was 13.2 pm. The characteristics of the used polypropylene and the processing speed of the film are shown in Table 1.
  • the BOPP film was prepared as in Example 1, except for using the polypropylene having the characteristics shown for Example 2 in Table 1, and the film consisting of five layers, each layer comprising of polypropylene.
  • the processing speed of the film is shown in Table 1.
  • a BOPP film was prepared as in Example 1, except that polypropylene was prepared using a Ziegler-Natta catalyst with dibutyl phthalate as internal electron donor and wherein the polypropylene had the characteristics shown in Table 1 for the comparative Example 3.
  • the processing speed of the film is shown in Table 1.
  • the BOPP film was prepared as in Example 1 , except for using polypropylene prepared using a Ziegler-Natta catalyst with 9,9-bis-methoxymethylfluorene as internal electron donor and wherein the polypropylene had the characteristics shown in Table 1 for the comparative Example 4.
  • the processing speed of the film is shown in Table 1.
  • the BOPP film was prepared as in Example 1, except for using polypropylene prepared using a Ziegler-Natta catalyst with a molar ratio of co-catalyst (Co) to an external donor (ED) [Co/ED ratio] of 40 (to achieve a low XCS), said polypropylene having characteristics listed in Table 1 for comparative Example 5.
  • the processing speed of the film is shown in Table 1.
  • a BOPP film was prepared as in Example 1, except that polypropylene was prepared using a Ziegler-Natta catalyst with isobutyl phthalate as internal electron donor and wherein the polypropylene had the characteristics shown in Table 1 for the comparative Example 6.
  • the processing speed of the film is shown in Table 1.
  • the amount of the xylene cold soluble fraction (XCS) in the polymer is within the range from 4.0 to 6.0 wt.%;

Abstract

L'invention concerne un polypropylène pour la préparation de films, en particulier de films de polypropylène bi-orienté (BOPP). Les caractéristiques structurales du polypropylène selon l'invention permettent d'augmenter la vitesse de traitement (450 m/min et plus) dans le procédé de production de films BOPP. L'invention concerne également des films BOPP dont au moins une couche comprend du polypropylène. Les films selon l'invention peuvent être utilisés pour la fabrication d'emballages, notamment d'emballages de produits alimentaires, de bandes adhésives, d'étiquettes, etc.
PCT/RU2018/000904 2018-12-28 2018-12-28 Polymère pour la production à grande vitesse d'un film bi-orienté, film et article fabriqué à partir de celui-ci WO2020139119A1 (fr)

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JP2021538031A JP7213989B2 (ja) 2018-12-28 2018-12-28 二軸延伸フィルムの高速製造のためのポリマー、それから製造されたフィルム及び物品
EA202191584A EA202191584A1 (ru) 2018-12-28 2018-12-28 Полимер для получения биаксиально-ориентированной пленки с высокой скоростью переработки, пленка и изделие из нее
CZ2021355A CZ2021355A3 (cs) 2018-12-28 2018-12-28 Polymer pro vysokorychlostní výrobu biaxiálně orientovaného filmu, film a produkt z něho vyrobený
PCT/RU2018/000904 WO2020139119A1 (fr) 2018-12-28 2018-12-28 Polymère pour la production à grande vitesse d'un film bi-orienté, film et article fabriqué à partir de celui-ci

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PCT/RU2018/000904 WO2020139119A1 (fr) 2018-12-28 2018-12-28 Polymère pour la production à grande vitesse d'un film bi-orienté, film et article fabriqué à partir de celui-ci

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US6071598A (en) * 1995-05-31 2000-06-06 Hoechst Aktiengesellschaft Biaxially oriented polyproylene film having a high surface modulus
RU2251562C2 (ru) * 1999-01-11 2005-05-10 Циба Спешиалти Кемикалз Холдинг Инк. Синтетические полимеры, содержащие смеси-добавки усиленного действия
RU2269547C2 (ru) * 2000-12-22 2006-02-10 Базелль Полиолефин Италия С.П.А. Двуосно-ориентированные полипропиленовые пленки
EA016807B1 (ru) * 2006-07-10 2012-07-30 Бореалис Текнолоджи Ой Двухосно-ориентированная полипропиленовая пленка и способ ее получения
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EA022392B1 (ru) * 2009-10-01 2015-12-30 Тотал Ресерч Энд Текнолоджи Фелюи Пропиленовый полимер с улучшенной обрабатываемостью в формовании листовых термопластов
EP2853563B1 (fr) * 2013-09-27 2016-06-15 Borealis AG Films approprié pour un traitement BOPP de polymères présentant une portion de xylène élevé et un point de fusion élevé

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SU785331A1 (ru) * 1979-01-03 1980-12-07 Всесоюзный научно-исследовательский институт синтетического волокна Полимерна композици
US6071598A (en) * 1995-05-31 2000-06-06 Hoechst Aktiengesellschaft Biaxially oriented polyproylene film having a high surface modulus
RU2251562C2 (ru) * 1999-01-11 2005-05-10 Циба Спешиалти Кемикалз Холдинг Инк. Синтетические полимеры, содержащие смеси-добавки усиленного действия
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RU2530490C2 (ru) * 2009-12-30 2014-10-10 Бореалис Аг Бопп пленка с гомогенной структурой
EP2853563B1 (fr) * 2013-09-27 2016-06-15 Borealis AG Films approprié pour un traitement BOPP de polymères présentant une portion de xylène élevé et un point de fusion élevé

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