WO1996031563A1 - Polyolefines modifiees - Google Patents

Polyolefines modifiees Download PDF

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Publication number
WO1996031563A1
WO1996031563A1 PCT/EP1996/001504 EP9601504W WO9631563A1 WO 1996031563 A1 WO1996031563 A1 WO 1996031563A1 EP 9601504 W EP9601504 W EP 9601504W WO 9631563 A1 WO9631563 A1 WO 9631563A1
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WO
WIPO (PCT)
Prior art keywords
polymer
reactive
agent
olefin polymer
polyolefin
Prior art date
Application number
PCT/EP1996/001504
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English (en)
Inventor
Wai Keung Wong
Stefan Bertil Ohlsson
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Exxon Chemical Patents Inc.
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 Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1996031563A1 publication Critical patent/WO1996031563A1/fr

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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

  • This invention relates to a method to provide a polyolefin composition having improved melt processing characteristics.
  • This invention also relates to a method which provides a polyolefin composition having a reduced number of gels.
  • This invention further realtes to a method to reduce blocking force in polyolef in f ilms .
  • U.S. 4,737,547 attempts to solve this problem and exemplifies a melt blending technique useful for reducing gels in polyethylene compositions modified with organic peroxides and optional cocuring agents such as triallyl cyanurate, triallylisocyanurate or 1,2 polybutadiene or modifying agents of unsaturated organic acids. Note that the films and molded items made in U.S. Patent 4,737,547 using the melt blending technique have no gel, while the films and items made not using the melt blending technique have gel . Note also that in the instances where triallylcyanurate or maleic anhydride was used in the examples, it was present as a coagent in addition to the peroxide.
  • South African Patent Application O. Z .00503/43314 (No. 934261) discloses partially crosslinked ethylene polymers obtained by crosslinking with a bismaleimido compound in the absence of a free radical initiator.
  • concentration of bismalemido compound in the examples indicates however that gels would most likely be produced in this process.
  • This invention provides, inter alia, a means of introducing branching into an olefin polymer while also reducing the number and/or size of resultant gels in the final product.
  • the invention relates to a process for modifying polymer which comprises:
  • this invention relates to a process for lowering the melt index (MI, as measured by ASTM 1238 condition E) of an olefin polymer. While application of this invention is useful for all
  • polyolefins preferred polymers include those comprising ethylene and/or propylene monomers.
  • this class includes but is not limited to, homopolyethylenes and copolymers of ethylene and any linear, cyclic or branched C 3 to C 30 ⁇ -olefin, such as propylene, butene, isobutene, pentene, isopentene, hexene, 4 -methyl -hexene- 1, 3-methyl-hexene -1, heptene, octene, nonene, decene, dodecene, heptadecene, 3 , 5 , 5-tr ⁇ methylhexene-1, cyclopentene , cyclohexene , norbornene, ethylidene norbornene, cyclooctene and the like.
  • this invention is also useful for polymers of propylene, including homopolypropylene and copolymers of propylene one or more of ethylene and any linear, cyclic or branched C 4 to C 30 ⁇ -olefin.
  • examples include copolymers of propylene and one or more of ethylene, butene, isobutene, pentene, isopentene, hexene, 4 -methyl-hexene- 1, 3-methyl-hexene-1, heptene, octene, nonene, decene, dodecene, heptadecene, 3, 5, 5-trimethylhexene-1,
  • Mw/Mn narrow molecular weight distribution
  • CDBI composition distribution breadth index
  • CDBI is defined and explained in WO 9303093, published February 18, 1993, which is incorporated by reference herein for the purposes of U.S. law. Catalyst systems that produce polymers having narrow molecular weights and/or high CDBI's are well described in the art and commercially available products that fall within this category are sold under the trade name EXACTTM by Exxon Chemical Company in Houston, Texas, U.S.A. Likewise, catalyst systems and processes that produce polymers having narrow molecular weights and/or high CDBI's are also described in WO 94/26816, published November 24, 1994.
  • Additional preferred polymers that may be modified according to this invention include all commercially available substantially linear ethylene polymers, including linear low density polyethylenes (LLDPE), high density polyethylenes (HOPE), very low density
  • VLDFE polyethylenes
  • ASTM 792 polyethylene based polymers having a density (as measured by ASTM 792 ) of between 0.88 and 0.97 g/cm 3 .
  • Substantially linear polymer is defined to be a polymer having no long chain branching or a polymer having a rheologically insignificant amount of long chain branching. Branching becomes rheologically significant when shear thinning occurs.
  • one or more of the olefin polymers described above is combined under conditions of heat and/or shear with a reactive co-agent having at least two functional groups capable of irreversibly reacting with free radicals on the polymer backbone.
  • a reactive co-agent is defined to be an agent having two or more sites capable of irreversibly reacting with free radicals on the olefin polymer backbone and "capable of ireversibly reacting" is defined to mean forming covalent bonds stable under the extrusion and processing
  • the free radicals on the polymer backbone are alkyl or alkoxy free radicals.
  • the reactive co-agent is any electrcphillic composition that is more reactive with the free radicals on the polymer backbone than the polymer backbone is reactive with the free radicals.
  • Such compositions include any compound having two or more vinyl unsaturations or other groups capable of irreversibly reacting with a free radical.
  • the reactive co-agent is a diene, an acrylic acid, an ester of an acrylic acid, a C 1 -C 30 alkyl acrylic acid, such as methacrylic acid, ethacrylic acid and the like, an ester of a C 1 -C 30 alkyl acrylic acid, and/or an allyl containing composition and is not a peroxide.
  • These reactive co-agent having two or more active sites preferably have three or more active sites.
  • Preferred species of the reactive co-agent include but are not limited to: trimerhylolpropane trimethacrylate, ethylene glycol dimethacrylate,
  • glycoldimethacrylate 1,6-hexanediol diacrylate
  • tripropylene glycol diacrylate trimethyolpropane- triacrylate, allyl methacrylate, and the like.
  • the free radicals on the polymer backbone are alkyl or alkoxy radicals.
  • the free radicals are
  • the polymer is heated to a molten state or more and/or is subjected to shear sufficient to evenly distribute the reactive co-agent into the polymer or more to generate the free radicals on the polymer back bone.
  • the reactive co-agents are used in the substantial absence of an initiator which generates free radicals.
  • an initiator which generates free radicals.
  • Such initiators are well known in the art and comprise the well known organic peroxides, such as all the peroxides available under the LUPERSOLTM and VULCUP TM trade names from the Lucidol division of Pennwalt Corp and Herculues Incorporated, respectively.
  • the tern substantial absence means that the peroxide or other free radical generating initiator is present at less than 0.5 weight percent, based upon the weight of the copolymer, preferably at 0.1 weight percent, even more preferably less than 0.05 weight percent, even more preferably less than 0 01 weight percent.
  • a neat polyolefin is a polyolefin that nas nad no additives or additive packages combined with the polymer prior to the treatment with the reactive co-agent.
  • an unstabilized polyolefin is a polyolefin that may have one or more additives combined therein but none of which compete for the free radicals along the backbone of the polymer being modified.
  • additives are included in the blend that do compete for the free radicals on the polymer backbone, one should compensate for the effect. For example, one might compensate for the presence of peroxide by adding more of the reactive co-agent.
  • antioxidants include well known fillers such as silica, oil, talc, carbon black and the like.
  • antioxidants such as IRGANOX TM IR1010 or IRGANOXTM IR1076, available from Ciba-Geigy will likely tend to compete wi th the react ive co- agents modif iers for react ion with the free radicals, as induced by heat or irradiation or some other action, of the base polymer chains. Therefore the effectiveness of the reactive co-agents as chain- extending agents may be diminished. Preferably, the modification will be made and the reaction will be completed prior to the inclusion of anti-oxidants. If antioxidants are added prior to completion of the
  • the antioxidant is added after the reaction of the polyolefin with the reactive co-agent.
  • the reactive co-agent may be used alone or in combination with another reactive co-agent and the reactive co-agent (s) is typically used in amounts as small as 10 parts per million (ppm) up to amounts of 750 ppm based upon the weight of the copolymer.
  • the reactive co-agent is used in amounts of 100 ppm to 600ppm, based upon the weight of the copolymer, preferably from 200 ppm to 550 ppm.
  • the polyolefin and the reactive co-agent may be combined by any method known in the art, however melt blending techniques are preferred. Any extruder can be used to combine the polyolefin and the reactive co-agent.
  • the polymer is heated to a temperature high enough to melt the polymer or more and subjected to shear.
  • the reactive co-agent may be added after the polymer has been heated and subjected to shear or may be added at any point prior to or after that .
  • the heat and shearing stresses are preferably maintained but may be increased, decreased or stopped altogether as desired. Typical temperatures that will for melt
  • blending the polymer and the reactive co-agent include those temperatures above the polyolefin's melting
  • the polyolefin is heated to a molten state, subjected to shear and combined with the reactive co- agent.
  • a preferred shear rate is aoout 50 sec -1 or greater, preferably about 100 sec -1 or ⁇ reater.
  • One of many non-limiting examples of how to combine the polymer and the reactive co-agent is, in a Brabender extruder, heating a linear low density ethylene-butene copolymer having a density of about 0.918 to about 0.92 g/cm 3 to a temperature of 230oC or more and subjecting the heated polymer before, during and/or after heating, to a shear rate of 50 sec -1 or more.
  • melt index of the polyolefin (as measured by ASTM 1238, condition D) is decreased by at least 10 %, preferably by at least 15 %, even more preferably at least 20 % as compared to the same polyolefin prior to modification.
  • this method modifies the polymer so as to improve processability, as measured by MI for example, without substantially increasing specific energy
  • polyolefin not substantially increased, more preferably the specific energy consumption is reduced by 20% or more, preferably reduced by 30% or more, preferably by 40% or more.
  • modified polyolefins exhibit reduced shear viscosity at typical extrusion-processing shear rates thereby reducing specific energy consumption.
  • the number and size of gels in films and molded articles made from polyolefin modified as disclosed herein is significantly reduced.
  • the number of gels of the size of 0.1mm 2 or less is 75 or less per square meter of film, even more preferably 50 or less, even more preferably 40 or less.
  • Gel measurements are taken using an on-line flow-vision camera. This camera scans the film surface at 2,000 lines per second and each measurement includes eleven scanned intervals of 500 cm each.
  • the reactive co-agents also appear to serve as anti-oxidants by efficiently scavenging alkyl or alkoxy radicals which may be formed in the polyolefin polymer upon mild oxidation or oxidative chain scission.
  • the reactive co-agents of this invention therefore, appear to be effective anti-oxidants which will stabilize the polymer resin against oxidation and prevent or minimize the typical discoloration or yellowing which accompanies such oxidative degradation
  • modified polymers of this invention show enhanced physical properties compared to peroxide treated polyolefins.
  • the modified polymers of this invention can be used in any typical extrusion, molding, spinning, film forming or other application.
  • Preferred processes include extrusion, film casting, film blowing, melt spinning, injection molding, melt blowing or combinations thereof.
  • Useful articles will include extrudates, pellets, films, and fibers including strands, webs and filaments.
  • Another benefit of this invention is that it may be used to cause chain extension, otherwise called long chain branching in a polyolefin by blending the polymer and the reactive co- agent under conditions of heat and/or shear as described above.
  • [ ⁇ ] is the intrinsic viscosity
  • Mw is the average molecular weight
  • subscripts 1 and 2 designate the unmodified polymer and the modified polymer respectively
  • R ⁇ is the radius of gyration of the coil in the ⁇ state.
  • Intrinsic viscosity numbers are determined according to well-known techniques such as that described by P. A. Lovell in
  • the average molecular weight is determined by gel
  • Sample A is neat Polymer A as described below.
  • Sample C is Polymer A blended with 2500 ppm of ATM 3 at 250 oC and 50 rpm and extruded three times in the extruder described in the Examples below.
  • Sample A has an intrinsic viscosity of 107.5 cm 3 /g and an Mw of 69,700.
  • Sample C has an intrinsic viscosity of 96.7 cm 3 /g and an Mw of 73,100.
  • the value is greater than 1, it indicates the presence of long chain branching.
  • the (R ⁇ 2 )/(R ⁇ 2 ) is greater than or equal to 1.01, more preferably greater than or equal to 1.015, even more preferably greater than or equal to 1.02, even more preferably greater than or equal to 1.025
  • shear thinning behavior of the modified polyolefin as compared to the neat polymer is also evidence of long chain branching being present.
  • the Ea for a given polyolefin modified according to this invention is higher than the Ea for the
  • the Ea of the modified polymer is 5% or more higher than the Ea of tne unmodified polymer, preferably 10 % or more
  • Ea is preferabLy
  • Ea may oe used as long as tne same method is jsed for both polymers.
  • TAC triallyl cyanurate
  • the polymers used were:
  • Polymer A is neat ESCORENE LL 3003TM, An ethylene-hexene copolymer having a melt index (MI) of 3.2 and a density of 0.9175 g/cm 3 .
  • Polymer B is ESCORENE LL 3001TM an ethylene-hexene copolymer having an MI of 1 g/10 min and a density of
  • Polymer C is ECD 103TM an ethylene-hexene copolymer having a Mw/Mn of less than 3, an MI of 1.2 g/10 min and a density of about 0.917 to about 0.918 g/cm 3 , and 2.75 mole % hexene.
  • IRGANOX 1076TM 200 ppm of polyethylene glycol and 500 ppm of zinc sterate.
  • IRGANOX 1076TM 200 ppm of polyethylene glycol and 500 ppm of zinc sterate.
  • Polymer H is ESCORENE LL 1030XV TM which is a linear low density polyethylene copolymer of ethylene and butene having an MI of 0.5 g/10 min and a density of 0.918 g/cm 2 stabilized with 800 ppm of IRGAFOS 168TM, 200 ppm of
  • IRGANOX 1076TM 200 ppm of polyethylene glycol and 500 ppm of zinc sterate.
  • Polymer I is an LLDPE copolymer of ethylene and 3.2 mole
  • Polymer J is an ethylene/hexene copolymer having 3.3 mole
  • Polymer K is an ethylene hexene copolymer having an MI of
  • TRIG B is TRIGANOX BTM (di-tert-butyl-peroxide), a commercially available peroxide sold by AKZO Chemicals.
  • B900 is a mixture of IRGANOX 1076TM and IRGAFOS 168TM in a
  • IRGANOX 1010TM is tetrakis [methylene (3, 5-di-t-butyl-4- hydroxyhydrocinnamate)] methane.
  • IRGANOX 1076TM is octadecyl-3,5-di-t-butyl-4-hydroxy cinnamate.
  • extrusion passes through a Brabender Plasticorder PL 2000 laboratory single-screw extruder with a 25/1 L/D ratio and compression ratio of 4/1.
  • the screw also includes a mixing zone.
  • the extruder has 3 heating zones and was fitted with a round capillary die a diameter of 3 mm; made by Brabender in Duisburg, Germany.
  • Melt index (MI) measurements were carried out with a Davenport Solo 2 melt indexer available from Daventest, Welwyn Garden City, England according to ASTM D-1238 using a preextrusion weight with a mass of 2.16 kg, pre-extrusion time of five minutes, with the barrel temperature set at 190°C, and a cut-off time cf one minute. The conditions and data are reported in Table 1
  • MI melt index (g/10 min)
  • the co-agents were added as liquid to the polymer in granular form and tumble blended for five minutes prior to being introduced into the extruder feed. The amount of each added was determined in a manner such that the number of methacrylate end groups present were equivalent among all test samples. A neat sample of Polymer A was run as a control.
  • Polymers C and E were blended with additives and different amounts of ATM 11 and then cast into films using a Collins film casting line with an L/D ratio of 25/1 and a compression ratio of 3/1 under a temperature profile of 160°C-170oC-180oC-210oC-230°C-230oC-230oC-230°C with a screw speed of 60 rpm.
  • Gel measurements were taken using an on-line flow-vision camera This camera scanned the film surface at 2,000 lines per second.
  • N* number of gels per square meter
  • #long gels the number of gels per square meter 1 cm or longer and 0 2 mm wide or wider
  • a first run
  • b second run.
  • ATM 11 has a Mw of 338.4 and viscosity at 25°C of 40 cSt.
  • Marcol 62 having Mw of 360 and viscosity of 36 cSt at 20 °C was thought to be a reasonable non-reactive match for the ATM 11. Torque was measured at 200°C while mixing at 50 rpm under nitrogen in the Brabender mixer. Table 5
  • Polymers C, G and F were blended with peroxide or ATM 11, formed into films following the procedure described above and tested and tested for physical properties according to the following tests:
  • Shrinkage was tested on a Shrinkage Tester Betex a temperature of 150 °C on samples of 5 cm diameter disks of polymer molten on a silicon oil layer on top of an aluminum plate, the shrinkage ratio is the final dimension in the transverse direction divided by the final dimension in the machine direction);
  • Table 8 presents comparison of specific energy consumption of Polymer C, Polymer C + 250 ppm ATM 11, and Polymer H blended in the brabender described above at 250-255-255-260 °C at 80 rpm then cast on a Collins film casting line under a temperature profile of 160-170-180-210-230-230-230-230 °C with a screw speed of 65 rpm as described above.
  • Polymer J, Polymer K and Polymer G were extruded upon a Leistritz twin screw extruder having an 1/d ratio of 36 and a die diameter of 34mm .
  • the barrell temperature ran through ten zones beginning at about 170 oC and ending at about 260 °C.
  • the extrusion conditions and the data are reported in Table 9.
  • Polymer C was combined with 500 ppm of ATM 11 in a pilot scale Werner and Pfeiderer twin screw extruder at a melt temperature of 290 °C and having an 1/d of 20 and 5 barrel. Polymer I was not combined with any modifiers but was otherwise treated the same . Films were blown from the sample prepared as in example 9. The samples were tested for blocking force according to ASTM D 3354. The data are reported in Table 10.
  • Another advantage to the invention described herein is that it also has the benefit of reducing blocking force, even in the absence of anti -block agents, typically by at least 30 %, even more preferably by about 50 % or more.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention se rapporte à un procédé de réduction des gels en polyoléfines ainsi qu'à un procédé d'introduction de ramifications de chaîne longue dans un polymère de polyoléfine en mélangeant la polyoléfine avec un co-agent réactif comportant deux ou plusieurs groupes fonctionnels susceptibles de réagir de façon irréversible avec des radicaux libres sur le squelette de la polyoléfine sous des conditions de chaleur et/ou de cisaillement. Cette invention décrit également un procédé de réduction de la force de blocage dans les films de polyoléfine.
PCT/EP1996/001504 1995-04-07 1996-04-09 Polyolefines modifiees WO1996031563A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9507321.9 1995-04-07
GBGB9507321.9A GB9507321D0 (en) 1995-04-07 1995-04-07 Method to reduce gel in polyolefins

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114486A (en) * 1996-03-05 2000-09-05 The Dow Chemical Company Rheology-modified polyolefins
US6232410B1 (en) 1997-08-27 2001-05-15 The Dow Chemical Company Elastomers with improved processability
US10336893B2 (en) 2014-12-23 2019-07-02 Dow Global Technologies Llc Process for preparing a modified ethylene-based polymer using a hydrocarbon initiator

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1322846A (fr) * 1962-01-15 1963-04-05 Kleber Colombes Procédé de polymérisation de monomères vinylidéniques, en présence de polyoléfines saturées
EP0027375A2 (fr) * 1979-10-12 1981-04-22 Toa Nenryo Kogyo Kabushiki Kaisha Elastomère modifié, et stratifié le comprenant
EP0210307A1 (fr) * 1985-06-27 1987-02-04 Du Pont Canada Inc. Procédé de greffage de monomères sur des polyoléfines
EP0269000A2 (fr) * 1986-11-20 1988-06-01 BASF Aktiengesellschaft Greffage sans peroxyde d'homo- ou copolymères d'éthylène d'une densité inférieure à 0,930g/cm3 et utilisation des polymères greffés pour la préparation d'ionomères ou de produits adhésifs
WO1994025498A1 (fr) * 1993-04-27 1994-11-10 Dupont Canada Inc. Greffe de monomeres sur des polyolefines en presence de peroxydes organiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1322846A (fr) * 1962-01-15 1963-04-05 Kleber Colombes Procédé de polymérisation de monomères vinylidéniques, en présence de polyoléfines saturées
EP0027375A2 (fr) * 1979-10-12 1981-04-22 Toa Nenryo Kogyo Kabushiki Kaisha Elastomère modifié, et stratifié le comprenant
EP0210307A1 (fr) * 1985-06-27 1987-02-04 Du Pont Canada Inc. Procédé de greffage de monomères sur des polyoléfines
EP0269000A2 (fr) * 1986-11-20 1988-06-01 BASF Aktiengesellschaft Greffage sans peroxyde d'homo- ou copolymères d'éthylène d'une densité inférieure à 0,930g/cm3 et utilisation des polymères greffés pour la préparation d'ionomères ou de produits adhésifs
WO1994025498A1 (fr) * 1993-04-27 1994-11-10 Dupont Canada Inc. Greffe de monomeres sur des polyolefines en presence de peroxydes organiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM B K ET AL: "CROSS-LINKING OF POLYPROPYLENE BY PEROXIDE AND MULTIFUNCTIONAL MONOMER DURING REACTIVE EXTRUSION", ADVANCES IN POLYMER TECHNOLOGY, vol. 12, no. 3, 1 January 1993 (1993-01-01), pages 263 - 269, XP000383265 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114486A (en) * 1996-03-05 2000-09-05 The Dow Chemical Company Rheology-modified polyolefins
US6689851B1 (en) 1996-03-05 2004-02-10 Dow Global Technologies Inc. Rheology-modified polyolefins
US6232410B1 (en) 1997-08-27 2001-05-15 The Dow Chemical Company Elastomers with improved processability
US10336893B2 (en) 2014-12-23 2019-07-02 Dow Global Technologies Llc Process for preparing a modified ethylene-based polymer using a hydrocarbon initiator

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