EP1200491A1 - Äthylen und/oder alpha-olefin / vinyl oder vinyliden aromatische copolymerzusammensetzungen - Google Patents

Äthylen und/oder alpha-olefin / vinyl oder vinyliden aromatische copolymerzusammensetzungen

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Publication number
EP1200491A1
EP1200491A1 EP00938163A EP00938163A EP1200491A1 EP 1200491 A1 EP1200491 A1 EP 1200491A1 EP 00938163 A EP00938163 A EP 00938163A EP 00938163 A EP00938163 A EP 00938163A EP 1200491 A1 EP1200491 A1 EP 1200491A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
vinyl
styrene
component
alpha
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Withdrawn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
EP00938163A
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English (en)
French (fr)
Inventor
Stephen F. Hahn
Oscar D. Redwine
Ravi B. Shankar
Francis J. Timmers
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.)
Dow Global Technologies LLC
Original Assignee
Dow Chemical Co
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Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP1200491A1 publication Critical patent/EP1200491A1/de
Withdrawn legal-status Critical Current

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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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08L23/04—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
    • C08L23/0838—Copolymers of ethene with aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention relates to compositions comprising interpolymers of vinyl or vinylidene aromatic monomers with ethylene and/or one or more alpha-olefin monomers.
  • the catalyst used to prepare these interpolymers [(4,5-methylene- phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers.
  • the resulting interpolymers contain successive vinyl or vinylidene aromatic monomer insertions and thus can have vinyl or vinylidene aromatic monomer incorporation in excess of 65 mole percent.
  • Copolymers of ethylene and styrene including materials with more than 50 mole percent styrene incorporation have been reported using an ansa metallocene catalyst as disclosed by Arai, T.; Ohtsu, T.; Suzuki, S. in Macromolecular Rapid Commun. 1998, and Polym. Prepr., 1998, 39(1), 220-221.
  • U.S. Patent No. 5,703,187 describes "pseudo random" ethylene styrene interpolymers characterized by a unique monomer distribution in which successive head-to-tail styrene monomer insertions are not observed that is no SS diads or SSS triads. Except for the absence of sequential head-to-tail styrene monomer insertions, the styrene distribution in interpolymers is still found to be well dispersed hence the term "pseudo-random".
  • a particular distinguishing feature of pseudo-random copolymers was the fact that all phenyl or bulky hindering groups substituted on the polymer backbone are separated by 2 or more methylene units.
  • the next monomer inserted must be ethylene or a vinyl or vinylidene aromatic monomers which is inserted in an inverted fashion (where inverted is taken to mean a 2,1 insertion where a normal insertion is taken to be 1,2, however it is understood by those skilled in the art that the opposite can be true and would not change the description or properties of the interpolymers of the present invention).
  • the next monomer must be ethylene, as the insertion of another vinyl or vinylidene aromatic monomer at this point would place the hindering substituent closer together than the minimum separation as described above.
  • WO 98/0999 describes the "substantially random" ethylene styrene interpolymers which, while including the aforementioned the pseudo random interpolymers, also included interpolymers prepared using specific metallocene polymerization catalysts. Use of these specific metallocene polymerization catalysts resulted in the formation of interpolymers characterized by a unique monomer distribution. In this distribution, although most of the polymer chains are pseudo random in styrene distribution, a small amount of sequences involving two head-to-tail vinyl aromatic monomer insertions preceded and followed by at least one ethylene insertion were observed.
  • the catalyst [(4,5-methylene- phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers in their polymerization with ethylene and/or one or more alpha-olefin monomers, and results in the preparation of new interpolymers which include, in the case of ethylene/styrene interpolymers, both SSS and higher (for example SSSS, SSSSS etc) sequences.
  • SSS SSSS
  • SSSSSSS higher sequences.
  • the present invention pertains to an interpolymer comprising;
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70
  • values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
  • detectable vinyl or vinylidene aromatic monomer triads is used herein to indicate a sequence of three successive vinyl or vinylidene aromatic insertions in the interpolymer. In the case of an ethylene/styrene inte ⁇ olymer this would correspond to an -SSS- triad.
  • triads When any atactic polystyrene impurity is separated out from the polymer, these triads are detectable by the presence of a peak in the 13 C NMR spectrum which occurs at a chemical shift corresponding to the methine carbons in the polymer backbone of an ethylene/styrene interpolymer at 44.6 ppm (ESSSE)
  • ESSSE ethylene/styrene interpolymer at 44.6 ppm
  • Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS tetrads, SSSSS pentads.
  • the inte ⁇ olymers of the present invention are prepared using the catalyst , [(4,5- methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium.
  • inte ⁇ olymers which include, in the case of ethylene/styrene inte ⁇ olymers, both SSS and higher (for example SSSS, SSSSS etc) sequences.
  • SSS ethylene/styrene inte ⁇ olymers
  • SSSSS higher sequences.
  • the resulting inte ⁇ olymers are able to exhibit upper limits to vinyl or vinylidene aromatic monomer contents in excess of 65 mol percent.
  • One method of preparation of the inte ⁇ olymers of the present invention includes polymerizing a mixture of polymerizable monomers in the presence of [(4,5-methylene- phenanthrenyl) (tert-butylamido) dimethylsilanejdimethyl titanium and a suitable activating compound.
  • the inte ⁇ olymers of the present invention can be prepared by the processes described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are inco ⁇ orated herein by reference in their entirety.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from - 50°C to 200°C.
  • Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures.
  • the presence of vinyl aromatic homopolymer is in general not detrimental for the pu ⁇ oses of the present invention and can be tolerated.
  • the vinyl aromatic homopolymer may be separated from the inte ⁇ olymer, if desired, by extraction techniques such as liquid chromatography or selective precipitation from solution with a non solvent for either the inte ⁇ olymer or the vinyl or vinylidene aromatic homopolymer.
  • the inte ⁇ olymers of the present invention include inte ⁇ olymers prepared by polymerizing i) ethylene and/or one or more alpha-olefin monomers and ii) one or more vinyl or vinylidene aromatic monomers and optionally iii) other polymerizable ethylenically unsaturated monomer(s).
  • Suitable alpha-olefins include for example, alpha-olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms. Particularly suitable are ethylene, propylene, . butene-l, 4-methyl-l-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1. These alpha-olefins do not contain an aromatic moiety.
  • ethylenically unsaturated monomer(s) include norbornene and C,. 10 alkyl or C 6.10 aryl substituted norbornenes, with an exemplary inte ⁇ olymers being ethylene/styrene/norbornene and ethylene/styrene/ethylidene norbornene.
  • Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the inte ⁇ olymers, include, for example, those represented by the following formula:
  • R l _ c C(R ) 2 wherein R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C M -alkyl, and C M -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, alpha-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, alpha-methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof.
  • a more preferred vinyl aromatic monomer is styrene.
  • the resulting inte ⁇ olymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated, using processes described in WO 99/20691, the entire contents of which are herein inco ⁇ orated by reference, chlorinated or otherwise functionalized, as described in copending US Application No. 09/244,921 filed on February 4 th , 1999 by R. E. Drumright et al., the entire contents of which are herein inco ⁇ orated by reference.
  • the compositions of the present invention may also be modified by various cross-linking processes. These include, but are not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems. A full description of the various cross-linking technologies is described in U.S.
  • Patent 5,869,591 and 5977,271 the entire contents of both of which are herein inco ⁇ orated by reference.
  • Dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed.
  • Dual cure systems are disclosed and claimed in U. S. Patent 5,911,940, the entire contents of which is inco ⁇ orated herein by reference.
  • Additives such as antioxidants (for example, hindered phenols such as, for example, Irganox® 1010 a registered trademark of Ciba Geigy), phosphites (for example, Irgafos® 168 a registered trademark of Ciba Geigy), U.V. stabilizers, cling additives (for example, polyisobutylene), slip agents (such as erucamide and/or stearamide), antiblock additives, colorants, pigments, tackifiers, flame retardants, coupling agents, fillers, plastcizers can also be included in the compositions of the present invention.
  • antioxidants for example, hindered phenols such as, for example, Irganox® 1010 a registered trademark of Ciba Geigy
  • phosphites for example, Irgafos® 168 a registered trademark of Ciba Geigy
  • U.V. stabilizers for example, polyisobutylene
  • organic and inorganic fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, ammonium polyphosphate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B 2 O 3 , nickel powder or chalk.
  • organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, felds
  • organic or inorganic fiber or mineral fillers include carbonates such as barium, calcium or magnesium carbonate; borates such as magnesium or zinc borate, fluorides such as calcium or sodium aluminum fluoride; hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystals. Mixtures of more than one such filler may be used as well.
  • the fillers may also be used in conjunction with a coupling agent and/or initiator selected from organic peroxides, silanes, titanates, zirconates, multi-functional vinyl compounds, organic azides, and mixtures thereof.
  • a coupling agent and/or initiator selected from organic peroxides, silanes, titanates, zirconates, multi-functional vinyl compounds, organic azides, and mixtures thereof.
  • Other additives include the hindered amine stabilizers.
  • Such stabilizers include hindered triazines such as substituted triazines and reaction products of triazines.
  • Suitable reaction products include the reaction product of triazine with, for example, diamines and/ or cycloaliphatic compounds such as cyclohexane.
  • a particularly suitable hindered amine stabilizer includes the reaction product of 1, 3-propanediamine, N,N"-l,2-ethanediylbis-, cyclohexane and peroxidized N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6- trichloro-l,3,5-triazine which ismade commercially by Ciba-Geigy and has the name "CG-116 having CAS Reg No. : 191680-81-6.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the inte ⁇ olymer.
  • Fillers may suitably be employed in the range 1-90 wt.percent.
  • the polymers of the present invention can be blended with additional polymers including but not limited to; other inte ⁇ olymers of different molecular weight and/or vinyl or vinylidene aromatic monomer content, substantially random inte ⁇ olymers vinyl and vinylidene halide polymers including but not limited to poly(vinyl chloride) and poly( vinylidene chloride), polyethylene, and other polyolefins including but not limited to LDPE, and HDPE, PP, homogeneous ethylene/alpha-olefin copolymers produced by metallocene catalysts, including but not limited to the substantially linear ethylene/alpha- olefin copolymers and heterogeneous and heterogeneous ethylene/alpha-olefin copolymers produced by Ziegler catalysts; styrenic polymers including but not limited to polystyrene, SBS copolymers, polyethers, polycarbonates, polyanilines, asphalt, or any combinations thereof.
  • additional polymers including but not limited to
  • the inte ⁇ olymers of the present invention, or blends thereof can be fabricated into various forms including but not limited to films, fibers, foams, sheets, injection molded articles, membranes, injection-blow molded articles and extruded profiles, and emulsions.
  • Applications for the inte ⁇ olymers of the present invention, or blends thereof include, but are not limited to, ignition resistant articles, pressure sensitive filmstock, coating compositions or paints, floor, ceiling and wall coverings, ca ⁇ et backing, barriers, gaskets, caps and closures, and, with the addition of conductive additives such as carbon black, various conductive applications including electrical devices, conductor shields, insulation shields, and other wire and cable applications.
  • Determining the composition of the ethylene/styrene inte ⁇ olymers of the present invention can be ambiguous using NMR methods of analysis. This ambiguity arises from the fact that the styrene triads and higher order styrene insertions have peaks in both the ⁇ and 13 C spectra that can not be distinguished from peaks of the ubiquitous amo ⁇ hous atactic polystyrene homopolymer (aPS) which is present in small amounts in the inte ⁇ olymers.
  • aPS ubiquitous amo ⁇ hous atactic polystyrene homopolymer
  • LC liquid chromatography
  • the inte ⁇ olymer compositions of the present invention comprise from 5 to 85, preferably from 20 to 85, more preferably from 50 to 85 mole percent of at least one vinyl or vinyl or vinylidene aromatic monomer and from 15 to 95, preferably from 15 to 80, more preferably from 15 to 50 mole percent of ethylene and/or at least one aliphatic alpha-olefin having from 3 to 20 carbon atoms.
  • the melt index (I 2 ) of the inte ⁇ olymer of the present invention is greater than 0.05, preferably of from 0.5 to 200, more preferably of from 0.5 to 100 g/10 min.
  • the molecular weight distribution (M M of the inte ⁇ olymers of the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to 5.
  • the inte ⁇ olymer compositions of the present invention contain detectable vinyl aromatic monomer triads. In the case of an ethylene/styrene inte ⁇ olymer this would correspond to an -SSS- triad. Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS tetrads, SSSSS pentads.
  • the molecular weight of the polymer compositions of the present invention is conveniently indicated using Gel Permeation Chromatography using both UV and Refractive Index detectors.
  • a five to ten weight percent polymer solution is prepared in a mixture consisting of 50 volume percent l,l,2,2-tetrachloroethane-d2 and 50 volume percent 0.10 molar chromium tris(acetylacetonate) in 1,2,4-trichlorobenzene.
  • NMR spectra are acquired at 130°C using an inverse gated decoupling sequence, a 90°-pulse width and a pulse delay of five seconds or more. The spectra are referenced to the isolated methylene signal of the polymer assigned at 30.000 ppm.
  • DSC Differential Scanning Calorimetry
  • Micro-tensile testing was performed using compression molded micro-tensile bars as per ASTM D638 testing protocol. The samples were pulled using an Instron 4507 Series instrument at a cross-head speed of 0.1 inches/minute and a 224.8 lbf load cell at room temperature.
  • Plain-strain fracture toughness, compact tension single-edge notch geometry samples were compression molded into 1" by 1" by 1/8" squares. These squares were machined to provide a side notch and holes for attachment to the testing apparatus. A pre- crack was formed in each sample by cooling with liquid nitrogen and cracking with a razor blade and hammer. Fracture toughness testing was performed using an Instron 8501 instrument at a cross-head speed of 0.02 in/min with a 224.8 lbf load cell. Dynamic mechanical spectroscopy was performed on a rectangular bar, which was compression molded at 100°C. Temperature sweeps ranging from -100°C to 150°C were performed at a set frequency of 1 rad/sec with an auto-strain function set by the DMS instrument. Density was measured using a helium pycnometer. Rockwell hardness was assessed using ASTM D785-93. L.C. Analysis.
  • the second and best column of the two was a nitro column obtained from Phenomenex: Nucleosil 5 NO2 250 x 4.60 mm, 5 micron, serial number 243745. There was a guard column on the nitro column. It was a Phenomenex Nucleosil 5 NO2 30 x 4.6 mm, 5 micron 100 angstrom, serial number 243747G. Below are the instrumental conditions used on the HP 1090 with the Nitro2 method (nitro column).
  • Alumina was previously activated at 375°C with nitrogen and Q5 reactant was activated at 200°C with 5percent hydrogen in nitrogen.
  • Manipulations of catalyst and cocatalyst were carried out in an inert atmosphere glove box.
  • the semi-batch reactor polymerization was conducted in a two liter Parr reactor with an electrical heating jacket, internal se ⁇ entine coil for cooling, and a bottom drain valve. Pressures, temperatures and block valves were computer monitored and controlled. Isopar E and styrene were measured in a solvent shot tank fitted to a balance. The resulting solution was then added to the reactor from the solvent shot tank. The contents of the reactor were stirred at 1200 ⁇ m. Hydrogen was added by differential expansion (ca. 50 psi) from a 75 ml shot tank initially at 300 psig. The contents of the reactor were then heated to the desired run temperature (90°C) under the desired ethylene pressure.
  • the catalyst [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane]- dimethyltitanium and cocatalyst, tris(pentafluorophenyl)borane, were combined in the glove box (as 0.0050 M solutions in toluene)and transferred from the glove box to the catalyst shot tank through 1/16 in (0.16 cm) tubing using toluene to aid in the transfer. The catalyst tank was then pressurized using nitrogen. After the contents of the reactor had stabilized at the desired run temperature, the catalyst solution was injected into the reactor via a dip tube. The temperature was maintained by allowing cold glycol to pass through the internal cooling coils. The reaction was allowed to proceed for the desired time with ethylene provided on demand. Additional injections of catalyst were prepared and added in the same manner during the course of the run.
  • the molecular weight data shows that the catalyst can produce high molecular weight polymers. Since a dual detector was used in the GPC analysis, it was possible to examine the ratio of refractive index divided by UV response across the molecular weight range. This ratio was found not to change much indicating that the composition was relatively uniform across the entire molecular weight range; a slight increase in the styrene content at very low molecular weights was seen in all of the samples. This was consistent with the presence of aPS in these materials. Materials Properties The thermal transition data as determined by DSC were given in Table III. Table III Thermal Transitions (DSC)
  • Micro-tensile testing and fracture toughness testing was performed to assess the mechanical properties of these materials, Table IV.
  • Short term tensile analysis showed a relatively glassy response with a high modulus at low tensile stress and a relatively linear stress/strain relationship for all of the materials up to about 2percent strain.
  • the Young's modulus for all of these materials was in the range of 350,000-430,000 psi (2.4-3 GPa). All of the materials underwent a ductile yield at relatively low strains, with the yield strain moving steadily to lower elongation with increasing styrene content. All of the polymers exhibited slight drawing past the yield point up to ultimate failure.
  • Table IV Microtensile, Fracture Toughness and Hardness Data
  • Fracture toughness was measured using compact tension geometry samples. These experiments were designed to quantify the polymer's resistance to initiation and propagation of the crack with respect to an applied load. The test was performed on a compression-molded square of the polymer, which was notched, and a razor blade was used to produce a crack at the V of the notch. A tensile load was then applied to the sample in plane stress; the specimen prepared was ideally thick enough to prevent twisting out the plane of the applied load. The resultant relationship between load and displacement allows for determination of the instantaneous stress required to propagate the crack, known as the stress intensity factor Klc. It was also useful to define the energy required to extend the crack over a given unit area; this quantity was denoted Glc, (the fracture energy or critical strain-energy release rate) and it related to Klc by equation 1 :
  • the improved toughness of these materials with respect to polystyrene may arise from the ability of the ethylene units inco ⁇ orated to induce a more ductile response to applied stress on the time scale of the fracture test.
  • DMS analysis of the non-crystalline inte ⁇ olymers was performed to determine the position of the glass transition and to identify other transitions associated with these materials.
  • the glass transition temperature and room sub-Tg storage modulus increase with increasing styrene content in the copolymer.
  • the physical properties of the high styrene content inte ⁇ olymers of the present invention indicate have improved resistance to fracture. This suggests that these inte ⁇ olymers may provide unique utility in certain applications.
  • the amo ⁇ hous inte ⁇ olymers at the highest styrene levels were transparent, so that these polymers may have utility in film applications and may be advantaged with respect to aPS due to their increased toughness.
  • foam sheets of these new polymers may show better resiliency than aPS sheets and may perform better in applications where improved durability was required.
  • These polymers might also be used to toughen aPS while retaining good transparency, if compositions can be found which display compatibility.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP00938163A 1999-06-22 2000-06-05 Äthylen und/oder alpha-olefin / vinyl oder vinyliden aromatische copolymerzusammensetzungen Withdrawn EP1200491A1 (de)

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US14019999P 1999-06-22 1999-06-22
US140199P 1999-06-22
PCT/US2000/015525 WO2000078831A1 (en) 1999-06-22 2000-06-05 Ethylene and/or alpha-olefin/vinyl or vinylidene aromatic interpolymer compositions

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US6239242B1 (en) 1999-08-21 2001-05-29 Nova Chemicals Corporation Vinylaromatic and olefin pseudoblock polymers
FR2876222A1 (fr) * 2004-10-06 2006-04-07 Renault Sas Pile a combustible a membrane non-fluoree ou partiellement fluoree et procede de preparation de ladite membrane
CN113968926B (zh) * 2021-10-29 2023-01-13 大连理工大学 一类乙烯/α-烯烃/功能化苯乙烯衍生物三元共聚物及其制备方法

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