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WO1996039451A1 - Interpolymeres multicomposants segmentes de monomeres aromatiques de monovinylidene - Google Patents

Interpolymeres multicomposants segmentes de monomeres aromatiques de monovinylidene Download PDF

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Publication number
WO1996039451A1
WO1996039451A1 PCT/US1996/006280 US9606280W WO9639451A1 WO 1996039451 A1 WO1996039451 A1 WO 1996039451A1 US 9606280 W US9606280 W US 9606280W WO 9639451 A1 WO9639451 A1 WO 9639451A1
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Prior art keywords
polymer segment
monovinylidene aromatic
group
ethylene
segmented
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PCT/US1996/006280
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English (en)
Inventor
Jorge Soto
Gary R. Marchand
James C. Stevens
Lenore H. Crawford
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The Dow Chemical Company
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Publication of WO1996039451A1 publication Critical patent/WO1996039451A1/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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F

Definitions

  • the present invention relates to segmented multicomponent interpolymers.
  • the present invention relates to such interpolymers containing a substantially linear or branched olefin polymer backbone and at least one segment of a monovinylidene aromatic polymer.
  • polymers possess the desirable properties of block copolymers, including the ability to form phase separated domains, however, significantly improved processability is believed to be hindered due to a general lack of significant branching in the backbone polymer.
  • Q the molecular weight distribution of the resulting polymers is believed to be broader than is desired, thereby resulting in a reduction of physical properties, especially tensile strength, in the resulting polymers.
  • polyolefins containing long chain branches of preformed poly ⁇ - olefins were disclosed.
  • the branches comprised vinyl terminated ⁇ -olefin polymers.
  • Such 5 polymers are entirely ⁇ -olefin based and lack desirable physical properties of segmented, multicomponent polymers such as block copolymers.
  • Figure 1 depicts the results of analyzing the polymer of Example 4 by Dynamic Mechanical Spectroscopy.
  • This invention relates to segmented, multicomponent interpolymers comprising:
  • At least one olefin polymer segment comprising a substantially linear ethylene o homopolymer or a substantially linear or branched copolymer of ethylene and at least one comonomer selected from the group consisting of C 3 20 ⁇ -olef ins, and
  • the present invention relates to a process for forming the above described segmented, multicomponent interpolymers comprising:
  • a macromonomer comprising a vinyl terminated, monovinylidene aromatic polymer segment by reacting the living monovinylidene aromatic polymer segment with a vinyl functional terminating agent, and 5 3) polymerizing ethylene or a mixture of ethylene and at least one comonomer selected from the group consisting of C 3 20 ⁇ -olefins in the presence of the vinyl terminated, monovinylidene aromatic polymer segment under Ziegier-Natta polymerization conditions.
  • the present segmented polymers possess desirable physical properties of typical segmented polymers. Moreover, melt Theological properties of the present polymers are 0 significantly improved compared to typical segmented polymers such as block copolymers or segmented multicomponent interpolymers prepared according to the prior art. More particularly, the viscosity versus shear rate of the present polymers is significantly different from that of traditional polymers thereby improving the polymers ability to flow in the melt.
  • the present polymers may incorporate significant quantities of monovinylidene aromatic 5 monomer into the olefin polymer segment, thereby enabling adjustment of the solubility parameters of the respective domains of the polymer, that is, domains attributable to the olefin polymer segment and to the monovinylidene aromatic polymer segment.
  • the segmented, multicomponent interpolymers of the invention are usefully employed as molding resins, as impact modifiers, compatibilizersfor otherwise incompatible polymer mixtures, oriented or unoriented films for packaging and other applications, asphalt modifiers, and in adhesive formulations.
  • the polymers of the present invention are prepared by modification of the techniques disclosed in US-A-3,235,626, US-A-3,786,116 and US-A-3,862,098.
  • a functionalized macromoiecule (referred to as the vinyl terminated, monovinylidene aromatic polymer segment), such as an allyl terminated polymer of a vinylaromatic monomer, especially allyl terminated polystyrene, is prepared by any suitable means, especially by anionic o polymerization.
  • the functionalized macromoiecule is then reacted with backbone forming monomers selected from ethylene and mixtures of ethylene with C 3 . 2 o ⁇ -olefins, under continuous, solution phase, Ziegler-Natta polymerization conditions.
  • melt index or l 2 is measured in accordance with ASTM D-1238 (190/2.16);
  • l 10 is measured in accordance with ASTM D-1238 (190/10).
  • substantially linear used with reference to the olefin polymer segment means that the polymer backbone is substituted with up to 3 long chain branches/ 1000 carbons.
  • Preferred polymers contain from 0.01 to 3 long chain branches/ 1000 carbons, more preferably from 0.01 to 2 long chain branches/1000 carbons, and especially from 0.3 to 1 long chain branches/1000 carbons.
  • the polymers of the invention are
  • Long chain branching is defined herein as a chain length longer than any chain attributable to the aliphatic moiety of any ⁇ -olefin comonomer deliberately added to the reactor and incorporated into the polymer.
  • the long chain branch can be as long as the same length as the length of the polymer back-bone.
  • the presence of long chain branching can be
  • NMR 13 C nuclear magnetic resonance spectroscopy
  • GPC-LALS and similar analytic techniques are further disclosed in i_ Liq. Chrom., 7, 1809-1821 (1984); and Mirabella, Advances in Chem., Ser. 227, Polymer Chem.,
  • branched used with reference to the olefin polymer segment means that the polymer backbone is substituted with at least some short chain branches attributable to incorporation of comonomer that is intentionally added to the reaction mixture, that is, pendant hydrocarbyl groups that are remnants of the vinyl substituents of the comonomer.
  • Preferred comonomers are C 3 _ ⁇ ⁇ -olefins, especially C4. 8 ⁇ -olefins. Such comonomer is generally incorporated into the polymer in an amount from 0.1 to 80 percent by weight, more preferably from 10 to 50 percent by weight, most preferably from 20 to 40 percent by weight.
  • Preferred ⁇ -olefin comonomers for use in the olefin polymer segment include propylene, 1 - butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, styrene, allylbenzene, 1-decene, and mixtures thereof.
  • the polymers are produced in a continuous solution process, as opposed to a batch process. That is, polymer is continuously removed from the reactor and monomer is continuously added at a rate to replenish consumed monomer, thereby maintaining steady state conditions within the reactor. Furthermore, the reactor is maintained at high monomer conversion. Preferred conditions include an ethylene content less than 10 percent by weight of the reactor contents and polymerization temperature from 50°C to 150°C. If a narrow molecular weight distribution polymer (M w /M n of from 1.0 to 2.5) is desired, the ethylene concentration in the reactor is preferably less than 8 percent by weight of the reactor contents, especially less than 4 percent by weight of the reactor contents. Under such conditions the olefin polymer segment incorporates the largest proportion of long chain branches.
  • the polymerization of the olefin polymer segment is conducted in the presence of a catalyst system comprising a Group 3, 4 or Lanthanide metal complex corresponding to the formula: LMXX' n X" , or a dimerthereof, wherein:
  • L is a delocaiized, ⁇ -bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
  • M is a metal of Group 3, 4 or the Lanthanide series of the Periodic Table of the Elements;
  • X is a divalent substituent of up to 50 non-hydrogen atoms that together with L forms a metallocycle with M;
  • X' is an optional neutral Lewis base ligand having up to 20 non-hydrogen a oms
  • X" each occurrence is a monovalent, anionic moiety selected from hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy, amide, siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, and aminohydrocarbyl, said X" having up to 20 non-hydrogen atoms, ortwo X" groups are joined together forming a group that is ⁇ -bonded or ⁇ -bonded to M; n is a number from 0 to 3; and p is an integer from 0 to 4.
  • the preformed, dissolved, vinyl terminated, monovinylidene aromatic polymer segment is added to the polymerization mixture by continuous, batch or multiple batch addition techniques, and the olefin polymer segment is polymerized in the presence thereof.
  • L is a single, delocaiized ⁇ -bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
  • M is a metal of Group 4 of the Periodic Table of the Elements in the + 2, +3 or +4 formal oxidation state;
  • X is a divalent substituent of up to 50 non-hydrogen atoms that together with L forms a metallocycle with M;
  • X' is a neutral Lewis base ligand having up to 20 non-hydrogen atoms; n is zero or one; X" each occurrence is a monovalent moiety selected from hydride, hydrocarbyl, silyl or germyl, having up to 20 non-hydrogen atoms; and p is O, 1 or 2.
  • Suitable divalent X substituents preferably include groups containing up to 30 nonhydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to the delocaiized ⁇ -bonded group, and a different atom, selected from nitrogen, phosphorus, oxygen or sulfur that is covalentiy bonded to M.
  • Suitable L groups for use herein include any ⁇ -eiectron containing moiety capable of forming a delocaiized bond with the Group 3, 4 or Lanthanide metal. Examples include cyclopen tadienyl, allyl and pentadienyl, as well as substituted derivatives of such groups.
  • Preferred L groups include, cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydr ofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyi, cyclosilahexadienyl, diphenylmethyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and methyl-substituted derivatives thereof.
  • each atom in the delocaiized ⁇ -bonded group may independently be substituted with a radical selected from hydrocarbyl radicals, substituted- hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, and hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements.
  • Suitable hydrocarbyl and substituted-hydrocarbyl radicals used to form derivatives of the substituted, delocaiized ⁇ -bonded group will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, aikyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
  • two or more such radicals may together form a fused ring system or a hydrogenated fused ring system. Examples of the latter are indenyl-, tetrahydroindenyl-, fluorenyl-, and octahydrofluorenyl- groups.
  • Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di- and trisubstituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. More particularly, suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl.
  • R' each occurrence is independently hydrogen or a moiety selected from halogen, alkyl, aryl, haloalkyi, alkoxy, aryloxy, silyl groups, and combinations thereof, said R' having up to 20 non-hydrogen atoms, ortwo or more R' groups together form an aliphatic or aromatic fused ring system; and the remaining bond indicates where the substituted, delocaiized ⁇ -bonded group is covalently bonded to X.
  • X corresponds to the formula: -Z-Y-, wherein
  • Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the
  • Y is a ligand group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y together form a fused ring system.
  • E each occurrence is independently carbon, silicon, or germanium; q is an integer from 1 to 4;
  • Y' is nitrogen or phosphorous
  • R * each occurrence independently is hydrogen or a hydrocarbyl, silyl, or halohydrocarbyl group, said R * having up to 20 non-hydrogen atoms,
  • R " each occurrence independently is a hydrocarbyl, silyl or silylhydrocarbyl group, said R'" having up to 10 carbon or silicon atoms; or two or more R* groups or one or more R* groups and R'" together form a fused ring system of up to 30 non-hydrogen atoms.
  • More highly preferred metal complexes for use according to the invention correspond to the formula: C P* — ⁇ .
  • M is zirconium or titanium
  • Cp* is a cyclopentadienyl group; or a group selected from indenyl, fluorenyl and hydrogenated or partially hydrogenated derivatives thereof; or one of the foregoing groups substituted with one or more hydrocarbyl moieties of up to 20 carbons;
  • Y is a nitrogen or phosphorus containing group corresponding to the formula - N(R"")- or -P(R"")-; wherein:
  • R"" is C 1 10 hydrocarbyl
  • X" each occurrence independently is halo, hydrocarbyl of up to 20 carbons or hydrocarbyloxy of up to 20 carbons, ortwo X" groups together are a ⁇ -bonded or ⁇ -bonded C 4 . 20 conjugated diene.
  • Examples of the above most highly preferred metal coordination compounds include compounds wherein the R"" on the amido or phosphido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, (such aliphatic groups including all branched or cyclic isomers), norbornyl, benzyl, or phenyl; Cp* is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl, or one of the foregoing groups further substituted with one or more methyl, ethyl, propyl, butyl, pentyl, hexyl, (such further substituents including all branched or cyclic isomers), norbornyl, benzyl, or phenyl groups; and X" is
  • M is titanium
  • Z is dimethylsilane
  • Y is tert-butyl amido
  • Cp* is tetramethylcyclopentadienyl
  • X" each occurrence is independently methyl or benzyl or two X" together are ⁇ -1 ,4-diphenyl-1 ,3-bu tadiene or ⁇ 4 -1 ,3-pentadiene.
  • Illustrative derivatives of Group 3, 4 or Lanthanide metals that may be employed in the practice of the present invention include hydrocarbyl-substituted monocyclopentadienyl compounds such as:
  • -Z-Y- is an amidosilane group of up to 10 nonhydrogen atoms, particularly, (tert-butylamido)(dimethylsilyl).
  • the metal complexes are rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique.
  • Suitable activating cocatalystsfor use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as C 1-30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, car bonium-, silylium- or
  • Combinations of neutral Lewis acids especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric aiumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric aiumoxane are especially desirable activating cocatalysts.
  • Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A-.
  • noncoordinating means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • a noncoordinating anion specifically refers to an anion which when o functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes.
  • Complementary anions are anions which are not degraded to neutrality when the initially formed complex decomposes and are nonin terfering with the desired subsequent polymerization or other uses of the complex.
  • Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined.
  • said anion should be sufficiently labile to be displaced by olefinic, diolef inic and acetyleni ally unsaturated compounds or other neutral Lewis bases such as ethers or 0 nitriies.
  • Suitable metals especially include aluminum.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. 5
  • cocatalysts may be represented by the following general formula:
  • L * is a neutral Lewis base; (L * -H) + is a Bronsted acid; 0 A d" is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3.
  • M' is an element selected from Group 13 of the Periodic Table of the Elements; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
  • suitable hydrocarbyloxide Q groups are disclosed in U. S. Patent 5,296,433.
  • d is one, that is, the counter ion has a single negative charge and is A-.
  • Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: wherein:
  • L * is as previously defined; B is boron in an oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
  • Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
  • boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri- substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenyiborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylaniiinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-2,4,6-trimethylanilinium tetraphenylborate, trimethylammonium
  • Preferred [L * -H]+ cations are N,N-dimethylanilinium and tributylammonium.
  • Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
  • Ox e+ is a cationic oxidizing agent having a charge of e + ; e is 1 , 2 or 3; and A d - and d are as previously defined.
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag + , or Pb+ 2 .
  • Preferred embodiments of A d - are those anions previously defined with respectto the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)bo rate.
  • Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
  • ® + is a C ⁇ _ 2 o carbenium ion
  • A- is as previously defined.
  • a preferred carbenium ion is the trityl cation, 10 triphenylmethylium.
  • a further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
  • R 3 Si(X') s + A wherein: 15 R is O
  • silylium salt activating cocatalysts aretrimethylsilylium tetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.
  • Silylium salts have been previously generically disclosed in J. Chem Soc. Chem.Comm., 1993, 383-384, as well as Lambert, J. B contend et al., Orqanometallics, 1994, 13, 20 2430-2443.
  • the technique of bulk electrolysis involves the electrochemical oxidation of the 25 metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion.
  • solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction.
  • suitable solvents are materials that are: liquids under the 30 conditions of the electrolysis (generally temperatures from 0 to 100°C), capable of dissolving the supporting electrolyte, and inert.
  • “Inert solvents” are those that are not reduced or oxidized underthe reaction conditions employed for the electrolysis.
  • Preferred solvents 35 include dif luorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof.
  • the electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively).
  • Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal.
  • the electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials.
  • an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment.
  • the working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex.
  • the counter electrode is immersed in a mixture of the solvent and supporting electrolyte.
  • the desired voltage may be determined by theoretical calculations or determined experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte.
  • the background cell current that is, the current draw in the absence of the desired electrolysis, is also determined.
  • the electrolysis is completed when the current drops from the desired level to the background level. In this manner, complete conversion of the initial metal complex can be easily detected.
  • Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion, A " .
  • Preferred supporting electrolytes are salts corresponding to the formula: G + A-, wherein,
  • G+ is a cation which is nonr eactive towards the starting and resulting complex
  • A- is as previously defined.
  • Examples of cations, G+, include tetra hydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms.
  • Preferred cations are the tetra-n- butylammonium- and tetraethylammonium- cations.
  • the cation of the supporting electrolyte passes to the counter electrode and A- migrates to the working electrode to become the anion of the resulting oxidized product.
  • Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed atthe working electrode.
  • Preferred supporting electrolytes aretetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfiuoroaryl group, especially tetra-n-butylammonium tetrakis(pentaf luorophenyl) borate.
  • a disilane especially bis(trimethylsilane) is included in the electrolysis along with a source of a noncoordinating compatible anion such as an quaternary alkyl ammonium salt of tetrakispentaf luorophenyl borate, thereby germanating in situ a siylium salt activing cocatalyst.
  • a source of a noncoordinating compatible anion such as an quaternary alkyl ammonium salt of tetrakispentaf luorophenyl borate, thereby germanating in situ a siylium salt activing cocatalyst.
  • the foregoing activating techniques and ion forming cocatalysts are also preferably used in combination with a tri(hydrocarbyl)aluminum ortri(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group, an oligomeric or polymeric alumoxane compound, or a mixture of a tri(hydrocarbyl)aluminum compound having from 1 to 4 carbons in each hydrocarbyl group and a polymeric or oligomeric alumoxane.
  • the molar ratio of catalyst/ cocatalyst employed preferably ranges from 1 : 10,000 to 100:1 , more preferably from 1 :5000 to 10:1, most preferably from 1 :10 to 1 :1.
  • the cocatalyst can be used in combination with a tri(hydrocarbyl)aluminum compound having from 1 to 10 carbons in each hydrocarbyl group or an oligomeric or polymeric alumoxane. Mixtures of activating cocatalysts may also be employed. It is possible to employ these aluminum compounds for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture.
  • Preferred aluminum compounds include trialkyl aluminum compounds having from 2 to 6 carbons in each alkyl group, especially those wherein the alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and methylalumoxane, modified methylalumoxane (that is, methylalumoxane modified by reaction with triisobutyl aluminum) (MMAO) and isobu tylalumoxane.
  • the alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl
  • methylalumoxane modified methylalumoxane (that is, methylalumoxane modified by reaction with triisobutyl aluminum) (MMAO) and
  • the molar ratio of metal complex to aluminum compound is preferably from 1 :10,000 to 100:1, more preferably from 1 :1000 to 10: 1, most preferably from 1 :500 to 1 : 1.
  • a most preferred activating cocatalyst comprises both a strong Lewis acid and an alumoxane, especially tris(pentafluorophenyl)borane and methylalumoxane, modified methylalumoxane, or diisobutylalumoxane.
  • the catalysts can be prepared by combining the metal complex and cocatalyst or activating the metal complex in a suitable solvent at a temperature within the range from -100 C C to 300°C.
  • the catalyst may be separately prepared prior to use by combining the respective components, or prepared in situ by combination of the respective components in the presence of the monomers to be polymerized. It is preferred to form the catalyst in situ due to the exceptionally high catalytic effectiveness of catalysts prepared in this manner.
  • the catalyst components are sensitive to both moisture and oxygen and should be handled and transferred in an inert atmosphere such as nitrogen, argon or helium.
  • the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250°C and pressures from atmospheric to 1000 atmospheres (0.1 to 100 MPa).
  • the molar ratio of catalyst:poiymerizable compounds employed in such polymerizations is preferably from 10" 12 : 1 to 10' 1 : 1, more preferably from 10" 12 :1 to 10" 5 :1.
  • Suitable solvents for the olefin polymer segment polymerization are noncoordinating, inert liquids, preferably those in which the monovinylidene aromatic polymer segment are soluble.
  • examples include cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C4.10 alkanes, aromatic and alkyl- substituted aromatic compounds such as benzene, toluene, xylene, and mixtures thereof; and mixtures of the foregoing solvents.
  • the preferred procedure is to form the vinyl terminated monovinylidene aromatic polymer segment by the use of a lithium alkyl initiator, separate any salt byproducts and add the resulting polymer solution to the Ziegler-Natta reaction mixture prior to or during the polymerization of the olefin polymer segment.
  • the monovinylidene aromatic polymer segment may also be recovered and separated from the reaction mixture used in its preparation, then later redissolved and added to the reaction mixture used for preparation of the olefin polymer segment.
  • Anionic polymerization conditions especially suited for use in the present polymerization of the monovinylidene aromatic polymer segment are those conditions previously known and utilized to prepare monovinylidene aromatic homopoiymers or block copolymers of vinylaromatic monomers and conjugated diene monomers.
  • the monovinylidene aromatic polymer segments are preferably monovinylidene aromatic homopoiymers or block copolymers of vinylaromatic monomers and conjugated diene monomers, terminating with vinyl unsaturation. If the monovinylidene aromatic polymer is a block copolymer, the same is desirably prepared via sequential polymerization of living polymer anions.
  • the monovinylidene aromatic polymer segment may include a diene polymer block.
  • Preferred diene monomers are conjugated dienes, preferably 1,3-butadiene, isoprene, and mixtures thereof.
  • Suitable monovinylidene aromatic monomers are compounds of the formula:
  • n is an integer from 0 to 3
  • R is an alkyl radical containing up to 5 carbon atoms and R 2 is hydrogen or methyl.
  • Preferred monovinylidene aromatic monomers are styrene, vinyl toluene (all isomers, alone or in admixture), ⁇ -methylstyrene, and mixtures thereof .
  • Particularly preferred alkenyi aromatic monomers are styrene and mixtures of styrene and ⁇ - methylstyrene.
  • the monovinylidene aromatic polymer segment contains from 1 to 100 weight percent monovinylidene aromatic monomer prior to functionaiization.
  • Monomer and solvent purities are carefully controlled during the anionic polymerization. Purification by contacting the monomer(s) or solvent with molecular sieves, or by distillation or degassing may be employed. Prior to addition of the lithium alkyl initiator, reactive impurities may also be removed by "blanking", that is, by addition of a small amount of lithium hydrocarbyl to react with and remove the contaminants, but not enough to begin polymerization of the purified monomer.
  • Preferred lithium alkyl compounds are those having from 2 to 6 carbons in the alkyl group, especially sec-butyl lithium.
  • Monomer addition may occur before initiation of polymerization or continuously or incrementally after initiation.
  • the polymerization is conducted for time periods suitable to achieve the desired product properties and conversions. Suitable reaction times are from 10 minutes to 3 hours, preferably from 20 minutes to 2 hours.
  • Vinyl termination orfunctionalization of the monovinylidene aromatic polymer segment may be accomplished by any known technique.
  • the living monovinylidene aromatic polymer segment prepared by the aforementioned technique of anionic polymerization is terminated by adding allyl chloride to the reaction mixture and subsequently separating the lithium chloride salt byproduct.
  • the reaction mixture is then passed to a second reactor operating under Ziegler-Natta polymerization conditions for formation of the finished polymer product.
  • the ratio of the two polymer segments may vary over a range from 1 to 99 percent by weight.
  • the monovinylidene aromatic polymer segment comprises from 1 to 50 percent by weight of the segmented multicomponent interpolymer and has a molecular weight (Mw) from 5,000 to 2,000,000.
  • Mw molecular weight
  • Molecular weights for the segmented multicomponent interpolymer may vary from 10,000 to 4,000,000, preferably from 15,000 to 100,000.
  • a 20 L stainless steel reactor was charged with 13 Kg of cyclohexane, which had been dried by passing through an alumina bed.
  • the reactor is heated to 50°C and impurities scavenged by addition of a small amount of polystyrllithium solution (12 g, 0.12 M) in cyclohexane until detection of a visible absorbance at 400 nm.
  • 772 g of a 0.16 M solution of sec-butyl lithium in cyclohexane was added to the reactor, followed by the addition of 1128 g of alumina purified styrene.
  • the reactor temperature was maintained at 36-42 °C while all the styrene monomer was consumed, 60 minutes.
  • the reaction mixture was cooled to 31 °C and the living polystyrene anion was terminated by the addition to the reaction mixture of 39 g of allyl chloride dissolved in cyclohexane (both components having been purified by passing through an alumina column).
  • the polymer solution was washed once with an equivalent volume of water and the solvent removed under reduced pressure at 100 °Cfor 3 hours.
  • the remaining polymer (designated a-1) was a brittle solid.
  • the molecular weight (Mw) determined by size exclusion chromatography (SEC) of the allyl terminated product was 5600 g/mole (polystyrene standard).
  • the mixture was allowed to react until ethylene uptake ceased and was then discharged into a nitrogen purged container.
  • the solution was poured into a mixture of 5 approximately 2 L of acetone and 0.5 L of methanol whereupon the segmented polymer precipitated.
  • the polymer was recovered by filtration and evaporated at 130 °C under reduced pressure, leaving 41 g of segmented, multicomponent polymer product.
  • the polymer was redissolved in toluene, antioxidant (0.1 percent of I rganox 1010, available from Ciba-Gigy Corp.) was added, and the polymer was reprecipitated using isopropanol.
  • antioxidant 0.1 percent of I rganox 1010, available from Ciba-Gigy Corp.
  • Morphologies of the copolymers were determined by transmission electron microscopy using a Philips CM12/STEM electron microscope. Sections of compression molded plaques of the segmented, multicomponent polymers were obtained cyrogenically using a Reichert-Jung FC4E Ultramicrotome and the sections stained with RUO4 vapor for 5-10 minutes. Images were taken at magnifications from 320 to 1290 kX. The images showed spherical clusters of polystyrene domains from 13 to 15 nm in diameter, indicating that the polymer had a phase separated morphology.
  • Dynamic mechanical properties of the polymers were obtained on circular sections of compression molded samples. The data was obtained on a Rheometrics Mechanical Spectrometer/ Dynamic Spectrometer RMS-800/RDS-II. Temperature scans were run and the storage modulus, loss modulus and Tan 6 obtained as a function of temperature at 1 sec-1. A representative DMS scan is shown in Figure 1 wherein a commercially available hydrogenated styrene block copolymer (Kraton * " G-1650 and the segmented, multicomponent polymer of example 4 were compared. The DMS of the segmented, multicomponent polymer shows similar low and high temperature glass transition temperature properties as the block copolymer, indicating the existence of separate polystyrene and polyolefin phases.

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Abstract

Cette invention concerne des interpolymères multicomposants segmentés comprenant: (A) au moins un segment polymère d'oléfine comportant un homopolymère d'éthylène sensiblement linéaire ou un copolymère d'éthylène sensiblement linéaire ou ramifié, ainsi qu'un ou plusieurs comonomères choisis dans le groupe comprenant des α-oléfines C3-20; et (B), au moins un segment polymère aromatique de monovinylidène. Le segment polymère d'oléfine et le segment polymère aromatique de monovinylidène sont liés par copolymérisation de la fonction vinyle de l'extrémité d'un macromonomère comprenant le segment polymère aromatique de monovinylidène, avec de l'éthylène ou un mélange d'éthylène et dudit ou desdits comonomères et dans des conditions de polymérisation de Ziegler-Natta.
PCT/US1996/006280 1995-06-06 1996-05-03 Interpolymeres multicomposants segmentes de monomeres aromatiques de monovinylidene WO1996039451A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998034985A1 (fr) * 1997-02-07 1998-08-13 Exxon Chemical Patents Inc. Compositions a base de polyethylene possedant une resistance elevee a la fusion
US6114457A (en) * 1997-02-07 2000-09-05 Exxon Chemical Patents Inc. High melt strength polyethylene compositions
EP1077224A1 (fr) * 1999-08-16 2001-02-21 Samsung Electronics Co., Ltd. Polymer statistique de styrene et un macromonomere presentant une excellente limite d'ecoulement et procede pour sa fabrication
WO2013126187A1 (fr) * 2012-02-22 2013-08-29 Exxonmobil Chemical Patents Inc. Oligomérisation de macromonomères à terminaison vinylique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3786116A (en) * 1972-08-21 1974-01-15 Cpc International Inc Chemically joined,phase separated thermoplastic graft copolymers
US5104952A (en) * 1990-11-15 1992-04-14 Minnesota Mining And Manufacturing Company Macromolecular monomers from living polymers
EP0559108A1 (fr) * 1992-03-03 1993-09-08 Idemitsu Kosan Company Limited Polymère greffé, son procédé de production et composition de résine le contenant
US5278272A (en) * 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3786116A (en) * 1972-08-21 1974-01-15 Cpc International Inc Chemically joined,phase separated thermoplastic graft copolymers
US5104952A (en) * 1990-11-15 1992-04-14 Minnesota Mining And Manufacturing Company Macromolecular monomers from living polymers
US5278272A (en) * 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
EP0559108A1 (fr) * 1992-03-03 1993-09-08 Idemitsu Kosan Company Limited Polymère greffé, son procédé de production et composition de résine le contenant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998034985A1 (fr) * 1997-02-07 1998-08-13 Exxon Chemical Patents Inc. Compositions a base de polyethylene possedant une resistance elevee a la fusion
US6114457A (en) * 1997-02-07 2000-09-05 Exxon Chemical Patents Inc. High melt strength polyethylene compositions
EP1077224A1 (fr) * 1999-08-16 2001-02-21 Samsung Electronics Co., Ltd. Polymer statistique de styrene et un macromonomere presentant une excellente limite d'ecoulement et procede pour sa fabrication
WO2013126187A1 (fr) * 2012-02-22 2013-08-29 Exxonmobil Chemical Patents Inc. Oligomérisation de macromonomères à terminaison vinylique

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