WO2011039314A1 - Films polyoléfiniques thermoscellables - Google Patents

Films polyoléfiniques thermoscellables Download PDF

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Publication number
WO2011039314A1
WO2011039314A1 PCT/EP2010/064571 EP2010064571W WO2011039314A1 WO 2011039314 A1 WO2011039314 A1 WO 2011039314A1 EP 2010064571 W EP2010064571 W EP 2010064571W WO 2011039314 A1 WO2011039314 A1 WO 2011039314A1
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WIPO (PCT)
Prior art keywords
ethylene
copolymer
film
propylene
component
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PCT/EP2010/064571
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English (en)
Inventor
Stefano Pasquali
Gianluca Musacchi
Enrico Beccarini
Inge Elisabeth Roucourt
Original Assignee
Basell Poliolefine Italia Srl
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Publication of WO2011039314A1 publication Critical patent/WO2011039314A1/fr

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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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B32B27/18—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
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    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
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    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2439/00—Containers; Receptacles
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    • B32B2439/06—Bags, sacks, sachets
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    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
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    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • 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
    • 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
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    • C—CHEMISTRY; METALLURGY
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    • 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

Definitions

  • the present invention relates to heat-sealable polyolefin films.
  • Such kind of polyolefin films is widely used in the packaging field, especially in the food packaging field, but also for the packaging non food products and for the production of non-packaging items.
  • Packaging examples are the primary packaging of hygienic items, textile articles, magazines, mailing films, secondary collation packaging, shrink packaging films and sleeves, stretch packaging films and sleeves, form-fill-seal packaging films for portionating various types of articles such as bags, pouches or sachets, vacuum formed blisters.
  • form-fill -seal applications are the packaging of peat and turf, chemicals, plastic resins, mineral products, food products, small size solid articles.
  • Non packaging items are for example synthetic clothing articles or medical and surgical films, films which are formed into flexible conveying pipes, membranes for isolation and protection in soil, building and construction applications, films which are laminated with non-woven membranes.
  • the film is characterized by the presence of at least one polyolefin layer that can be easily sealed to itself or to other materials by applying heat and pressure (heat- sealable layer).
  • the features of the seal are determined by the choice and the relative amounts of the olefin polymers composing the sealing layer.
  • polymer products made up of heterophasic mixtures of propylene crystalline polymers and elastomeric olefin copolymers, typically obtained by sequential stereospecific polymerization, are establishing themselves in the polypropylene industry. These products possess a satisfying compromise of elastic properties and mechanical resistance and can easily be transformed into manufactured articles by using the equipments and processes normally used for thermoplastic materials. As disclosed in particular in EP0477662, such polymer products can be used to produce films with improved elongation at break and Elmendorf tear properties and good optical properties.
  • heterophasic composition comprising a crystalline propylene homo or copolymer (matrix), and a copolymer of ethylene with C 4 -Cio a-olefins (in the examples an ethylene/butene-1 rubber) having low values of MFR that are suitable for film applications, particularly for cast and bioriented films, exhibiting high gas permeability (breath-ability).
  • heterophasic compositions impact polymers
  • certain amounts of at least one ethylene based copolymer plastomer provide polyolefin compositions exhibiting improved seal strength high enough for industrial use and the above said advantageous balance of properties.
  • the composition according to the invention exhibit improved heat sealability (seal initiation temperature is lowered and seal strength is maintained or improved). The effect is observed also at a low amount of ethylene copolymer plastomer added (lower than 10 wt%).
  • Heat sealability is combined with a valuable balance of mechanical properties that are substantially maintained or even in some case improved in comparison to the base heterophasic composition of reference. The mechanical properties are maintained even up to 20 wt% of plastomer addition. Mechanical resistance (Elmendorf) is improved, tensile properties (elongation and stress) are generally maintained and improved optical properties (Haze) are observed.
  • the said polyolefin compositions are suitable to be used as sealing layer (outermost layer) in a heat-sealing film. Good seal properties are maintained also after retorting.
  • an object of the present invention is a film or sheet comprising at least one layer of a polyolefin composition (I) comprising, in percent by weight referred to the sum of component (a1 ), (a2) and (b):
  • copolymer refers to both polymers with two different recurring units and polymers with more than two different recurring units in the chain, such as terpolymers.
  • copolymer plastomer refers to ethylene based copolymers and compositions thereof, having from elastomeric to plastomeric behaviour and generically also referred to as "plastomers".
  • the plastomers used in the present invention are ethylene based copolymers preferably produced by polymerization of ethylene and at least one alfa-olefin comonomer having from 5-10 carbons atoms. Preferably the polymerization is made in presence of a metallocene catalyst or other single site catalyst. The amount of comonomer is preferably less than 20 wt% with respect to the weight of the copolymer plastomer component (b). Preferred are ethylene/octene copolymer plastomers.
  • Such plastomers are available commercially (e.g. Dow AFFINITY® PL 1850G, Dow AFFINITY® PL 1880, or Exact polymer plastomers from DEXplastomers of the Netherland).
  • the plastomer is present in the composition from 0.5 to 30 wt%, preferably from 2 to 25 wt% with respect to the weight of the composition (I) according to the invention.
  • the composition (I) according to the invention preferably has a value of melt flow rate "L" of from 0.1 to 50g/10 min, preferably of less than 20 g/10 min, even more preferably of less than 10 g/10 min.
  • the composition of the present invention exhibits seal initiation temperature of from 120 to 140. Seal initiation temperature is herewith defined as the temperature at 50% of the maximum force plateau in the sealing strength curve obtained as described in the experimental part hereinbelow (substantially corresponding to the temperature at which a seal strength of at least 2N is measured).
  • Components (a1 ) (a2) and (b) can be mechanically blended together.
  • a preferred embodiment is a film or sheet comprising at least one layer of a polyolefin composition (I) comprising, in percent by weight referred to the sum of component (a) and (b):
  • XSm room temperature
  • the heterophasic composition (a1 )+(a2) is a polyolefin composition having a value of melt flow rate (MFR) at 230 °C, 2.16 kg of from 0.5 to 10 g/10 min, preferably of from 2 to 8 g/10 min.
  • MFR melt flow rate
  • Particularly preferred features for the compositions (a1 +a2) are:
  • Tm-DSC melting temperature of component (a1 ) equal to or higher than 150°C preferably higher than 154°C.
  • the value of the intrinsic viscosity of the total fraction soluble in xylene at room temperature is equal to or less than 3, preferably less than 2, more preferably less than 1 .7 dl/g;
  • melt flow rate MFR (at 230°C, 2.16Kg) of the matrix component (1 ) is from 2 to 10 g/10min.
  • R is an alkyl radical, linear or branched, with 2-8 carbon atoms or an aryl (in particular phenyl) radical.
  • Examples of said C 4 -Cio a-olefins are 1 -butene, 1 -pentene, 1 - hexene, 4-methyl-1 -pentene and 1 -octene.
  • the amount of units derived from ethylene and /or one or more C 4 -Cio a-olefin(s) is more preferably less than 1 .5 wt%, even more preferably less than 0.5 wt% of the component (a1 ) (minirandom copolymer).
  • the preferred matrix component (a1 ) is a copolymer of propylene with ethylene, even more preferred is a propylene homopolymer matrix (a1 ).
  • elastomeric component (a2) are the copolymers of ethylene with one or more C 4 -Cio a-olefin(s).
  • the most preferred component (a2) is an ethylene-butene-1 copolymer containing 50-95 wt% of ethylene derived units and consisting of 20-95 wt% of a crystalline fraction (I), with a polyethylene-type crystallinity, insoluble in xylene at room temperature, and for 50-80wt% of an amorphous fraction (II), soluble in xylene at room temperature, containing 40-70wt% of ethylene derived units.
  • the elastomeric ethylene copolymer component (a2) can further comprise a diene.
  • the diene is typically in amounts ranging from 0.5 to 10 wt% with respect to the weight of copolymer (a2).
  • the diene can be conjugated or not and is selected from butadiene, 1 ,4-hexadiene, 1 ,5- hexadiene, and ethylidene-norbornene-1 , for example.
  • heterophasic polymer composition (a1 )+(a2) is preferably obtained as a reactor blend of components (a1 ) and (a2) by sequential polymerization in two or more stages, using highly stereospecific Ziegler-Natta catalysts.
  • component (a1 ) is prepared before component (a2).
  • the process comprising at least two sequential polymerization stages with each subsequent polymerization being conducted in the presence of the polymeric material formed in the immediately preceding polymerization reaction, wherein the polymerization stage of propylene to the polymer component (a1 ) is carried out in at least one stage, then at least one copolymerization stage of mixtures of ethylene with propylene and/or one or more C 4 -Cio a-olefin(s) to the elastomeric polymer component (a2) is carried out.
  • the polymerisation stages can be carried out in the presence of a stereospecific Ziegler-Natta catalyst.
  • all the polymerisation stages are carried out in the presence of a catalyst comprising a trialkylaluminium compound, optionally an electron donor, and a solid catalyst component comprising a halide or halogen- alcoholate of Ti and an electron-donor compound supported on anhydrous magnesium chloride.
  • a catalyst comprising a trialkylaluminium compound, optionally an electron donor, and a solid catalyst component comprising a halide or halogen- alcoholate of Ti and an electron-donor compound supported on anhydrous magnesium chloride.
  • the polymerisation catalyst is a Ziegler-Natta catalyst comprising a solid catalyst component comprising: a) Mg, Ti and halogen and an electron donor (internal donor),
  • the internal donor is preferably selected from the esters of mono or dicarboxylic organic acids such as benzoates, malonates, phthalates and certain succinates. They are described in US patent 4522930, European patent 45977 and international patent applications WO 00/63261 and WO 01/57099, for example. Particularly suited are the phthalic acid esters and succinate acids esters. Alkylphthalates are preferred, such as diisobutyl, dioctyl and diphenyl phthalate and benzyl-butyl phthalate.
  • succinates they are preferably selected from succinates of formula (I) below: o
  • radicals Ri and R2 equal to, or different from, each other are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyi, aryl, arylalkyi or alkylaryl group, optionally containing heteroatoms
  • the radicals R3 to R6 equal to, or different from, each other, are hydrogen or a C1-C20 linear or branched alkyl, alkenyl, cycloalkyi, aryl, arylalkyi or alkylaryl group, optionally containing heteroatoms, and the radicals R3 to R6 which are joined to the same carbon atom can be linked together to form a cycle; with the proviso that when R 3 to R 5 are contemporaneously hydrogen, R 6 is a radical selected from primary branched, secondary or tertiary alkyl groups, cycloalkyi, aryl, arylalkyi or alkylaryl groups having from 3 to 20 carbon atoms;
  • radicals Ri and R2 are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyi, aryl, arylalkyi or alkylaryl group, optionally containing heteroatoms and the radical R3 is a linear alkyl group having at least four carbon atoms optionally containing heteroatoms.
  • the Al-al kyl compounds used as co-catalysts comprise Al-trialkyls, such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO 4 or SO3 groups.
  • the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
  • the external donor (c) can be of the same type or it can be different from the succinates of formula (I) or (II).
  • Suitable external electron-donor compounds include silicon compounds, ethers, esters such as phthalates, benzoates, succinates also having a different structure from those of formula (I) or (II), amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine, ketones and the 1 ,3-diethers of the general formula (III):
  • R 1 and R" are the same or different and are C1-C18 alkyl, C3-C18 cycloalkyi or C7-C18 aryl radicals;
  • R m and R IV are the same or different and are Ci-C 4 alkyl radicals; or the 1 ,3-diethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6 or 7 carbon atoms and containing two or three unsaturations.
  • Preferred electron-donor compounds that can be used as external donors include aromatic silicon compounds containing at least one Si-OR bond, where R is a hydrocarbon radical.
  • a particularly preferred class of external donor compounds is that of silicon compounds of formula R a 7 Rb 8 Si(OR 9 ) c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 7 , R 8 , and R 9 , are C1 -C18 hydrocarbon groups optionally containing heteroatoms.
  • Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t- butyltrimethoxysilane, t-hexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, 3,3,3- trifluoropropyl-2-ethylpiperidyl-dimethoxysilane, diphenyldimethoxysilane, methyl-t- butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t- butyldimethoxysilane, (1 ,1 ,1 -trifluoro-2-propyl)-methyldimethoxysilane and (1 ,1 ,1 - trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane.
  • Particularly preferred specific examples of silicon compounds are (tert-butyl) 2 Si(OCH 3 )2, (cyclohexyl)(methyl) Si(OCH 3 ) 2 , (phenyl) 2 Si(OCH 3 ) 2 and (cyclopentyl) 2 Si(OCH 3 ) 2 .
  • the electron donor compound (c) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of from 0.1 to 500, more preferably from 1 to 300 and in particular from 3 to 30.
  • the solid catalyst component comprises, in addition to the above electron donors, Ti, Mg and halogen.
  • the catalyst component comprises a titanium compound, having at least a Ti-halogen bond and the above mentioned electron donor compounds supported on a Mg halide.
  • the magnesium halide is preferably MgCI 2 in active form, which is widely known from the patent literature as a support for Ziegler-Natta catalysts. Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
  • magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerisation of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
  • the preferred titanium compounds are TiCI 4 and TiCI 3 ; furthermore, also Ti- haloalcoholates of formula Ti(OR)n-yXy can be used, where n is the valence of titanium, y is a number between 1 and n, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • the preparation of the solid catalyst component can be carried out according to several methods, well known and described in the art.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)n-yXy, where n is the valence of titanium and y is a number between 1 and n, preferably TiCI 4 , with a magnesium chloride deriving from an adduct of formula MgC pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1 - 18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130° C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles.
  • spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermally controlled dealcoholation (80-130° C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCI 4 (generally 0° C); the mixture is heated up to 80-130° C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCI 4 can be carried out one or more times.
  • the electron donor compound(s) can be added during the treatment with TiCI 4 .
  • the final amount of the electron donor compound(s) is preferably such that the molar ratio with respect to the MgC ⁇ is from 0.01 to 1 , more preferably from 0.05 to 0.5.
  • the catalysts may be precontacted with small quantities of olefin (prepolymerisation), maintaining the catalyst in suspension in a hydrocarbon solvent, and polymerising at temperatures from ambient to 60° C, thus producing a quantity of polymer from 0.5 to 3 times the weight of the catalyst.
  • the operation can also take place in liquid monomer, producing, in this case, a quantity of polymer 1000 times the weight of the catalyst.
  • the polyolefin compositions are obtained in spheroidal particle form, the particles having an average diameter from about 250 to 7,000 ⁇ , a flowability of less than 30 seconds and a bulk density (compacted) greater than 0.4 g/ml.
  • the polymerisation stages may occur in liquid phase, in gas phase or liquid-gas phase.
  • the polymerisation of the polymer component 1 ) is carried out in liquid monomer (e.g. using liquid propylene as diluent), while the copolymerisation stages of the elastomeric copolymer component 2) is carried out in gas phase.
  • all the sequential polymerisation stages can be carried out in gas phase.
  • the reaction temperature in the polymerisation stage for the preparation of the polymer component 1 ) and in the preparation of the elastomeric copolymer component 2) may be the same or different, and is preferably from 40 to 100° C; more preferably, the reaction temperature ranges from 50 to 80° C in the preparation of polymer component 1 ), and from 70 to 100° C for the preparation of polymer component 2).
  • the pressure of the polymerisation stage to prepare polymer component 1 is the one which competes with the vapor pressure of the liquid propylene at the operating temperature used, and it may be modified by the vapor pressure of the small quantity of inert diluent used to feed the catalyst mixture, by the overpressure of optional monomers and by the hydrogen used as molecular weight regulator.
  • the polymerisation pressure preferably ranges from 33 to 43 bar, if done in liquid phase, and from 5 to 30 bar if done in gas phase.
  • the residence times relative to the stages depend on the desired ratio between polymer components 1 ) and 2), and can usually range from 15 minutes to 8 hours.
  • Conventional molecular weight regulators known in the art such as chain transfer agents (e.g. hydrogen or ZnEt 2 ), may be used.
  • the polyolefin composition according to the present invention can be prepared according to conventional methods, for examples, mixing component (a), and component (b) and well known additives in a blender, such as a Henschel or Banbury mixer, to uniformly disperse the said components, at a temperature equal to or higher than the polymer softening temperature, then extruding the composition and pelletizing.
  • a blender such as a Henschel or Banbury mixer
  • Conventional additives, fillers and pigments commonly used in olefin polymers, may be added, such as nucleating agents, extension oils, mineral fillers, and other organic and inorganic pigments.
  • inorganic fillers such as talc, calcium carbonate and mineral fillers, also brings about an improvement to some mechanical properties, such as flexural modulus and HDT. Talc can also have a nucleating effect.
  • the heat-sealable film according to the invention comprises at least one sealing layer.
  • it can be a mono-layer film, but preferably it is multilayer, and in particular it comprises at least one support layer composed of or comprising a polymeric material, in particular a polyolefin material.
  • R is a hydrogen atom or a C1 -C6 alkyl radical, as for instance 1 -butene, 1 -hexene, 1 -octene, 4-methyl-1 - pentene.
  • Particularly preferred are the following polymers:
  • heterophasic copolymers comprising (a) a propylene homopolymer and/or one of the copolymers of item 2), and an elastomeric fraction (b) comprising copolymers of ethylene with propylene and/or a C4-C8 a-olefin, optionally containing minor amounts of a diene, such as butadiene, 1 ,4-hexadiene, 1 ,5- hexadiene, ethylidene-1 -norbornene.
  • a diene such as butadiene, 1 ,4-hexadiene, 1 ,5- hexadiene, ethylidene-1 -norbornene.
  • the amount of diene in (3) is from 1 to 10 wt%.
  • the heterophasic copolymers (3) are prepared according to known methods by mixing the components in the molten state, or by sequential copolymerization, and generally contain the copolymer fraction (b) in amounts ranging from 5 to 80wt%.
  • Other olefin polymers employable for the support layers are HDPE, LDPE and LLDPE polyethylenes.
  • polymeric materials different from polyolefins employable for the support layers, are polystyrenes, polyvinylchlorides, polyamides, polyesters and polycarbonates.
  • Both the support layers and the heat-sealable layers may comprise additives commonly employed in the art, like stabilizers, pigments, fillers, nucleating agents, slip agents, lubricant and antistatic agents, flame retardants, plasticizers and biocidal agents.
  • Preferred structures for said films are of A B type and A B/A type, where A is the heat-sealable layer according to the present invention and B is the support layer.
  • A is the heat-sealable layer according to the present invention and B is the support layer.
  • the thickness of the layers of heat-sealing composition according to the present invention is preferably from 5 to 15 ⁇ , while the thickness of the support layers is preferably from 15 to 65 ⁇ .
  • the overall thickness of the said films is preferably of from 20 to 80 ⁇ .
  • the thickness of the layers of heat-sealing composition according to the present invention is preferably from 1 to 100 ⁇ , more preferably from 5 to 20 ⁇ , while the thickness of the support layers is preferably from 20 to 200 ⁇ , preferably from 30 to 100 ⁇ .
  • the overall thickness of the said films is preferably of from 20 to 300 ⁇ .
  • the said packaging films are produced by using processes well known in the art. In particular, extrusion processes can be used.
  • the polymer materials to be used for the heat-sealing layers and those to be used for the support layers are molten in different extruders and extruded through a narrow slit.
  • the extruded molten material is pulled away from the slit and cooled before winding- up.
  • extrusion processes are the blown film and cast film processes hereinbelow explained.
  • the molten polymer materials are forced through a circular shaped slit.
  • the extrudate which is drawn off has the shape of a tube, which is inflated by air to form a tubular bubble.
  • the bubble is cooled and collapsed before winding-up.
  • the molten polymer materials are forced through a long, thin, rectangular shaped slit.
  • the extrudate has the shape of a thin film.
  • the film is cooled before winding-up.
  • the percent by weight of polymer insoluble in xylene at ambient temperature is considered the isotactic index of the polymer. This value corresponds substantially to the isotactic index determined by extraction with boiling n-heptane, which by definition constitutes the isotactic index of polypropylene.
  • Standard specimen are cut from strands extruded from a grader (MFR measurement). The specimen is inserted in the gradient column where density is measured according to ISO 1 183.
  • Cast films have been prepared by extruding each test composition in a single screw Dr. Collin cast film extruder equipped with a three layers co-extrusion cast film line (main extruder screw diameter 45 mm, L/D 30; two side extruders screw diameter 30 mm, L/D 30), at a melt temperature of 190-250 °C.
  • the throughput was ca.18.5kg/h.
  • the cast film has been winded at a film drawing speed between 12 and 13m/min with a nominal thickness of ⁇ , which is the final specimen thickness. Some films were produced in the same way also with a nominal thickness of 70 ⁇ .
  • Seal strength was measured in (N) with reference to ASTM F2029/ ASTM F88.
  • two of the above prepared film specimens (same sample composition and thickness) are superimposed in alignment, the adjacent layers being layers of the particular test composition.
  • the superimposed specimens are sealed in transverse direction with a RPM Sealer, model HSE-3 multi seal. Sealing time is 1 .2 seconds at a pressure of 5 bars.
  • the sealing temperature is increased for each seal, starting from 30°C.
  • the sealed samples are left to cool and stored 24h under Standard conditions (23°C and 50% relative humidity).
  • the sealed samples are cut in 15 mm wide strips, which unsealed ends are attached to an Instron machine, where they are tested at a traction speed of 100 mm/min with an initial distance between the grips of 50mm.
  • the maximum force measured during the tensile test is defined as the seal strength.
  • component (b) As component (b) according to the invention the following plastomers were used:
  • Component (a) and (b) are dry-blended in amount as indicated in the tables in the extruder directly equipped with a cast or blown film line as described in the preparation of the film specimens above.
  • heterophasic compositions HECO1 and HECO2 where extruded neat and used for producing film specimens characterized as reference material.
  • the properties are reported under reference examples ref 1 and ref 2 respectively.
  • the examples show that commercial plastomer (e.g. ethylene/octene copolymers) provide a valuable balance of physical-mechanical properties, substantially maintained or slightly reduced seal strength with respect to the base material, and lower seal initiation temperature (higher than 2N at temperatures over 120°C , while for the base materials the threshold value is reached over 130°C).
  • seal strength after sterilization is improved already when a small amount of plastomer is added (2-10wt%, preferably less than 5 wt% of component (b) referred to the weight of the total composition a1 +a2+b according to the invention).
  • Table 2 cast film samples from component (a) (HECO1 ) as base material

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Abstract

La présente invention concerne un film ou un feuillet comprenant au moins une couche d'une composition polyoléfinique constituée, en pourcentage en poids sur la base du total des composants (a1), (a2) et (b), de a1) 42 à 88 % en poids d'un homopolymère de propylène ou d'un copolymère de propylène et d'éthylène et/ou d'une ou plusieurs α-oléfines en C4-C10, ledit homopolymère ou copolymère présentant une solubilité dans le xylène à température ambiante (XSm) inférieure ou égale à 10 % en poids ; a2) 7 à 39 % en poids d'un copolymère d'éthylène et de propylène et/ou d'une ou plusieurs α-oléfines en C4-C10 contenant de 50 à 80 % en poids de motifs dérivés de l'éthylène et présentant une solubilité dans le xylène à température ambiante égale à 50 à 80 % en poids ; et b) 0,5 à 30 % en poids d'un plastomère de type copolymère à base d'éthylène présentant une densité inférieure ou égale à 0,910 g/cc et un indice de fluidité (IF), comme mesuré à 190°C/2,16 kg de charge, au moins égal à 0,5 g/10 minutes.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8691916B2 (en) 2012-05-07 2014-04-08 Dow Global Technologies Llc Retortable easy opening seals for film extrusion
WO2016083266A1 (fr) * 2014-11-24 2016-06-02 Borealis Ag Compositions polymères et articles revêtus par extrusion
EP3031852A1 (fr) * 2014-12-12 2016-06-15 Borealis AG Films de polypropylène présentant un meilleur comportement d'étanchéité, notamment en termes de propriétés de scellage améliorées
EP3168261A1 (fr) * 2015-11-10 2017-05-17 Borealis AG Composition de polypropylène hétérophasique
US10385196B2 (en) 2014-12-12 2019-08-20 Borealis Ag Polypropylene films with improved printability
EP3458513B1 (fr) 2016-05-18 2021-10-06 Borealis AG Copolymères de propylène souple et transparent
CN114829484A (zh) * 2019-10-15 2022-07-29 博里利斯股份公司 用于涂覆聚烯烃织物基材的聚合物组合物

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US8691916B2 (en) 2012-05-07 2014-04-08 Dow Global Technologies Llc Retortable easy opening seals for film extrusion
KR101818899B1 (ko) * 2014-11-24 2018-02-21 보레알리스 아게 폴리머 조성물 및 압출 코팅된 물품
WO2016083266A1 (fr) * 2014-11-24 2016-06-02 Borealis Ag Compositions polymères et articles revêtus par extrusion
EA033640B1 (ru) * 2014-11-24 2019-11-12 Borealis Ag Полимерные композиции и изделия с экструзионным покрытием
US9976020B2 (en) 2014-11-24 2018-05-22 Borealis Ag Polymer compositions and extrusion coated articles
CN107001740B (zh) * 2014-11-24 2018-03-20 博里利斯股份公司 聚合物组合物和挤出涂覆的制品
CN107001740A (zh) * 2014-11-24 2017-08-01 博里利斯股份公司 聚合物组合物和挤出涂覆的制品
JP2018501329A (ja) * 2014-11-24 2018-01-18 ボレアリス エージー ポリマー組成物および押出被覆された物品
US10385197B2 (en) 2014-12-12 2019-08-20 Borealis Ag Polypropylene films with improved sealing behaviour, especially in view of improved sealing properties
US10385196B2 (en) 2014-12-12 2019-08-20 Borealis Ag Polypropylene films with improved printability
WO2016091923A1 (fr) * 2014-12-12 2016-06-16 Borealis Ag Films de polypropylène ayant un comportement de scellage amélioré, en particulier en vue de propriétés de scellage améliorées
EP3031852A1 (fr) * 2014-12-12 2016-06-15 Borealis AG Films de polypropylène présentant un meilleur comportement d'étanchéité, notamment en termes de propriétés de scellage améliorées
RU2716598C2 (ru) * 2014-12-12 2020-03-13 Бореалис Аг Полипропиленовые пленки с улучшенной герметичностью, в частности улучшенными герметизирующими свойствами
WO2017081018A1 (fr) * 2015-11-10 2017-05-18 Borealis Ag Composition de polypropylène hétérophasique
EP3168261A1 (fr) * 2015-11-10 2017-05-17 Borealis AG Composition de polypropylène hétérophasique
EP3458513B1 (fr) 2016-05-18 2021-10-06 Borealis AG Copolymères de propylène souple et transparent
US11634571B2 (en) 2016-05-18 2023-04-25 Borealis Ag Soft and transparent propylene compolymers
CN114829484A (zh) * 2019-10-15 2022-07-29 博里利斯股份公司 用于涂覆聚烯烃织物基材的聚合物组合物

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