WO1995025140A2 - Procedes pour produire des polyolefines ayant des proprietes accrues a l'etat fondu a des vitesses de cisaillement faibles - Google Patents

Procedes pour produire des polyolefines ayant des proprietes accrues a l'etat fondu a des vitesses de cisaillement faibles Download PDF

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Publication number
WO1995025140A2
WO1995025140A2 PCT/US1995/003253 US9503253W WO9525140A2 WO 1995025140 A2 WO1995025140 A2 WO 1995025140A2 US 9503253 W US9503253 W US 9503253W WO 9525140 A2 WO9525140 A2 WO 9525140A2
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin
sorbitol
sec
melt viscosity
network
Prior art date
Application number
PCT/US1995/003253
Other languages
English (en)
Other versions
WO1995025140A3 (fr
Inventor
Jean-Marc Dekoninck
Original Assignee
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 WO1995025140A2 publication Critical patent/WO1995025140A2/fr
Publication of WO1995025140A3 publication Critical patent/WO1995025140A3/fr

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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • 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

Definitions

  • This invention relates to polyolefin compositions modified by an additive capable of producing high viscosity at low shear rates but does not substantially alter the viscosity at high shear rates.
  • Sorbitol and other such nucleating agents are known for their use in polyolefins, especially polypropylene, to alter the crystallization rate of the polyolefin.
  • sorbitol is used in polypropylene to increase the crystallization rate thus decreasing time spent in a mold waiting for the resin to harden.
  • Sorbitol and like nucleating agents are also used in ascorbic acid fermentation, in cosmetic creams and lotions, toothpastes, tobaccos, gelatins, bodying agents (for paper, textiles, and liquid pharmaceuticals) , softeners (candy) , sugar crystallization inhibitors, surfactants (urethane resins and rigid foams) , plasticisers, stabilizers for vinyl resins, food additives, sweeteners, humectants, emulsifiers, thickeners, anti-caking agents and dietary supplements. These agents, however, have not been used before to modify the rheology of a polyolefin.
  • This invention relates to a method to increase the melt viscosity of a polyolefin at low shear rates comprising blending a composition that forms a network at low deformation rates between about 0.01 and 10 sec" 1 but does not form or maintain networks at high deformation rates of greater than 100 sec" 1 with a polyolefin.
  • compositions capable of forming a light network such as a fibril network, at low shear rates, while not forming such networks at high shear rates, will act to increase the melt viscosity and the melt strength at low shear rates of a given polymer, while not affecting the melt viscosity at high deformation rates.
  • a networking agent that forms a light microfibril network is employed in accordance with a preferred embodiment of the present invention. Sorbitol and its substituted and/or isomeric forms and/or derivatives thereof are the preferred agents. Substituted sorbitol such as, di-benzylidene sorbitol and other commercial substiuted sorbitols are particularly preferred agents.
  • the agent is blended typically at 1 weight percent or less with a polyolefin. This very small amount of the networking agent has the unique effect of increasing melt strength and viscosity of the polyolefin blend at low shear rates.
  • Preferred polyolefins for use in this invention comprise, but are not limited to, any polymer of a C2 to c 1 00 olefin, preferably C 2 to C 30 olefins, even more preferably C 2 to C 30 alpha-olefins.
  • Preferred monomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, hexadecene, dodecyldodecene, 3-methyl-pentene-1, 3,5,5-trimethylhexene-l, vinyl acetate and the like.
  • Preferred polyolefins include polyethylene, polypropylene, polybutene, ethylene propylene rubber, ethylene propylene diene monomer rubber, ethylene- butene copolymer, ethylene vinyl acetate copolymer and the like.
  • preferred polyolefins may be of any weight average molecular weight and any molecular weight distribution (Mw/Mn) .
  • Mw/Mn molecular weight distribution
  • the polyolefin has a composition distribution breadth index (CDBI) of 50% or greater, preferably about 60% or greater, even more preferably 70% or greater.
  • Composition distribution breadth index (CDBI) is measured by a method defined and described in Patent Cooperation Treaty publication WO 9303093 published February 18, 1993.
  • preferred polyolefins may also comprise a diene co- or ter-polymer.
  • Preferred comonomers include dienes having 3 to 60 carbon atoms, even more preferably 3 to 30 carbon atoms.
  • Representative examples of dienes that may be used as the second or third monomer include:
  • Branched chain acyclic dienes such as: 5- methyl-l,4-hexadiene; 3,7-dimethyl 1,6-octadiene; 3,7- dimethyl 1,7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene.
  • Single ring alicyclic dienes such as: 1,4- cyclo-hexadiene; 1,5-cyclooctadiene; 1,5-cyclo- dodecadiene; 4-vinylcyclohexene; 1-allyl, 4- isopropylidene cyclo-hexane; 3-allyl-cyclopentene; 4- allyl cyclohexene and l-isopropenyl-4-(4-butenyl) cyclohexane.
  • Multi-single ring alicyclic dienes such as: 4,4'-dicyclo-pentenyl and 4,4'-dicyclohexenyl.
  • Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene; bicyclo (2.2.1) hepta 2,5-diene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as: ethylidene norbornene; 5-methylene-6- methyl-2- norbornene; 5-methylene-6, 6-dimethyl-2-norbornene; 5- propenyl-2-norbornene; 5-(3-cyclo-pentylidene)-2- norbornene and 5-cyclohexylidene-2-norbornene; etc.
  • homopolymers and copolymers of ethylene having up to 30 wt% of a C 3 to C 30 alpha-olefin comonomer are blended with up to 1.0 wt% of the networking agent, preferably substituted sorbitol or a derivative thereof.
  • Substituted sorbitol can be purchased as Millad 3905TM from Milliken Chemical.
  • the networking agent can be any agent that forms a light network under low shear. This network is light enough that it does not remain when subjected to high shear rates and thus does not alter the viscosity by more than 10% at higher shear rates.
  • the networking agent is preferably present at or about 1 weight percent or less based upon the weight of the polyolefin, preferably about 1.0 wt% to about 0.005 wt%, even more preferably about 0.8 to about 0.01 wt%, even more preferably 0.6 wt% to 0.05 wt%, even more preferably 0.6 to 0.2 wt%.
  • the blends of this invention can be produced by methods known in the art for blending additives into polyolefins.
  • polyethylene can be dry- blended with networking agents such as sorbitol in a standard mixing vessel, and thereafter can be transferred into a standard extruder.
  • the blended product has the properties of low viscosity at high shear rates and high viscosity and high melt strength at low shear rates.
  • the networking agents reduce haze and enhance strength properties such as tear (in both machine and transverse directions) .
  • the modified polyolefins of this invention have one or more of: increased melt strength at low shear rates, increased viscosity at low shear rates, increased tear strength, increased dart impact and reduced haze.
  • the melt viscosity at a shear or deformation rate of 1 sec" 1 or less is usually increased by at least about 50%, even more preferably at least about 100%, even more preferably at least about 200%, while the melt viscosity at a shear rates of 100 sec" 1 or more is increased by no more than 10%.
  • MI Melt index
  • Rheometrics RMS-800 rotational Rheometer operated in oscillatory (sinusoidal deformation) mode with the molten sample between parallel plates of 25mm diameter and with a sample thickness of 1 to 2 mm.
  • the frequency range is 0.1 to 100 radians per second at a maximum strain amplitude of 10%.
  • Exact 3011ATM an ethylene polymer commercially available from Exxon Chemical Co. produced using a cyclopentadienyl transition metal compound in combination with methylalumoxane catalysts, having an MI of 1.0 dg/min, a density of 0.9 g/cc, and a CDBI of > 50%, and Millad 3905TM ( dibenzylidene sorbitol), were blended in varying proportions in a plastograph brabender. The polyolefin was first melted at 190°C, 60 rpm, under nitrogen for 3 minutes. Different levels of Millad 3905TM were added and blended for 3 minutes more.
  • the blends were then compression molded into films of about 1 mm thickness, at 218 ⁇ C (425 ⁇ F) for a total of 5 minutes and cooled for three minutes at about 27°C (80°F).
  • Rheology data were accumulated on a Rheometrics RMS 800 at 140°C under a 10% strain.
  • Melt extensional deformation data were obtained using the combination of a Goettfert Rheograph 2001 capillary rheometer as the extrudate source and a Goettfert Rheotens extensional rheometer to stretch the extruding filament.
  • the capillary rheometer had a barrel diameter of 15mm, and used a 10mm long x 2mm diam. x 180° entry angle die. Data were taken at 160°C with plunger speed set to yield a constant 20 sec" 1 shear rate in the die, with initial wheel velocity in the Rheotens set (as per standard operating method) to yield zero balance arm force and accelerated at
  • Table II reports the melt strength of one polyolefin of the blend.
  • An ethylene/hexene copolymer having a melt index of 1.0 dg/min and a density of 0.920 g/cm 3 and 0.4 wt% sorbitol are blended in an extruder at about 220°C and subsequently blown into a film on an Egan 1.5 inch (3.81 cm) film blowing machine.
  • Haze is measured by ASTM D-1003 161 Procedure A. Tear (MD and TD) is measured by ASTM D-1922. Dart impact is measured by ASTM D-1709/75 Method A (PL/002) .

Abstract

Cette invention se rapporte à un procédé qui sert à augmenter les propriétés d'une polyoléfine à l'état fondu, telle que sa résistance à l'état fondu, sa viscosité à l'état fondu, sa tenue à chaud et sa transformabilité, en combinant cette polyoléfine avec un agent de formation de réseau, lequel est constitué de préférence par du sorbitol substitué ou insubstitué ou des isomères ou dérivés de ce sorbitol.
PCT/US1995/003253 1994-03-16 1995-03-16 Procedes pour produire des polyolefines ayant des proprietes accrues a l'etat fondu a des vitesses de cisaillement faibles WO1995025140A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US21388894A 1994-03-16 1994-03-16
US08/213,888 1994-03-16

Publications (2)

Publication Number Publication Date
WO1995025140A2 true WO1995025140A2 (fr) 1995-09-21
WO1995025140A3 WO1995025140A3 (fr) 1995-10-26

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PCT/US1995/003253 WO1995025140A2 (fr) 1994-03-16 1995-03-16 Procedes pour produire des polyolefines ayant des proprietes accrues a l'etat fondu a des vitesses de cisaillement faibles

Country Status (2)

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US (1) USH1656H (fr)
WO (1) WO1995025140A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042263A1 (fr) * 1996-05-03 1997-11-13 Milliken Research Corporation Procede pour thermoformer de la resine polyolefinique
EP0969036A1 (fr) * 1997-11-06 2000-01-05 New Japan Chemical Co.,Ltd. Procede de moulage de gel de composition de resine polyolefinique orientee et objet moule produit par ce procede
EP1002833A1 (fr) * 1998-11-19 2000-05-24 Mitsui Chemicals, Inc. Compositions de résine basées sur des polyoléfines et produits fabriqués avec celles-ci
WO2019084360A1 (fr) * 2017-10-27 2019-05-02 W.R. Grace & Co.-Conn. Polymères de polyoléfine ayant une résistance accrue à l'état fondu

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070080485A1 (en) * 2005-10-07 2007-04-12 Kerscher Christopher S Film and methods of making film

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0092940A2 (fr) * 1982-04-23 1983-11-02 E.C. Chemical Ind. Co., Ltd. Composition de résine polyoléfinique

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JPS5122740A (fr) * 1974-08-16 1976-02-23 Kenzo Hamada
JPS6113252A (ja) * 1984-06-29 1986-01-21 Canon Inc 電子写真感光体
JPS61133252A (ja) * 1984-12-04 1986-06-20 Ube Ind Ltd 射出成形法
US5084534A (en) * 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
JPH0777754B2 (ja) * 1987-07-07 1995-08-23 三井石油化学工業株式会社 ストレッチ包装用フィルム
JPH089679B2 (ja) * 1988-09-16 1996-01-31 新日本理化株式会社 樹脂改質用ジアセタール組成物及び結晶性樹脂組成物
US5049605A (en) * 1989-09-20 1991-09-17 Milliken Research Corporation Bis(3,4-dialkylbenzylidene) sorbitol acetals and compositions containing same
EP0728158A4 (fr) * 1993-11-08 1997-09-03 Mobil Oil Corp Composition comprenant un melange d'un polymere ou d'un copolymere d'ethylene avec du sorbitol ou un derive de sorbitol

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Publication number Priority date Publication date Assignee Title
EP0092940A2 (fr) * 1982-04-23 1983-11-02 E.C. Chemical Ind. Co., Ltd. Composition de résine polyoléfinique

Non-Patent Citations (2)

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DATABASE WPI Week 8631, Derwent Publications Ltd., London, GB; AN 86-201001 & JP,A,61 133 252 (UBE IND. KK) 20 June 1986 *
DATABASE WPI Week 9424, Derwent Publications Ltd., London, GB; AN 94-277168 & RESEARCH DISCLOSURE, vol.1994, no.36406, 4, EMSWORTH, GB page 406, XP000468930 KATSOULIS ET. AL. 'method of gelling non polar oils with dibenzylidene sorbitol...' *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042263A1 (fr) * 1996-05-03 1997-11-13 Milliken Research Corporation Procede pour thermoformer de la resine polyolefinique
AU707227B2 (en) * 1996-05-03 1999-07-08 Milliken Research Corporation Method of thermoforming polyolefin resin
US5961914A (en) * 1996-05-03 1999-10-05 Milliken & Company Method of thermoforming polyolefin resin
CN1080741C (zh) * 1996-05-03 2002-03-13 米利肯研究公司 聚烯烃树脂的热成型方法
US6238615B1 (en) 1997-11-06 2001-05-29 New Japan Chemical Co., Ltd. Orientated gel molding method of polyolefin based resin composition
EP0969036A4 (fr) * 1997-11-06 2000-02-23 New Japan Chem Co Ltd Procede de moulage de gel de composition de resine polyolefinique orientee et objet moule produit par ce procede
EP0969036A1 (fr) * 1997-11-06 2000-01-05 New Japan Chemical Co.,Ltd. Procede de moulage de gel de composition de resine polyolefinique orientee et objet moule produit par ce procede
US6593427B2 (en) 1997-11-06 2003-07-15 New Japan Chemical Co., Ltd. Orientated gel molding method of polyolefin-based resin composition and molded article obtainable by the method
KR100548863B1 (ko) * 1997-11-06 2006-02-02 신닛폰 리카 가부시키가이샤 폴리올레핀계 수지 조성물의 배향 겔 성형 방법 및 이 방법에의해 제조되는 성형체
EP1002833A1 (fr) * 1998-11-19 2000-05-24 Mitsui Chemicals, Inc. Compositions de résine basées sur des polyoléfines et produits fabriqués avec celles-ci
SG82031A1 (en) * 1998-11-19 2001-07-24 Mitsui Chemicals Inc Polyolefin-based resin compositions and fabricated products produced therefrom
US6534579B1 (en) 1998-11-19 2003-03-18 Mitsui Chemicals, Inc. Polyolefin-based resin compositions and fabricated products produced therefrom
WO2019084360A1 (fr) * 2017-10-27 2019-05-02 W.R. Grace & Co.-Conn. Polymères de polyoléfine ayant une résistance accrue à l'état fondu

Also Published As

Publication number Publication date
USH1656H (en) 1997-06-03
WO1995025140A3 (fr) 1995-10-26

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