WO2003027016A1 - Nanocomposite contenant des matieres de remplissage fibreuse et lamellaire de dimensions nanometriques - Google Patents

Nanocomposite contenant des matieres de remplissage fibreuse et lamellaire de dimensions nanometriques Download PDF

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WO2003027016A1
WO2003027016A1 PCT/US2002/016355 US0216355W WO03027016A1 WO 2003027016 A1 WO2003027016 A1 WO 2003027016A1 US 0216355 W US0216355 W US 0216355W WO 03027016 A1 WO03027016 A1 WO 03027016A1
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layered silicate
silicate material
cation exchanging
exchanging layered
grams
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PCT/US2002/016355
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English (en)
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Juan M. Garces
Steve R. Lakso
Tao Sun
Zoran R. Jovanovic
Alex Kuperman
Richard F. Fibiger
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The Dow Chemical Company
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the instant invention relates to polyolefin (such as polyethylene or polypropylene) reinforced with cation-exchanging multi-layered silicates.
  • the cation-exchanging multi-layered silicate delaminates or exfoliates, at least to some degree, into the polymer matrix.
  • Such composite materials are known in the art as a "nanocomposite polymers" when at least one dimension of the exfoliated multi-layered silicate material is less than sixty nanometers.
  • Nanocomposite polymers generally have enhanced mechanical property characteristics vs. conventionally filled polymers, for example, increased tensile or flex modulus together with increased impact toughness.
  • the thickness of a single layer of a delaminated multi-layered silicate material is in the range of 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 usually show a dispersion of multiple layer units of the multi-layered silicate material in the polymer, for example, two, three, four and more 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.
  • the multi-layered silicate material is only swelled with the bulk polymer, that is, "intercalated". If the multi-layered silicate material is not at least partially exfoliated or intercalated, then the mechanical property improvement of the polymer composite will usually be no better than if a conventional micron sized filler is dispersed in the polymer.
  • Multi-layered silicate materials have been treated with organic onium ions to facilitate exfoliation when blended with polar polymers such as polyamide polymers, United States Patent 5,973,053.
  • polar polymers such as polyamide polymers
  • non-polar polymers such as polyethylene or polypropylene
  • a compatibalizer by incorporating more than ten percent of a polar substituted main guest molecule as a compatibalizer, it is possible to achieve an effective degree of exfoliation of the onium treated multi-layered silicate material into the non-polar polymer.
  • the layers of platy cation-exchanging multi-layered silicates such as montmorillonite, are held together by ionic bonds to the exchangeable cations.
  • the resulting shear forces are not sufficient to delaminate or exfoliate the silicate layers even when the cation is a quaternary ammonium ion because polyolefins are a relatively non-polar material.
  • the second approach of Usuki et al. was to blend a quaternary ammonium exchanged multi-layered silicate with a maleic anhydride modified polypropylene polymer.
  • the maleic anhydride modified polypropylene polymer had sufficient polarity to exfoliate the silicate under the shear conditions of the blending process.
  • the improvement of the properties of the resulting nanocomposite are about the same as if the same amount of a conventional macro sized filler (such as talc) had been used.
  • the instant invention is a polyolefin nanocomposite composition, comprising: from one to twenty weight percent of a platy cation exchanging layered silicate material, from one to twenty weight percent of a fibrous cation exchanging layered silicate material and from ninety eight to sixty weight percent of a polyolefin polymer matrix, the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material being dispersed in the polyolefin polymer matrix.
  • the use of both the platy and the fibrous cation exchanging layered silicate material results in a synergistic improvement of the physical properties of the composition.
  • the composition can be made by melt blending the polymer with the platy and fibrous material.
  • the composition can be made by polymerizing the polymber with a metallocene polymerization catalyst treated dispersion of an acid treated platy and fibrous material in a solvent so that the olefin polymerizes to form the composition.
  • Fig. 1 is an idealized drawing of a composition of the instant invention showing platy and fibrous cation exchanging layered silicate material dispersed in a polymer matrix.
  • the instant invention is a polyolefin nanocomposite composition, comprising: from one to twenty weight percent of a platy cation exchanging layered silicate material, from one to twenty weight percent of a fibrous cation exchanging layered silicate material and from ninety eight to sixty weight percent of a polyolefin polymer matrix, the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material being dispersed in the polyolefin polymer matrix.
  • plaque cation exchanging layered silicate material is well known in the art and includes the “clay mineral” of United States Patent 5,973,053.
  • Examples of cation exchanging layered silicate materials include:
  • 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.
  • fibrous cation exchanging layered silicate material includes materials such as attapulgite, boehmite, imogolite and sepiolite.
  • the fibrous cation exchanging layered silicate materials can exfoliate to produce multi-fiber units (herein multi-layer or multi-fiber units) and most preferably they exfoliate to produce single fiber units (herein single layer or single fiber units) dispersed in the polyolefin polymer.
  • Single fibers of a fibrous cation exchanging layered silicate material are typically about 500 nanometers long and can have a diameter of about 20 nanometers.
  • an "onium treated cation exchanging layered silicate material” is a cation exchanging layered silicate material that has been exposed to onium cations (usually organic quaternary ammonium compounds) so that the original cation of the cation exchanging layered silicate material is exchanged, at least in part, for the onium cations.
  • Onium treated cation exchanging layered silicate materials are well known in the instant art, for example, see the above-mentioned United States Patent 5,973,053.
  • Onium treated cation exchanging layered silicate materials are commercially available from, for example, Southern Clay Company in the United States.
  • the polyolefin polymer used in the instant invention is polypropylene. Maleated or non-maleated polypropylene may be used. Onium treated or non-onium treated cation exchanging layered silicate materal may be used.
  • the weight percent of platy cation exchanging layered silicate material used in the composition is from 0.5 to 1.5 times the weight percent of fibrous cation exchanging layered silicate material. Most preferably, the weight percent of platy cation exchanging layered silicate material used in the composition is from 0.8 to 1.2 times the weight percent of fibrous cation exchanging layered silicate material.
  • the amount of platy cation exchanging layered silicate material plus the amount of fibrous cation exchanging layered silicate material used in the composition is from 3 to 20 weight percent. Most preferably, the amount of platy cation exchanging layered silicate material plus the amount of fibrous cation exchanging layered silicate material used in the composition is from 8 to 12 weight percent.
  • the instant invention is also a process for making a polyolefin nanocomposite composition
  • a polyolefin nanocomposite composition comprising from one to twenty weight percent of a platy cation exchanging layered silicate material, from one to tweinty weight percent of a fibrous cation exchanging layered silicate material and from ninety eight to sixty weight percent of a polyolefin polymer matrix, the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material being dispersed in the polyolefin polymer matrix: the process comprising the step of blending the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material with the polyolefin polymer at a temperature sufficiently high to melt or soften the polyolefin polymer.
  • the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material have been pretreated by dispersing them in water under high shear (such as by sonication or high shear mixing) followed by drying (such as spray drying or more preferably by freeze drying).
  • high shear such as by sonication or high shear mixing
  • drying such as spray drying or more preferably by freeze drying.
  • the instant invention is also a process for making the polyolefin nanocomposite composition
  • a process for making the polyolefin nanocomposite composition comprising from one to twenty weight percent of a platy cation exchanging layered silicate material, from one to tweinty weight percent of a fibrous cation exchanging layered silicate material and from ninety eight to sixty weight percent of a polyolefin polymer matrix, the platy cation exchanging layered silicate material and the fibrous cation exchanging layered silicate material being dispersed in the polyolefin polymer matrix, the process comprising the step of: adding an olefin to a metallocene polymerization catalyst treated dispersion of an acid treated cation exchanging layered silicate material and a fibrous cation exchanging layered silicate material in a solvent so that the olefin polymerizes to form the nanocomposite polymer.
  • the acid treated platy and fibrous cation exchanging layered silicate material is dispersed under high shear in water to form an aqueous dispersion that is then frozen and then freeze dried to produce a dried mixture of acid treated platy and fibrous cation exchanging layered silicate material that is then contacted with a metallocene polymerization catalyst to produce a metallocene polymerization catalyst treated dispersion of an acid treated cation exchanging layered silicate material and a fibrous cation exchanging layered silicate material.
  • an aqueous dispersion of the acid treated platy and fibrous cation exchanging layered silicate material can dried by any known technique such as spray drying.
  • the dispersion of the acid treated cation exchanging layered silicate material is contacted with a metallocene polymerization catalyst to produce the metallocene polymerization catalyst treated dispersion of an acid treated cation exchanging layered silicate material.
  • 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 nonco ⁇ jugated, 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 include Ci _20 straight, branched and cyclic alkyl radicals, Cg ⁇ O aromatic radicals, C ⁇ _20 alkyl- substituted aromatic radicals, and 07.20 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, fiuorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and boratabenzene groups, as well as C 1-10 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., 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' 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 O or l
  • 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.
  • M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;
  • R 3 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 (that is, 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 symmetry or possesses a chiral, stereorigid structure.
  • 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(IN) were disclosed for preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include rac bis-indenyl complexes. Similar systems based on Ti(IN) or Zr(IN) were disclosed for preparation of isotactic olefin polymers in Wild et al., Organomet. Chem.. 232, 233-47, (1982).
  • Exemplary bridged ligands containing two ⁇ -bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien- 1 -yl)silane, dimethylbis(2-t-butylcyclopentadien- 1 - 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, dimethylbis(2-methylinden- 1 -yl)silane, di
  • 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.
  • a further class of metal complexes utilized in the present invention corresponds to the preceding formula K' ⁇ MZ' ⁇ L fl Xp, 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- hydrogen 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 K', and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M.
  • a preferred class of such Group 4 metal coordination complexes used 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 3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R 3 groups together form a divalent derivative (that is, 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'-;
  • 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, cyclopentadienyltitanium-2,4-dimethylpentadienyl «trimethylphosphine, cyclopentadienyltitaniumdimethylmethoxide, cyclopentadienyltitaniumdimethylchlor
  • 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 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 When an olefin is added to the metallocene polymerization catalyst treated dispersion of the acid treated cation exchanging layered silicate material, the olefin 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 preferred temperature of the polymerization should be relatively low so that more of the polymerization occurs between the layers of the layered silicate in order to promote a greater degree of such exfoliation.
  • the fibrous cation exchanging layered silicate material may prevent the agglomeration or relamination of platy cation exchanging layered silicate material in the polymer matrix, thereby helping to maintain the degree or extent of exfoliation of the platy cation exchanging layered silicate material.
  • the polyolefin used in the instant invention is selected from the group of poiyolefins polymerized from olefin monomers having from two to ten carbon atoms.
  • olefin monomers include, for example, ethylene, propylene, octene, butadiene and mixtures thereof.
  • the polyolefin used is polypropylene.
  • Grade PD-191 polypropylene from Montell is ground into a sand like powder that is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882.
  • the test indicates a tensile modulus of 220,000 pounds per square inch.
  • Ten grams of talc are blended with ninety grams of grade PD-191 polypropylene from Montell at 165 degrees Celsius for 10 minutes in a Haake torque reometer at a speed of 60 rpm to produce a polymer blend.
  • the polymer blend is cooled and ground into a sand like powder which is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882.
  • the test indicates a tensile modulus of 319,000 pounds per square inch.
  • COMPARATIVE EXAMPLE 4 Ten grams of sepiolite are blended with ninety grams of grade PD- 191 polypropylene from Montell at 165 degrees Celsius for 10 minutes in a Haake torque reometer at a speed of 60 rpm to produce a polymer blend. The polymer blend is cooled and ground into a sand like powder which is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882. The test indicates a tensile modulus of 344,000 pounds per square inch.
  • Attapulgite and thirty grams of montmorillonite are stirred for one hour in one liter of one molar hydrochloric acid.
  • the acidified attapulgite and montmorillonite are sedimented by centrifugation and then stirred for one hour in one liter of fresh one molar hydrochloric acid.
  • the acidified attapulgite and montmorillonite are again sedimented by centrifugation and then stirred for one half hour in two liters of deionized water.
  • the acidified attapulgite and montmorillonite are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water.
  • the acidified attapulgite and montmorillonite are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water to form an acidified and washed dispersion of attapulgite and montmorillonite in water.
  • the acidified and washed dispersion of attapulgite and montmorillonite in water is then frozen.
  • the frozen acidified and washed dispersion of attapulgite and montmorillonite in water is then freeze-dried to produce a dried mixture of acidified attapulgite and montmorillonite.
  • Two grams of the dried mixture of acidified attapulgite and montmorillonite are mixed with 0.4 liter of dry toluene, 5 ml of one molar tripropylaluminum in dry toluene and then 1 ml of 2.5 micromolar metallocene polymerization catalyst (dimethylsilyl- bis(2-methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1,3 -butadiene) in dry toluene that is sonicated for one half hour and then let stand for twenty four hours to produce a mixed attapulgite and montmorillonite catalyst slurry.
  • metallocene polymerization catalyst dimethylsilyl- bis(2-methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1,3 -butadiene
  • Propylene gas at a pressure of 20 pounds per square inch is contacted with the mixed attapulgite and montmorillonite catalyst slurry at a temperature of 50 degrees Celsius for one hour to produce 23 grams of polypropylene nanocomposite polymer containing one gram of attapulgite and one gram of montmorillonite dispersed therein.
  • the polypropylene nanocomposite is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882. The test indicates a modulus of 402,000 pounds per square inch.
  • Attapulgite and thirty grams of fluoromica are stirred for one hour in one liter of one molar hydrochloric acid.
  • the acidified attapulgite and fluoromica are sedimented by centrifugation and then stirred for one hour in one liter of fresh one molar hydrochloric acid.
  • the acidified attapulgite and fluoromica are again sedimented by centrifugation and then stirred for one half hour in two liters of deionized water.
  • the acidified attapulgite and fluoromica are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water.
  • the acidified attapulgite and fluoromica are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water to form an acidified and washed dispersion of attapulgite and fluoromica in water.
  • the acidified and washed dispersion of attapulgite and fluoromica in water is then frozen.
  • the frozen acidified and washed dispersion of attapulgite and fluoromica in water is then freeze-dried to produce a dried mixture of acidified attapulgite and fluoromica.
  • Two grams of the dried mixture of acidified attapulgite and fluoromica are mixed with 0.4 liter of dry toluene, 5 ml of one molar tripropylaluminum in dry toluene and then 1 ml of 2.5 micromolar metallocene polymerization catalyst (dimethylsilyl- bis(2-methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1,3 -butadiene) in dry toluene that is sonicated for one half hour and then let stand for twenty four hours to produce a mixed attapulgite and fluoromica catalyst slurry.
  • metallocene polymerization catalyst dimethylsilyl- bis(2-methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1,3 -butadiene
  • Propylene gas at a pressure of 20 pounds per square inch is contacted with the mixed attapulgite and fluoromica catalyst slurry at a temperature of 50 degrees Celsius for one hour to produce 20.7 grams of polypropylene nanocomposite polymer containing one gram of attapulgite and one gram of fluoromica dispersed therein.
  • the polypropylene nanocomposite is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882. The test indicates a modulus of 442,000 pounds per square inch.
  • Attapulgite and thirty grams of hectorite are stirred for one hour in one liter of one molar hydrochloric acid.
  • the acidified attapulgite and hectorite are sedimented by centrifugation and then stirred for one hour in one liter of fresh one molar hydrochloric acid.
  • the acidified attapulgite and hectorite are again sedimented by centrifugation and then stirred for one half hour in two liters of deionized water.
  • the acidified attapulgite and hectorite are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water.
  • the acidified attapulgite and hectorite are sedimented by centrifugation and then stirred for one half hour in two liters of fresh deionized water to form an acidified and washed dispersion of attapulgite and hectorite in water.
  • the acidified and washed dispersion of attapulgite and hectorite in water is then frozen.
  • the frozen acidified and washed dispersion of attapulgite and hectorite in water is then freeze-dried to produce a dried mixture of acidified attapulgite and hectorite.
  • Two grams of the dried mixture of acidified attapulgite and hectorite are mixed with 0.4 liter of dry toluene, 5 ml of one molar tripropylaluminum in dry toluene and then 1 ml of 2.5 micromolar metallocene polymerization catalyst (dimethylsilyl-bis(2- methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1 ,3-butadiene) in dry toluene that is sonicated for one half hour and then let stand for twenty four hours to produce a mixed attapulgite and hectorite catalyst slurry.
  • metallocene polymerization catalyst dimethylsilyl-bis(2- methyl-4-phenylindenyl) zirconium (II) 1 ,4-diphenyl- 1 ,3-butadiene
  • Propylene gas at a pressure of 20 pounds per square inch is contacted with the mixed attapulgite and hectorite catalyst slurry at a temperature of 50 degrees Celsius for one hour to produce 19.3 grams of polypropylene nanocomposite polymer containing one gram of attapulgite and one gram of hectorite dispersed therein.
  • the polypropylene nanocomposite is then molded at 170 degrees Celsius and 30,000 pounds per square inch to form test bars for modulus testing using ASTM test method D882. The test indicates a modulus of 422,000 pounds per square inch.
  • Amoco brand 9934x high crystalline polypropylene pellets are compression molded at 200 degrees Celsius into 1/16 inch type V tensile bars, stored for at least two days to form test bars for modulus testing using ASTM test method D882. The test indicates a modulus of 365,000 pounds per square inch with a 4 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 471,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 559,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 603,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 570,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 603,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 506,000 pounds per square inch with a 2 percent elongation at break.
  • EXAMPLE 18 7.5 grams of sepiolite (Pangel S9 from Tolsa Chemical) is shaken with 95 grams of water and then sonicated at about 50 degrees Celsius for 4 hours. 2.5 grams of fluoromica (Somasif ME100 from Coop Chemical) is shaken with 95 grams of water and then sonicated at about 50 degrees Celsius for 4 hours.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 552,000 pounds per square inch with a 2 percent elongation at break.
  • the polymer is premelted for 3 minutes prior to the addition of the sepiolite/fluoromica.
  • the resulting blend is molded and tested as in comparative example 5. The test indicates a modulus of 569,000 pounds per square inch with a 2 percent elongation at break.

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  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract

La présente invention se rapporte à une composition de nanocomposite polyoléfinique comportant de 1 à 20 % en poids d'une matière lamellaire à base de silicate en couches échangeuse de cations (telle que de la magadiite), de 1 à 20 % en poids d'une matière fibreuse à base de silicate en couches échangeuse de cations (telle que de la sépiolite) et de 98 à 60 % en poids d'une matrice polymère polyoléfinique (telle que du polypropylène), la matière lamellaire à base de silicate en couches échangeuse de cations et la matière fibreuse à base de silicate en couches échangeuse de cations étant dispersées dans la matrice polymère polyoléfinique. L'utilisation simultanée de la matière lamellaire à base de silicate en couches échangeuse de cations et de la matière fibreuse à base de silicate en couches échangeuse de cations permet une amélioration synergique des propriétés physiques de la composition. Cette composition peut être fabriquée par mélange à l'état fondu du polymère et des matières lamellaire et fibreuse. Elle peut également être fabriquée par polymérisation du polymère avec une dispersion traitée au moyen d'un catalyseur de polymérisation métallocène et composée de matière lamellaire et fibreuse traitée par un acide dans un solvant de sorte que l'oléfine se polymérise et forme la composition.
PCT/US2002/016355 2001-05-22 2002-05-22 Nanocomposite contenant des matieres de remplissage fibreuse et lamellaire de dimensions nanometriques WO2003027016A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997017398A1 (fr) * 1995-11-07 1997-05-15 Southern Clay Products, Inc. Compositions a base d'argile riche en matieres organiques permettant de gelifier des systemes de resine polyester non saturee
US5973053A (en) * 1995-06-05 1999-10-26 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite clay material and method for producing the same, blend material and composite clay rubber using the same and production method thereof
WO2001025149A2 (fr) * 1999-10-07 2001-04-12 The Dow Chemical Company Composition de gel de silice et procede de fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5973053A (en) * 1995-06-05 1999-10-26 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite clay material and method for producing the same, blend material and composite clay rubber using the same and production method thereof
WO1997017398A1 (fr) * 1995-11-07 1997-05-15 Southern Clay Products, Inc. Compositions a base d'argile riche en matieres organiques permettant de gelifier des systemes de resine polyester non saturee
WO2001025149A2 (fr) * 1999-10-07 2001-04-12 The Dow Chemical Company Composition de gel de silice et procede de fabrication

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