WO2001030864A2 - Polymeres nanocomposites - Google Patents

Polymeres nanocomposites Download PDF

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Publication number
WO2001030864A2
WO2001030864A2 PCT/US2000/027840 US0027840W WO0130864A2 WO 2001030864 A2 WO2001030864 A2 WO 2001030864A2 US 0027840 W US0027840 W US 0027840W WO 0130864 A2 WO0130864 A2 WO 0130864A2
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composition
layered silicate
acid
cation exchanging
acid treated
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PCT/US2000/027840
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WO2001030864A3 (fr
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Tao Sun
Juan M. Garces
Zoran R. Jovanovic
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The Dow Chemical Company
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Publication of WO2001030864A3 publication Critical patent/WO2001030864A3/fr

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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the instant invention relates to nanocomposite polymers.
  • European Patent Application publication number EP 0 747 322 Al describes nanocomposite polymers made by blending quaternary ammonium treated cation exchanging layered silicate materials with a polar group modified polymer.
  • Such nanocomposite polymers exhibit improved properties such as increased tensile modulus relative to the base polymer.
  • the degree of improvement in the properties of such nanocomposite polymers is not as great as desired. It would be an advance in the art of nanocomposite polymers if the degree of improvement were greater. For example, it would be a clear advance in the art if a polypropylene nanocomposite were developed which had a tensile modulus of more than four hundred thousand pounds per square inch using ten percent or less filler.
  • the instant invention is a solution to the above mentioned problem to a large degree.
  • using the instant invention it is possible to prepare a polypropylene nanocomposite having a tensile modulus of more than four hundred thousand pounds per square inch using ten percent or less filler.
  • the instant invention is a method for producing a nanocomposite polymer, comprising the step of adding an olefin to a metallocene polymerization catalyst treated dispersion of an acid treated cation exchanging layered silicate material in a solvent so that the olefin polymerizes to form the nanocomposite polymer.
  • the instant invention is a composition of matter comprising an exfoliated acid treated cation exchanging layered silicate material dispersed in a polymer matrix, wherein more than about fifty percent of the acid treated cation exchanging layered silicate material is found by electron microscopy to have five or fewer layers.
  • the instant invention is a composition of matter, comprising a metallocene polymerization catalyst treated, acid treated cation exchanging layered silicate material.
  • Fig. 1 is a drawing reproduction of a photomicrograph of a nanocomposite polymer of the instant invention.
  • the invention is a method for producing a nanocomposite polymer.
  • a nanocomposite polymer is by definition herein a polymer having dispersed therein sufficiently exfoliated cation exchanging layered silicate material.
  • the term "sufficiently exfoliated” means that more than about twenty five percent by weight of the acid treated layered silicate material is found by electron microscopy of the nanocomposite polymer to have five or fewer layers.
  • the thickness of a single layer of such material is one to two nanometers while the length and width of such layer can be in the range of, for example, one hundred to one thousand nanometers.
  • Photomicrographs of nanocomposite polymers typically show a dispersion of multiple layer units of the multi-layered silicate material in the polymer, such as, two, three, four, five and more than five layer units dispersed in the polymer. It is generally desired to achieve a high degree of exfoliation of the multi-layered silicate material. Ideally the degree of such exfoliation is so extensive that only single layer units are present.
  • FIG. 1 therein is shown a drawing reproduction of an idealized representative photomicrograph of a nanocomposite polymer of the instant invention.
  • Fig. 1 shows two one layer units and one each of a two, three, four, five, six and seven layer unit.
  • the nanocomposite polymer shown in Fig. 1 has about 55 percent five or fewer layer units on a weight percent basis since each of the layers are essentially the same size.
  • Examples of cation exchanging layered silicate materials include: 1) biophilite, kaolinite, dickalite or talc clays, 2) smectite clays, 3) vermiculite clays,
  • Zeolitic layered materials such as ITQ-2, MCM-22 precursor, exfoliated ferrierite and exfoliated mordenite.
  • clay materials exist in nature, and also can be synthesized, generally in higher purity than the native material. Any of the naturally occurring or synthetic cation exchanging layered silicate clay materials may be used in the present invention. Preferred are smectite clays, including montmorillonite, bidelite, saponite and hectorite.
  • cation exchanging layered silicate material also includes the “layered fiber” silicate materials such as attapulgite and sepiolite.
  • Layered fiber silicate materials exfoliate to produce multi-fiber units (herein multi-layer units) and most preferably they exfoliate to produce single fiber units (herein single layer units) dispersed in the polymer.
  • the cation exchanging layered silicate material is acidified by contacting it with a Bronsted acid (such as, hydrochloric acid, sulfuric acid, a carboxylic acid, an amino acid or any material which forms an acidic aqueous dispersion such as acidic metal salts like zinc sulfate) or by contacting it with an acidified amine (such as, an amine hydrochloride such as 4-tetradecyl aniline hydrochloride).
  • a Bronsted acid such as, hydrochloric acid, sulfuric acid, a carboxylic acid, an amino acid or any material which forms an acidic aqueous dispersion such as acidic metal salts like zinc sulfate
  • an acidified amine such as, an amine hydrochloride such as 4-tetradecyl aniline hydrochloride.
  • a Bronsted acid such as, hydrochloric acid, sulfuric acid, a carboxylic acid, an amino acid or any material which forms an acidic aqueous dis
  • the acidified layered silicate material is dispersed with a solvent (such as, toluene). Most preferably, such dispersion is accomplished by sonication. However, such dispersions can also be made by any suitable technique such as high shear mixing or wet ball milling.
  • the dispersion may then contacted with a metallocene polymerization catalyst to produce a metallocene treated sonicated dispersion.
  • Metallocene polymerization catalysts are well known in the art and include derivatives of Group 3, 4, or Lanthanide metals which are in the +2, +3, or +4 formal oxidation state.
  • Preferred compounds include metal complexes containing from 1 to 3 ⁇ -bonded anionic or neutral ligand groups, which may be cyclic or non-cyclic delocalized ⁇ -bonded anionic ligand groups.
  • ⁇ -bonded anionic ligand groups are conjugated or nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, and arene groups.
  • ⁇ -bonded is meant that the ligand group is bonded to the transition metal by a sharing or donating of electrons from a partially delocalized ⁇ -bond.
  • Each atom in the delocalized ⁇ -bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals further substituted with a Group 15 or 16 hetero atom containing moiety.
  • hydrocarbyl C ⁇ _20 straight, branched and cyclic alkyl radicals, C6_20 aromatic radicals, C7.20 alkyl-substituted aromatic radicals, and C7.20 aryl-substituted alkyl radicals.
  • two or more such radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may form a metallocycle with the metal.
  • Suitable hydrocarbyl- substituted organometalloid radicals include mono-, di- and tri-substituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms.
  • hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.
  • Group 15 or 16 hetero atom containing moieties include amine, phosphine, ether or thioether moieties or divalent derivatives thereof, e. g., amide, phosphide, ether or thioether groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group or to the hydrocarbyl- substituted metalloid containing group.
  • Suitable anionic, delocalized ⁇ -bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and boratabenzene groups, as well as Cj-io hydrocarbyl-substituted or C 1-10 hydrocarbyl-substituted silyl substituted derivatives thereof.
  • Preferred anionic delocalized ⁇ -bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclo- pentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4- phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.
  • boratabenzenes are anionic ligands which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich. et al maneuver in Organometallics. 14,1, 471-480 (1995). Preferred boratabenzenes correspond to the formula:
  • R" is selected from the group consisting of hydrocarbyl, silyl, or germyl, said R" having up to 20 non-hydrogen atoms.
  • R" is selected from the group consisting of hydrocarbyl, silyl, or germyl, said R" having up to 20 non-hydrogen atoms.
  • a suitable class of catalysts are transition metal complexes corresponding to the formula: K' j MZ'mLiXp, or a dimer thereof
  • K' is an anionic group containing delocalized ⁇ -electrons through which K' is bound to M, said K' group containing up to 50 atoms not counting hydrogen atoms, optionally two K' groups may be joined together forming a bridged structure, and further optionally one K' may be bound to Z' ;
  • M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state;
  • Z' is an optional, divalent substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M;
  • L is an optional neutral ligand having up to 20 non-hydrogen atoms;
  • X each occurrence is a monovalent, anionic moiety having up to 40 non- hydrogen atoms
  • two X groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M
  • 2 X groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is bound to M by means of delocalized ⁇ -electrons (whereupon M is in the +2 oxidation state), or further optionally one or more X and one or more L groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto by means of Lewis base functionality
  • k is 0, 1 or 2
  • m is 0 or 1;
  • 1 is a number from 0 to 3; p is an integer from 0 to 3; and the sum, k+m+p, is equal to the formal oxidation state of M, except when 2 X groups together form a neutral conjugated or non-conjugated diene that is bound to M via delocalized ⁇ -electrons, in which case the sum k+m is equal to the formal oxidation state of M.
  • Preferred complexes include those containing either one or two K' groups.
  • the latter complexes include those containing a bridging group linking the two K' groups.
  • Preferred bridging groups are those corresponding to the formula (ER'2) X wherein E is silicon, germanium, tin, or carbon, R' independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R' having up to 30 carbon or silicon atoms, and x is 1 to 8.
  • R' independently each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.
  • Examples of the complexes containing two K' groups are compounds corresponding to the formula:
  • M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the
  • R in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R 3 having up to 20 non-hydrogen atoms, or adjacent R 3 groups together form a divalent derivative (for example, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, and
  • X independently each occurrence is an anionic ligand group of up to 40 non- hydrogen atoms, or two X" groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms bound by means of delocalized ⁇ -electrons to M, whereupon M is in the +2 formal oxidation state, and
  • R', E and x are as previously defined.
  • the foregoing metal complexes are especially suited for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex possesses C s or C 2 symmetry or possesses a chiral, stereorigid structure.
  • Examples of the first type are compounds possessing different delocalized ⁇ -bonded ligand groups, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 1 10, 6255-6256 (1980).
  • Examples of chiral structures include rac WO 01/30864 PCT/TJSOO/27840 bis-indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem.. 232, 233-47, (1982).
  • Exemplary bridged ligands containing two ⁇ -bonded groups are: 5 dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-l-yl)silane, dimethylbis(2-t-butylcyclopentadien-l- yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden- 1 -yl)silane, dimethylbis(tetrahydroinden- 1 -yl)silane, dimethylbis(fluoren- 1 -yl)silane, dimethylbis(tetrahydrofluoren- 1 -yl)silane, dimethylbis(2-methyl-4-phenylinden- 1 -yl)-silane, o dimethylbis(2-methylinden- 1 -yl)silane
  • Preferred X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, or two X" groups together form a divalent derivative of a conjugated diene or else together they form a neutral, ⁇ -bonded, conjugated diene. Most preferred X" groups are C ⁇ _20 hydrocarbyl groups. 0
  • a further class of metal complexes utilized in the present invention corresponds to the preceding formula or a dimer thereof, wherein Z' is a divalent substituent of up to 50 non-hydrogen atoms that together with K' forms a metallocycle with M.
  • Preferred divalent Z' substituents include groups containing up to 30 non- 5 hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of
  • a preferred class of such Group 4 metal coordination complexes used o according to the present invention corresponds to the formula:
  • M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state;
  • R in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R 3 having up to 20 non-hydrogen atoms, or adjacent R 3 groups together form a divalent derivative (for example, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system
  • each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups together form a neutral C5.30 conjugated diene or a divalent derivative thereof;
  • Y is -O-, -S-, -NR'-, -PR'-; and
  • Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: cyclopentadienyltitaniumtrimethyl, cyclopentadienyltitaniumtriethyl, cyclopentadienyltitaniumtriisopropyl, cyclopentadienyltitaniumtriphenyl, cyclopentadienyltitaniumtribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl»triethylphosphine, WO 01/30864 PCT/TJSOO/27840 cyclopentadienyltitanium-2,4-dimethylpentadienyl»trimethylphosphine, cyclopentadienyltitaniumdimethylmethoxide, cyclopen
  • Complexes containing two K' groups including bridged complexes suitable for use in the present invention include: bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)zirconium methyl benzyl, bis(cyclopentadienyl)zirconium methyl phenyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadienyl)titanium-allyl, bis(cyclopentadienyl)zirconiummethylmethoxide, bis(cyclopentadienyl)zirconiummethylchloride, bis(pentamethylcyclopentadienyl)zirconiumdimethyl, bis(pentamethylcyclopentadienyl)titaniumdimethyl, bis(indenyl)zirconiumdimethyl, indenylfluor
  • metallocene polymerization catalysts including Ziegler-Natta catalysts and Brookhart/Gibson catalysts
  • the metallocene polymerization catalyst can alternatively be added during the dispersion of the layered silicate material.
  • the relative amount of metallocene polymerization catalyst is the same in the instant invention as in the prior art of metallocene catalysts and depends on the specific catalyst used. It should be 0 understood that the instant invention may be used for any polymerization process including solution, slurry and gas phase polymerization and that any polymerization catalyst may be used that is acid activated.
  • the olefin 5 polymerizes to form the nanocomposite polymer. It is believed that the acid component of the acidified layered silicate material activates the metallocene polymerization catalyst to produce polymer between the layers of the layered silicate material and thereby separate or exfoliate such layers to a greater degree into the developing polymer matrix. In addition, it is believed that the temperature of the polymerization should be sufficiently low so that o more of the polymerization occurs between the layers of the layered silicate in order to promote a greater degree of such exfoliation.
  • the residual hydroxyl or other reactive functionality of the acid treated cation exchanging layered silicate material is capped or reacted with a reactive 5 material, especially a Lewis acid.
  • a reactive 5 material especially a Lewis acid.
  • Preferred Lewis acids include trialkyl aluminum compounds having from 1 to 10 carbons in each alkyl group.
  • metallocene polymerization catalyst treated, acid treated cation exchanging layered silicate material means a cation exchanging layered silicate material that has been contacted with an acid and a metallocene polymerization catalyst as discussed o above. It should be understood that a metallocene polymerization catalyst treated, acid treated cation exchanging layered silicate material may be used in a solution, slurry or gas phase polymerization system.
  • the resulting nanocomposite polymer preferably comprises an exfoliated acid treated cation exchanging layered silicate material dispersed in a polymer matrix, wherein more than about fifty percent by weight of the acid treated layered silicate material is found by electron microscopy of the nanocomposite polymer to have five or fewer layers.
  • the weight percent of acid treated cation exchanging layered silicate material in the nanocomposite polymer is more than one percent and less than ten percent.
  • Such nanocomposite polymers are capable of unexpected tensile modulus, such as, more than four hundred thousand pounds per square inch. With specific regard to polypropylene nanocomposites, unexpected tensile modulus of more than five hundred thousand pounds per square inch are described below.
  • the standard test method for determining tensile modulus herein is ASTM Method Number D882.
  • the olefin used in the instant invention is selected from the group of olefins having from two to ten carbon atoms.
  • olefins include, for example, styrene, divinylbenzene, norborene, ethylene, propylene, octene, butadiene and mixtures thereof.
  • the polymer product of or by way of the instant invention may be, for example, a rubber, a thermoplastic elastomer, polyethylene and polypropylene.
  • One half gram of vacuum dried 4-tetradecylanilinium exchanged montmorillonite is added to one hundred and twenty milliliters of dry toluene to produce a slurry.
  • Six hundred microliters of tripropylaluminum is added to the slurry.
  • Five hundred microliters of a two and one half millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4-phenylindenys) zirconium (II) l,4-diphenyl-l,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for fifteen minutes.
  • the sonicated slurry is then aged for one hour.
  • Example 1 is repeated except that the polymerization reaction is one half hour at room temperature followed by one half hour at eighty degrees Celcius. Seven grams of polypropylene nanocomposite is recovered by acetone precipitation. The polymer has a number average molecular weight of 17,100. Electron microscopy of the polymer shows substantial single layer exfoliation of the montmorillonite but to a somewhat lesser degree than the polymer of Example 1.
  • Example 1 is repeated except that one-quarter gram of treated montmorillonite is used and the polymerization reaction is one hour at eighty degrees Celcius. Seven grams of polypropylene nanocomposite is recovered by acetone precipitation. The polymer has a number average molecular weight of 6,200. Electron microscopy of the polymer shows substantial single layer exfoliation of the montmorillonite but to a somewhat lesser degree than the polymer of Example 2.
  • Example 1 is repeated except that one-quarter gram of treated montmorillonite is used and the polymerization reaction is three quarters of one hour at room temperature. Seven grams of polypropylene nanocomposite is recovered by acetone precipitation. The polymer has a number average molecular weight of 103,000. Electron microscopy of the polymer shows substantial single layer exfoliation of the montmorillonite to about the same degree than the polymer of Example 1.
  • Example 1 is repeated except that one-quarter gram of treated montmorillonite is used and the polymerization reaction is one quarter of one hour at eighty- five degrees Celcius. Ten grams of polypropylene nanocomposite is recovered by acetone precipitation. The polymer has a number average molecular weight of 18,700. Electron microscopy of the polymer shows some single layer exfoliation of the montmorillonite but less than that of Example 3.
  • Two grams of vacuum dried 4-tetradecylanilinium exchanged montmorillonite is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of tripropylaluminum is added to the slurry.
  • Five hundred microliters of a two and one half millimolar solution of metallocene polymerization catalyst (dimethylsilyl- bis(2-methyl-4-phenylindenys) zirconium (II) l ,4-diphenyl-l ,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for sixteen hours.
  • Example 6 is repeated except that the polymerization reaction is carried out for fifteen minutes. Fifteen grams of the resulting polypropylene nanocomposite is recovered. The tensile modulus of the resulting polypropylene nanocomposite is four hundred and eighty three thousand pounds per square inch. Electron microscopy examination of the resulting polypropylene nanocomposite shows substantial single layer exfoliation of the montmorillonite but to a somewhat lesser degree than that of Example 6.
  • Two grams of vacuum dried 4-tetradecylanilinium exchanged fluoromica is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2- methyl-4-phenylindenys) zirconium (II) 1,4-diphenyl- 1,3 -butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for five hours.
  • Two grams of vacuum dried 4-tetradecylanilinium exchanged fluoromica is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2- methyl-4-phenylindenys) zirconium (H) 1,4-diphenyl- 1,3 -butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for one day.
  • propylene gas at twenty pounds per square inch is contacted with the slurry for thirty minutes at room temperature.
  • Twenty five grams of polypropylene nanocomposite is recovered by acetone precipitation.
  • the polymer has a number average molecular weight of 170,000.
  • the tensile modulus of the polypropylene nanocomposite is 434,000 pounds per square inch (psi).
  • Example 9 The experiment of Example 9 is repeated six times using the polymerization times noted below. Pol. Time Molecular Wt. Tensile Mod. Pol. Wt.
  • Two grams of vacuum dried 4-tetradecylanilinium exchanged montmorillonite is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2- methyl-4-phenylindenys) zirconium (II) 1,4-diphenyl- 1 ,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for twenty minutes.
  • the sonicated slurry is then aged for one hour.
  • propylene gas at twenty pounds per square inch is contacted with the slurry for thirty minutes at room temperature.
  • Twenty grams of polypropylene nanocomposite is recovered by acetone precipitation.
  • the polymer has a number average molecular weight of 303,000.
  • the tensile modulus of the polypropylene nanocomposite is 522,000 pounds per square inch (psi).
  • Example 11 The experiment of Example 11 is repeated five times with the following results. Molecular Wt. Tensile Mod. Pol. Wt.
  • One gram of vacuum dried anilinium exchanged montmorillonite is added to one hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4- phenylindenys) zirconium (ET) 1,4-diphenyl- 1,3 -butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for one hour.
  • propylene gas at twenty pounds per square inch is contacted with the slurry at the temperatures shown below with the following results.
  • One gram of vacuum dried anilinium exchanged montmorillonite is added to one hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • Two milliliters of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4- phenylindenys) zirconium (II) 1,4-diphenyl- 1,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for one hour.
  • propylene gas at twenty pounds per square inch is contacted with the slurry at the temperatures shown below with the following results.
  • One gram of freeze dried hydrochloric acid treated attapulgite is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4- phenylindenys) zirconium (II) 1,4-diphenyl- 1,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for one hour.
  • propylene gas at twenty pounds per square inch is contacted with the slurry at the temperatures shown below with the following results.
  • One gram of freeze dried hydrochloric acid treated attapulgite is added to four hundred milliliters of dry toluene to produce a slurry.
  • Five milliliters of one molar tripropylaluminum in toluene is added to the slurry.
  • Two milliliters of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4- phenylindenys) zirconium (II) 1,4-diphenyl- 1,3-butadiene) is added to the slurry.
  • the slurry is then sonicated for thirty minutes.
  • the sonicated slurry is then aged for one hour.
  • propylene gas at twenty pounds per square inch is contacted with the slurry at the temperatures shown below with the following results.
  • tetradecylanalinium treated fluoromica Two grams of tetradecylanalinium treated fluoromica is added to four hundred milliliters of dry toluene to produce a slurry. Five milliliters of one molar tripropylaluminum in toluene is added to the slurry. One milliliter of a one and one quarter millimolar solution of metallocene polymerization catalyst (dimethylsilyl-bis(2-methyl-4- phenylindenys) zirconium (II) 1,4-diphenyl- 1,3-butadiene) is added to the slurry. The slurry is then sonicated for thirty minutes. The sonicated slurry is then aged for one day. Then, ethylene gas at ten pounds per square inch is contacted with the slurry at the temperatures shown below with the following results.
  • metallocene polymerization catalyst dimethylsilyl-bis(2-methyl-4- phenylindeny

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Abstract

Ce procédé de production d'un polymère nanocomposite comprend l'étape consistant à ajouter, dans un solvant, une oléfine à une dispersion -traitée au moyen d'un catalyseur de polymérisation à base de métallocène- d'un matériau de silicate multicouches, échangeur de cations et traité à l'acide, de façon que l'oléfine se polymérise pour former le polymère nanocomposite. L'invention concerne également un matériau de silicate multicouches, échangeur de cations, traité à l'acide, exfolié, dispersé dans une matrice polymère, et caractérisé en ce qu'environ cinquante % de ce matériau de silicate comprend à l'examen au microscope électronique cinq couches ou moins. L'invention concerne encore un matériau de silicate multicouches, échangeur de cations, traité à l'acide, traité au moyen d'un catalyseur de polymérisation à base de métallocène.
PCT/US2000/027840 1999-10-07 2000-10-06 Polymeres nanocomposites WO2001030864A2 (fr)

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WO2001030864A3 (fr) 2002-03-28
AU1330701A (en) 2001-05-10

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