EP1102805A1 - Film en polymere de propylene oriente avec propriete de barriere a l'oxygene amelioree - Google Patents

Film en polymere de propylene oriente avec propriete de barriere a l'oxygene amelioree

Info

Publication number
EP1102805A1
EP1102805A1 EP00900759A EP00900759A EP1102805A1 EP 1102805 A1 EP1102805 A1 EP 1102805A1 EP 00900759 A EP00900759 A EP 00900759A EP 00900759 A EP00900759 A EP 00900759A EP 1102805 A1 EP1102805 A1 EP 1102805A1
Authority
EP
European Patent Office
Prior art keywords
film according
propylene polymer
alkyl
group
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00900759A
Other languages
German (de)
English (en)
Inventor
Anthony J. De Nicola, Jr.
Tinh N. Nguyen
Lin-Chen Yu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Technology Co BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Technology Co BV filed Critical Basell Technology Co BV
Publication of EP1102805A1 publication Critical patent/EP1102805A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • This invention resides in the chemical arts. It relates to film formed from polymers of propylene.
  • Predominately crystalline homopolymer of propylene the polypropylene of commerce, has achieved tonnage use in many applications.
  • One of them is the manufacture of film, especially biaxially oriented film used in the packaging of, for example, snack foods such as potato chips and the like. Indeed, such film has become known as "BOPP" film.
  • Polypropylene film while having advantageous properties, for example, chemical resistance and excellent barrier to moisture, is not a good barrier to oxygen; oxygen transmission through the film is too high for many packaging film uses. This problem of oxygen barrier property also exists in the case of films formed from predominately crystalline, random copolymers of propylene and other l-olefins such as ethylene and 1- butene.
  • This invention is based on the discovery that melt blending with predominantly crystalline polypropylene a graft copolymer of predominantly crystalline polypropylene and certain polymerized monomer material gives a composition that in the form of biaxially oriented film is a good barrier to oxygen transmission.
  • the invention is broader than this discovery.
  • the invention in summary, broadly comprises oriented film formed from a melt blend consisting essentially of
  • propylene polymer material selected from the group consisting of predominantly crystalline polypropylene and predominantly crystalline copolymers and terpolymers of propylene and 1-olefin material selected from the group consisting of ethylene and the butenes, which copolymers and terpolymers have more than 50 mole % propylene units;
  • graft copolymer material selected from the group consisting of graft copolymers of (a) propylene polymer material selected from the group consisting of predominantly crystalline polypropylene and predominantly crystalline copolymers and terpolymers of propylene and 1-olefin material selected from the group consisting of ethylene and the butenes, which copolymers and terpolymers have more than 50 mole % propylene units, and (b) polymerized monomer material selected from the group of monomers consisting of styrene, p-alkylstyrenes, acrylic acid, alkacrylic acids, alkyl acrylates, alkyl alkacrylates, acrylonitrile, and vinyl acetate with or without ethylene, the alkyls in these monomers with alkyl substituents having one-four carbons, the concentration of the graft copolymer material being such that the rate of oxygen transmission through the film is substantially less than if no graft copolymer material were present
  • the propylene polymer material in one general embodiment of the blend from which the oriented film of this invention is formed is composed of only one propylene polymer of the recited group. In another general embodiment it is composed of more than one such polymer. All of the members of the group from which the propylene polymer material is selected, and processes for making them, are generally known.
  • the graft copolymer material in one general embodiment of the blend from which the oriented film of this invention is formed is composed of only one graft copolymer of the recited group. In another general embodiment it is composed of more than one such grafted polymer. In more specific embodiments of these general embodiments, the grafted, polymerized monomer material comprises only one grafted, polymerized monomer. In other, more specific embodiments of these general embodiments, the grafted, polymerized monomer material comprises more than one grafted, polymerized monomer.
  • the members of the group of graft copolymers, and processes for making them, are generally known.
  • the graft copolymer product furnishes not only the graft copolymer material component, but all of the propylene polymer material component of the blend. However, in most embodiments the graft copolymer product supplies only part of the propylene product material.
  • non-grafted polymerized monomer material is formed.
  • the quantity of such can be as much as 50% by weight of the graft copolymer material product of the process in each case.
  • the presence of such in the melt blend generally can be tolerated.
  • the concentration of the graft copolymer material in the blend being about 10-90 weight % of the propylene polymer material.
  • melt blend comprise at conventional concentrations stabilizer material selected from the group consisting of antioxidants, heat stabilizers, ultraviolet light inhibitors, and the like.
  • embodiments of the melt blend can comprise at conventional concentrations other additives, for example, nucleating agent material, filler material, extender material, colorant material, antacid material, mechanical property improver material (for example, a polyolefin type rubber such as ethylene-octene copolymer rubber), and the like.
  • the melt blend and the oriented film thereof are made by conventional ways and means.
  • the monomer material used to make the various grafted polymers were these mixtures: methyl methacrylate and methyl acrylate, methyl methacrylate and methacrylic acid, and methyl methacrylate and acrylonitrile.
  • the concentration of the methyl acrylate in these mixtures was 5 mole %.
  • the peroxide was t-butyl peroxy-2-ethyl hexanoate. It was used while in solution (50 wt%) in mineral spirits.
  • the solution is commercially available from Elf Atochem North America, Inc., as Lupersol PMS.
  • Example 100 parts (all parts are by weight) of the resin were introduced into a mechanically agitated reactor, the interior of the reactor was inerted by nitrogen flushing, and the reactor contents were heated to and maintained at reaction temperature. Then, 95 parts of monomer material per 100 parts of resin were introduced into the reactor at the rate per minute of 1 part of monomer material per 100 parts of resin, while at the same time the peroxide solution was introduced into the reactor at a rate equivalent to 1 mole of peroxide per 100 moles of monomer material being introduced.
  • BMWD PP broad molecular weight distribution polypropylene resin
  • the quantity of BMWD PP in the sample was such as to give the Effective Add Level of the total polymerized monomer material (both that which was grafted to the KPO10 polymer, and that which was not grafted to the KP010 polymer) reported for the Example in the following tables.
  • the stabilizer material in all examples comprised a conventional-for-film antacid and a conventional-for-film phenolic antioxidant at a 1:4 wt ratio.
  • the stabilizer material comprised a different, but conventional-for-film, antacid, a different, but conventional-for-film, phenolic antioxidant, and a conventional-for-film, phosphite type stabilizer at approximately a 1 :1 :1 wt ratio.
  • Example 5 While the different composition of the stabilizer material in Example 5 is believed not to have skewed the results, it is reported here for accuracy. In this regard, because the stabilizer material is not at the heart of the invention, it is not considered necessary to enable the best mode to be practiced to identify specifically the stabilizer material components, as long as the chemical types of the components are disclosed.
  • Each sample was melt extruded from either a 34 mm co-rotating, intermeshing Leistritz LSM twin screw extruder at a barrel temperature of 240oC, a screw speed of 250 rpm, and a throughput rate of 13.6 kg/hr, or a 40mm co-rotating, intermeshing Werner & Pfleiderer ZSK twin screw extruder at a barrel temperature of 210oC, a screw speed of 500 rpm, and a throughput rate of 73 kg/hr.
  • the thus extruded sample was cast at 250oC into a 25 mil (635aem) thick sheet which was quenched on a water-cooled chill roll.
  • ORR Oxygen transmission rate
  • YK Haze-Guard meter The following tables set forth the composition of the oriented film of each Example, and the data obtained in measuring the physical properties thereof. These data were obtained on samples made at different times. In the case of multiple samples of a composition made at different times there were normal variations in the physical measurement data. These were averaged and the averages are reported in the tables along with the number of values averaged as indicated in the "No. of Data Points" lines. Further, the first table includes for comparison the data obtained on a commercial, film grade, polypropylene resin (polypropylene + conventional stabilizer material).
  • AN means acrylonitrile
  • MAA means methacrylic acid.
  • MeAc means methyl acrylate.
  • PP means polypropylene.
  • PP-g-PMMA means the graft copolymer product that consists essentially of polypropylene grafted with polymerized methyl methacrylate and polymerized methyl acrylate.
  • PP-g-PMMA/ AN means the graft copolymer product that consists essentially of polypropylene grafted with polymerized methyl methacrylate and polymerized acrylonitrile.
  • PP-g-PMMA/MAA means the graft copolymer product that consists essentially of polypropylene grafted with polymerized methyl methacrylate and polymerized methacrylic acid.
  • film as used in this specification means a sheet, the thickness of which is 10 mils (254 -em) or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Packages (AREA)

Abstract

Cette invention se rapporte à un film en polymère de propylène orienté, dont la propriété de barrière à l'oxygène est considérablement améliorée. On obtient cette amélioration en incorporant dans la composition de polymère de propylène à partir de laquelle est fabriqué ledit film un matériau copolymère greffé renfermant essentiellement un matériau polymère de propylène cristallin, dont le ou les polymères possèdent des greffes d'un matériau monomère polymérisé d'un groupe constitué par du styrène, des p-alkylstyrènes, de l'acide acrylique, des acides alcacryliques, des alcacrylates d'alkyle, de l'acrylonitrile et, avec ou sans éthylène, de l'acétate de vinyle.
EP00900759A 1999-01-29 2000-01-24 Film en polymere de propylene oriente avec propriete de barriere a l'oxygene amelioree Withdrawn EP1102805A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US24021899A 1999-01-29 1999-01-29
US240218 1999-01-29
PCT/IB2000/000060 WO2000044815A1 (fr) 1999-01-29 2000-01-24 Film en polymere de propylene oriente avec propriete de barriere a l'oxygene amelioree

Publications (1)

Publication Number Publication Date
EP1102805A1 true EP1102805A1 (fr) 2001-05-30

Family

ID=22905627

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00900759A Withdrawn EP1102805A1 (fr) 1999-01-29 2000-01-24 Film en polymere de propylene oriente avec propriete de barriere a l'oxygene amelioree

Country Status (12)

Country Link
EP (1) EP1102805A1 (fr)
JP (1) JP2002535466A (fr)
KR (1) KR20010072562A (fr)
CN (1) CN1293690A (fr)
AU (1) AU3068800A (fr)
BR (1) BR0004531A (fr)
CA (1) CA2326808A1 (fr)
ID (1) ID26404A (fr)
NO (1) NO20004874L (fr)
PL (1) PL343282A1 (fr)
TR (1) TR200002823T1 (fr)
WO (1) WO2000044815A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050203232A1 (en) * 2004-03-05 2005-09-15 Rolland Loic P. Ethylene copolymer modified oriented polypropylene
CN100404115C (zh) * 2005-08-24 2008-07-23 中国石油天然气股份有限公司 一种接枝苯乙烯改性膜及其制备方法和应用
KR100660006B1 (ko) * 2006-03-20 2006-12-20 주식회사 한국종합기술 철도도심구간의 소음저감형 궤도 설치 구조
KR20220049824A (ko) 2020-10-15 2022-04-22 한화토탈 주식회사 기체 차단성이 우수한 복합 수지 조성물 및 이로부터 제조된 성형품

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5688481A (en) * 1979-12-21 1981-07-17 Mitsubishi Petrochem Co Ltd Easily releasable heat-sealing material
US5300570A (en) * 1989-03-01 1994-04-05 Rohm And Haas Company Plastic articles with compatibilized barrier resin
DE3915533A1 (de) * 1989-05-12 1990-11-15 Hoechst Ag Bedruckbare und metallisierbare orientierte polyolefinfolie
AU5576198A (en) * 1997-01-22 1998-08-18 Mitsubishi Chemical Corporation Resin film for sealant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0044815A1 *

Also Published As

Publication number Publication date
PL343282A1 (en) 2001-08-13
ID26404A (id) 2000-12-21
CN1293690A (zh) 2001-05-02
NO20004874L (no) 2000-11-29
BR0004531A (pt) 2000-11-21
AU3068800A (en) 2000-08-18
TR200002823T1 (tr) 2000-12-21
JP2002535466A (ja) 2002-10-22
NO20004874D0 (no) 2000-09-28
CA2326808A1 (fr) 2000-08-03
KR20010072562A (ko) 2001-07-31
WO2000044815A1 (fr) 2000-08-03

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