WO2002094920A2 - Nanocomposite de polyolefine modifie de resine hydrogene - Google Patents

Nanocomposite de polyolefine modifie de resine hydrogene Download PDF

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Publication number
WO2002094920A2
WO2002094920A2 PCT/US2002/016354 US0216354W WO02094920A2 WO 2002094920 A2 WO2002094920 A2 WO 2002094920A2 US 0216354 W US0216354 W US 0216354W WO 02094920 A2 WO02094920 A2 WO 02094920A2
Authority
WO
WIPO (PCT)
Prior art keywords
layered silicate
silicate material
cation exchanging
weight percent
exchanging layered
Prior art date
Application number
PCT/US2002/016354
Other languages
English (en)
Other versions
WO2002094920A3 (fr
WO2002094920A9 (fr
Inventor
Juan M. Garces
Steve R. Lakso
Original Assignee
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AU2002326301A priority Critical patent/AU2002326301A1/en
Publication of WO2002094920A2 publication Critical patent/WO2002094920A2/fr
Publication of WO2002094920A3 publication Critical patent/WO2002094920A3/fr
Publication of WO2002094920A9 publication Critical patent/WO2002094920A9/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0838—Copolymers of ethene with aromatic monomers

Definitions

  • the instant invention relates to polyolefin (such as polyethylene or polypropylene) reinforced with delaminated or exfoliated cation-exchanging multi- layered silicates.
  • polyolefin such as polyethylene or polypropylene
  • 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, herein fully incorporated by reference.
  • polar polymers such as polyamide polymers
  • non-polar polymers such as polyethylene or polypropylene
  • 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.
  • a maleated polypropylene has poorer modulus characteristics than its non-maleated polypropylene counterpart. Blending a certain amount of a cation- exchanging milti-layered silicate with such maleated polypropylene is therefore necessary just to make the resulting modulus be the same as the modulus of the non- maleated polypropylene counterpart. It would be an advance in the art of polyolefin nanocomposites if an additive were discovered to facilitate the dispersion of a cation exchanging layered silicate material into a polyolefin that did not suffer from the above- mentioned problem associated with the use of maleated polypropylene.
  • the instant invention is a solution to the above-mentioned problem.
  • the instant invention is a nanocomposite composition, comprising: from one to thirty weight percent hydrogenated C9 aromatic polymer, from one to thirty weight percent cation . exchanging layered silicate material, and from ninty eight to forty weight percent polyolefin, the hydrogenated C9 aromatic polymer and the cation exchanging layered silicate material being dispersed in the polyolefin polymer.
  • the instant invention is also a method for making such nanocomposite composition by blending the hydrogenated C9 aromatic polymer, the cation exchanging layered silicate material and the polyolefin at a temperature sufficiently high to melt or soften the polyolefin polymer.
  • Fig. 1 is an idealized drawing made from an electron photo micrographic examination of a composition of the instant invention showing more than one half of the cation exchanging layered silicate material being present as one, two, three, four or five layer units.
  • the nanocomposite of the instant invention comprises from one to thirty weight percent hydrogenated C9 aromatic polymer, from one to thirty weight percent cation exchanging layered silicate material, and from ninety eight to forty weight percent polyolefin, the hydrogenated C9 aromatic polymer and the cation exchanging layered silicate material being dispersed in the polyolefin polymer.
  • Preferably, more than one half of the cation exchanging layered silicate material is present as one, two, three, four or five layer units upon examination by electron microscopy (and most preferably, more than one half of the material is so apparent as one, two or three layer units).
  • Photomicrographs of nanocomposite polymer compositions typically show a dispersion of multiple layer units of the cation exchanging multi-layered silicate material 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 electron photomicrograph of a polypropylene nanocomposite composition of the instant invention.
  • the layered silicate material is shown delaminated or exfoliated as: three single layer units, one two layer unit, one three layer unit, one four layer unit, one five layer unit and two eight layer units.
  • a one-layer unit typically is a platelet about 1 nanometers thick and 100-1000 nanometers wide.
  • weight average molecular weight is well known in the instant art and can be determined by, for example, gel permeation chromatography.
  • cation exchanging layered silicate material is well known in the instant art and includes the "clay mineral” of United States Patent 5,973,053, fully incorporated herein by reference. Examples of cation exchanging layered silicate materials of the platy type include: l) biophilite, kaolinite, dickalite or talc 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 "fibrous cation exchanging layered silicate material”.
  • 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 units) and most preferably they exfoliate to produce single fiber units (herein single layer 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. It should be understood that onium treated or non-onium treated cation exchanging layered silicate material may be used in the instant invention.
  • Hydrogenated C9 aromatic polymer is specifically defined herein as a polymer consisting of more than fifty weight percent of polymer having the following formula:
  • Hydrogenated C9 aromatic polymer is commercially available from Arakawa Chemical Industries, LTD as ARKON brand hydrogenated hydrocarbon resin. Hydrogenated C9 aromatic polymer can be made by polymerizing the C9 fraction of a naphtha cracker and then hydrogenating the resulting polymer. Preferably, the weight average molecular weight of the hydrogenated C9 aromatic polymer is in the range of from one thousand to five thousand as determined by gel permeation chromatography.
  • the term "hydrogenated C9 aromatic polymer" is more broadly defined herein as any polymer that is equivalent in the instant invention to the specific hydrogenated C9 aromatic polymber defined above in this paragraph.
  • the amount of hydrogenated C9 aromatic polymer used is from 0.5 to 1.5 times the weight percent of cation exchanging layered silicate material.
  • the amount of hydrogenated C9 aromatic polymer used is about the same as the amount of cation exchanging layered silicate material, that is, wherein the weight percent of hydrogenated C9 aromatic polymer is from 0.8 to 1.2 times the weight percent of cation exchanging layered silicate material.
  • the amount of cation exchanging layered silicate material used is from 3 to 20 weight percent.
  • the amount of cation exchanging layered silicate material used is from 8 to 12 weight percent.
  • the cation exchanging layered silicate material can be onium treated or not onium treated.
  • the polyolefin used in the instant invention is selected from the group of polyolefins 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.
  • the instant invention is also a method for making a nanocomposite composition
  • a nanocomposite composition comprising from one to thirty weight percent hydrogenated C9 aromatic polymer, from one to thirty weight percent cation exchanging layered silicate material, and from ninety eight to forty weight percent polyolefin, the hydrogenated C9 aromatic polymer and the cation exchanging layered silicate material being dispersed in the polyolefin polymer, the method comprising the step of: blending the hydrogenated C9 aromatic polymer, the cation exchanging layered silicate material and the polyolefin at a temperature sufficiently high to melt or soften the polyolefin.
  • the cation exchanging layered silicate material has been pretreated by dispersing it in water under high shear conditions (such as by sonication or high shear mixing) followed by drying (such as spray drying or more preferably by freeze drying).
  • EXAMPLE 5 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. 5 grams of fiuoromica (Somasif ME 100 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 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 659,000 pounds per square inch with a 1 percent elongation at break.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne une composition nanocomposite contenant entre un et trente pour cent par poids de polymère aromatique C9 hydrogéné, entre un et trente pour cent par poids de matériau de silicate en couches à échange de cations et entre quatre vingt dix-huit et quarante pour cent par poids de polyoléfine. Le polymère aromatique C9 hydrogéné et le matériau de silicate en couches à échange de cations sont dispersés dans le polymère de polyoléfine. L'invention concerne également un procédé de fabrication de cette nanocomposition par mélange du polymère aromatique C9 hydrogéné, du matériau de silicate en couches à échange de cations et de la polyoléfine à une température suffisamment élevée pour fondre ou ramollir le polymère de polyoléfine.
PCT/US2002/016354 2001-05-22 2002-05-22 Nanocomposite de polyolefine modifie de resine hydrogene WO2002094920A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002326301A AU2002326301A1 (en) 2001-05-22 2002-05-22 Hydrogenated resin modified polyolefin nanocomposite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29275801P 2001-05-22 2001-05-22
US60/292,758 2001-05-22

Publications (3)

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WO2002094920A2 true WO2002094920A2 (fr) 2002-11-28
WO2002094920A3 WO2002094920A3 (fr) 2003-03-27
WO2002094920A9 WO2002094920A9 (fr) 2003-09-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004039451A1 (de) * 2004-08-13 2006-03-02 Süd-Chemie AG Polymerblend aus nicht verträglichen Polymeren
WO2006135397A2 (fr) * 2004-09-27 2006-12-21 3M Innovative Properties Company Nanocomposite et procede de fabrication de celui-ci
US7691932B2 (en) 2004-09-27 2010-04-06 3M Innovative Properties Company Method of making a composition and nanocomposites therefrom
US7884150B2 (en) 2007-08-17 2011-02-08 Teknor Apex Company Flame retardant thermoplastic elastomer compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004117A1 (fr) * 1991-08-12 1993-03-04 Allied-Signal Inc. Formation par traitement en fusion d'un nanocomposite polymere en materiau stratifie ecaille
WO1997038027A1 (fr) * 1996-04-09 1997-10-16 The Texas A & M University System Procede de polymerisation par multiplication se pretant a la realisation de films polymeres hyperramifies sur une surface
WO1999047598A1 (fr) * 1998-03-16 1999-09-23 The Dow Chemical Company Nanocomposites polyolefiniques
WO2000061676A1 (fr) * 1999-04-12 2000-10-19 Sekisui Chemical Co., Ltd. Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique
WO2000078540A1 (fr) * 1999-06-17 2000-12-28 Triton Systems, Inc. Nanocomposites a hautes performances

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004117A1 (fr) * 1991-08-12 1993-03-04 Allied-Signal Inc. Formation par traitement en fusion d'un nanocomposite polymere en materiau stratifie ecaille
US5747560A (en) * 1991-08-12 1998-05-05 Alliedsignal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
WO1997038027A1 (fr) * 1996-04-09 1997-10-16 The Texas A & M University System Procede de polymerisation par multiplication se pretant a la realisation de films polymeres hyperramifies sur une surface
WO1999047598A1 (fr) * 1998-03-16 1999-09-23 The Dow Chemical Company Nanocomposites polyolefiniques
WO2000061676A1 (fr) * 1999-04-12 2000-10-19 Sekisui Chemical Co., Ltd. Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique
WO2000078540A1 (fr) * 1999-06-17 2000-12-28 Triton Systems, Inc. Nanocomposites a hautes performances

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004039451A1 (de) * 2004-08-13 2006-03-02 Süd-Chemie AG Polymerblend aus nicht verträglichen Polymeren
WO2006135397A2 (fr) * 2004-09-27 2006-12-21 3M Innovative Properties Company Nanocomposite et procede de fabrication de celui-ci
WO2006135397A3 (fr) * 2004-09-27 2007-03-08 3M Innovative Properties Co Nanocomposite et procede de fabrication de celui-ci
US7495051B2 (en) 2004-09-27 2009-02-24 3M Innovative Properties Company Nanocomposite and method of making the same
US7691932B2 (en) 2004-09-27 2010-04-06 3M Innovative Properties Company Method of making a composition and nanocomposites therefrom
US7884150B2 (en) 2007-08-17 2011-02-08 Teknor Apex Company Flame retardant thermoplastic elastomer compositions

Also Published As

Publication number Publication date
AU2002326301A1 (en) 2002-12-03
WO2002094920A3 (fr) 2003-03-27
WO2002094920A9 (fr) 2003-09-25

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