EP1203053A1 - Compositions interpolymeres utilisees dans la gestion du son - Google Patents

Compositions interpolymeres utilisees dans la gestion du son

Info

Publication number
EP1203053A1
EP1203053A1 EP00936469A EP00936469A EP1203053A1 EP 1203053 A1 EP1203053 A1 EP 1203053A1 EP 00936469 A EP00936469 A EP 00936469A EP 00936469 A EP00936469 A EP 00936469A EP 1203053 A1 EP1203053 A1 EP 1203053A1
Authority
EP
European Patent Office
Prior art keywords
composition
inteφolymer
vinyl
polymer
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00936469A
Other languages
German (de)
English (en)
Inventor
Brian W. Walther
Timothy E. Clayfield
Stephen R. Betso
Stephen M. Hoenig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Chemical Co
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
Priority claimed from US09/374,096 external-priority patent/US6319969B1/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP1203053A1 publication Critical patent/EP1203053A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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 present invention pertains to certain novel compositions containing an ⁇ - 5 olefin/vinyl or vinylidene interpolymer, an organic acid and optionally one or more coupling agents and optionally one or more fillers.
  • the interpolymers contained in the compositions of the claimed inventions may further contain polymerizable ethylenically unsaturated monomers, or may be blended with additional polymers.
  • the present invention also pertains to the use of such compositions in sound management.
  • materials containing ⁇ -olefm/vinyl or vinylidene substantially o random inte ⁇ olymers display good elastic properties and energy dissipation capacities, and thus are also useful in adhesive systems, as described in U.S. Patent No. 5,244,996.
  • inte ⁇ olymer-containing materials For example, it is desired to extend the range of temperatures in which these inte ⁇ olymers may be utilized.
  • Other properties which are desirable to modify include processing and/or fabrication characteristics, glass transition temperatures (T g ), modulus, hardness, viscosity, elongation, fire retardation, density, melt index (MI), tensile strength, compatibility 0 with other materials in composition, and virtually any other property.
  • compositions disclosed and claimed herein provide industry with economical and advantageous forms of materials effective, in particular, for applications requiring sound management.
  • the compositions provided by the present inventions are typically effective for both sound blocking and vibration damping.
  • the compositions generally display excellent physical properties amenable to a wide range of fabrication techniques, and are often recyclable, thus may be re-used or re-applied to various applications.
  • the present invention pertains to compositions comprising a substantially random inte ⁇ olymer comprising polymer units derived from ethylene and/or at least one C 3- 0 ⁇ -olefin with at least one vinyl or vinylidene aromatic monomer, or at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, or a combination of at least one vinyl or vinylidene aromatic monomer and at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer.
  • the inte ⁇ olymer component of the disclosed compositions may also further comprise polymer units derived from additional and different ethylenically unsaturated polymerizable monomers.
  • the inte ⁇ olymer component of the disclosed compositions may even be blended with a one or more other polymers.
  • the composition still further comprises, in addition to the inte ⁇ olymer, an organic acid. They composition may also comprise a processing agent, a filler, or both, as well as other additives.
  • the present invention provides a process for making the disclosed compositions.
  • the present invention provides products made from the disclosed compositions, and products made by the disclosed processes. Further additional embodiments provide sound management compositions fabricated with the disclosed compositions and according to the disclosed processes.
  • FIGURE. 1 is a cross-sectional illustration of an Oberst test bat having a free length, L, a total length, L T , a width, W, a thickness in the vibration direction, H , and a thickness of damping material, Hi.
  • novel compositions comprising substantially random ethylene and/or ⁇ -olefin/vinyl or vinylidene inte ⁇ olymers, and an organic acid.
  • the inte ⁇ olymers may further comprise additional monomers to form te ⁇ olymers, or higher level polymers. They also may be blended with additional polymers, and may further include a variety of processing agents and fillers. It may also be the case that the individual monomers, or the claimed inte ⁇ olymers and polymer blends, interact with each other or any of the other constituents of the claimed compositions, to form compositions that are more properly identified as the reaction products of the initial components. All such compositions are specifically contemplated to be within the scope of the present invention.
  • compositions of this invention prove particularly useful as a new and novel means of managing sound in a variety of circumstances.
  • compositions comprising ethylene and/or ⁇ -olefin and vinyl or vinylidene substantially random inte ⁇ olymers and organic acid. Further provided are methods of using these compositions in sound management.
  • inte ⁇ olymer is used herein to indicate a polymer wherein two or more different monomers are polymerized to make the inte ⁇ olymer.
  • substantially random in the substantially random inte ⁇ olymer comprising ethylene and/or an ⁇ -olefin and a vinyl or vinylidene monomer as used herein means that the distribution of the monomers of said inte ⁇ olymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION. Carbon 13 NMR Method. Academic Press New York, 1977, pp. 71-78.
  • the substantially random inte ⁇ olymer comprising an ⁇ -olefin and a vinyl or vinylidene monomer does not contain more than 15 percent of the total amount of vinyl or vinylidene monomer in blocks of more than 3 units. More preferably, the inte ⁇ olymer was not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon "13 NMR spectrum of the substantially random inte ⁇ olymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • composition includes a mixture of the materials which comprise the composition, as well as, products formed by the reaction or the decomposition of the materials which comprise the composition.
  • grafted or coupled compositions wherein a coupling agent is present and reacts with at least a portion of the one or more inte ⁇ olymers and/or at least a portion of the one or more fillers.
  • compositions "derived from” specified materials may be simple mixtures of the original materials, and may also include the reaction products of those materials, or may even be wholly composed of reaction or decomposition products of the original materials.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • the polymers of the present invention include inte ⁇ olymers derived from ethylene and/or ⁇ -olefin monomers and vinyl or vinylidene monomers. Ideally, the inte ⁇ olymers of the present invention are at least copolymers, with the constituent comonomers distributed substantially randomly to form a substantially random inte ⁇ olymer. Also specifically contemplated by the present invention are substantially random inte ⁇ olymers made by polymerizing more than two monomeric species. The monomers that are polymerized to form the inte ⁇ olymers of the disclosed compositions may remain substantially intact during the polymerization process, or may be substantially transformed or inter-react during the polymerization process.
  • Monomers that are acceptable for use in the inte ⁇ olymers of the present invention include, for example, ethylene and/or any ⁇ -olefin and any vinyl or vinylidene monomer.
  • Suitable ⁇ -olefins include, for example, ⁇ -olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms.
  • ethylene, propylene, butene-1, 4-methyl-l-pentene, hexene-1 and octene-1 are particularly suitable.
  • ⁇ -olefins do not contain an aromatic moiety.
  • Examples of useable vinyl or vinylidene monomers include vinyl or vinylidene aromatic monomers, cycloaliphatic monomers, and any sterically hindered vinyl or vinylidene monomers.
  • the inte ⁇ olymers of the present invention may also include one or more additional polymerizable ethylenically unsaturated monomers.
  • Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the inte ⁇ olymers used in the compositions of the present invention, include, for example, those represented by the following formula:
  • R 1 _ C C(R 2 ) 2
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C ⁇ - -alkyl, and C ⁇ -4 -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl or vinylidene aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds.
  • Particularly suitable monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof
  • Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (Ci - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof.
  • a more preferred aromatic vinyl or vinylidene monomer is styrene.
  • hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds by which is meant addition polymerizable vinyl or vinylidene monomers corresponding to the formula:
  • a 1 is a hindered aliphatic or cycloaliphatic substituent of up to 20 carbons
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • R 1 and A 1 together form a ring system and in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • hindered means that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert- butyl, norbornyl.
  • hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene.
  • Particular suitable are 1-, 3-, and 4-vinylcyclohexene.
  • Simple linear non-branched ⁇ -olefins including for example, ⁇ -olefins containing from 3 to 20 carbon atoms such as propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1 are not examples of sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds.
  • strained ring olefins such as norbornene and C O alkyl or C -]0 aryl substituted 5 norbornenes, with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
  • the most prefered substantially random inte ⁇ olymers for use in the present invetion are the ethylene/styrene and ethylene/propylene/styrene inte ⁇ olymers.
  • the inte ⁇ olymers of one or more ⁇ -olefins and one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or 0 vinylidene monomers employed in the present invention are substantially random polymers.
  • inte ⁇ olymers usually contain from 0.5 to 65, preferably from 5 to 55, more preferably from 8 to 50 mole percent of at least one vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and from 35 to 99.5, preferably from 45 to 95, more preferably from 50 to 92 mole percent s of ethylene and/or at least one aliphatic ⁇ -olefin having from 3 to 20 carbon atoms.
  • the melt index, I 2 (ASTM D-1238, 190°C/2.16 kg) of the substantially random inte ⁇ olymers is from 0.01 to 100, preferably from 0.1 to 30, more preferably from 0.3 to 15 g/10 min.
  • inte ⁇ olymers in a blended o composition with other polymers are also within the scope of this invention. Any other polymer may be used for blending with the inte ⁇ olymer according to this invention. Additional polymers blended with the inte ⁇ olymers of the present invention may prove especially useful in manipulating the properties and/or processability of the total composition. For example, a certain degree of mechanical strength is required for the shaping process when molding the claimed 5 compositions into sound managing articles. If these requirements are not met, the shaping process is degraded, and automation of the thermoforming process is not possible. The use of additional polymers to form a blended polymer-inte ⁇ olymer component in the claimed compositions may provide more preferred mechanical strength or tensile strength characteristics. One of skill in the art will choose polymers o that impart certain desired characteristics to the final blend-containing composition.
  • inte ⁇ olymer with another polymer is economic in nature.
  • the inte ⁇ olymers of the claimed compositions may be made increasingly cost efficient when combined with less expensive polymers in a blended composition that displays desirable characteristics. Indeed, the cost savings provided by integrating less expensive materials into the claimed compositions is acknowledged as an important manufacturing advantage of the disclosed compositions.
  • one attribute of the present invention is that the inte ⁇ olymer component of the claimed composition is particularly amenable to blending with other polymers.
  • inte ⁇ olymers an important factor in converting manufacturers from the use of current formulations to compositions containing ⁇ -olefin/vinyl or vinylidene inte ⁇ olymers is compatibility with the materials currently in use by that manufacturer. If a manufacturer uses the inte ⁇ olymer compositions disclosed herein alongside existing formulations, any mixtures made during transition from one material to the next is of saleable quality and may even display superior characteristics. Furthermore, the provided inte ⁇ olymers may be blended with other production scrap, such as edge-trim or rejected parts within the factory, or from post consumer waste or recycled vehicle parts to provide particularly economical compositions.
  • the present invention expressly includes compositions in which an additional polymer is blended with the inte ⁇ olymer in amounts necessary to impart desirable qualities to the composition as a whole.
  • additional polymers may be "blended" with the inte ⁇ olymer of the composition such that no measurable change in composition characteristics is observed.
  • This embodiment is advantageous when the disclosed inte ⁇ olymer compositions are manufactured in a system still containing residual amounts of polymer that may have been previously synthesized or otherwise processed in that system.
  • a further advantage of the presently disclosed compositions is that they can be mixed with any number of such materials in manufacturing processes.
  • Acceptable polymers to blend with the claimed inte ⁇ olymers include styrenic homopolymers and copolymers, and ethylene homopolymers and copolymers such as HDPE, LDPE and LLDPE.
  • Prefered polymers include EngageTM (a trademark and product of Du Pont Dow Elastomers), polyolefins (PO) and polyolefm elastomers (POE), including any co-polymers such as ethylene/octene, ethylene/hexene and ethylene/butene, ethylene/propylene, EPDM, ExactTM polymers (a trademark and product of Exxon Chemical), very- or ultra- low density polyethylenes (VLDPE or ULDPE) such as Enichem's ClearflexTM, styrene-butadiene random co-polymers (SBR) or (SBS) or styrenic block polymers, ethyl vinyl acetate (EVA), AffinityTM (a trademark and product of
  • the claimed compositions can be filled to 65 percent or more by volume. Further, the claimed compositions maintain their capacity to be highly filled even upon addition of still other polymers to form a blended polymer inte ⁇ olymer-containing composition.
  • the ability to blend these additional polymers with the disclosed inte ⁇ olymers is further advantageous because the other polymers amenable to blending may be generally less expensive than the inte ⁇ olymers alone.
  • scrap or recycle polymer to the composition, or by adding these polymers in virgin form, the economics of the plant and the product produced can be kept at very favorable levels, and the need to separate waste streams within the plant is eliminated (adding further economic value to the disclosed compositions).
  • the use of blend polymers in these compositions therefore increases the value per pound of the composition, allowing the formulation of extremely cost-efficient compositions amenable to a variety of applications.
  • an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl or vinylidene aromatic monomer at elevated temperatures, at some point in the manufacturing process.
  • the presence of vinyl or vinylidene aromatic homopolymer is in general not detrimental for the pu ⁇ oses of the present invention and may be tolerated.
  • the vinyl or vinylidene aromatic homopolymer may be separated from the inte ⁇ olymer, if desired, by extraction techniques such as selective precipitation from solution with a non-solvent for either the inte ⁇ olymer or the vinyl or vinylidene aromatic homopolymer.
  • the level of the vinyl or vinylidene aromatic homopolymer be no more than 20, preferably less than 15, more preferably less than 10 weight percent, of the total weight of the polymer component of the composition.
  • the substantially random inte ⁇ olymers may be modified by typical grafting, hydrogenation, functionalizing, crosslinking or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • the substantially random inte ⁇ olymers are prepared by polymerizing a mixture of polymerizable monomers in the presence of metallocene or constrained geometry catalysts. For example, they can be prepared as described in US Application Serial Number 545,403 filed July 3, 1990 (corresponding to EP-A-0,416,815) by James C. Stevens et al., and in U.S. Patent No. 5,872,201.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres (300 MPa) and temperatures from -30°C to 200°C.
  • the substantially random ⁇ -olefin/vinyl or vinylidene aromatic inte ⁇ olymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992).
  • substantially random ⁇ -olefin/vinyl or vinylidene aromatic inte ⁇ olymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp 2 R 2 1 where (Cp and Cp are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other; R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxyl groups, or aryloxyl groups, independently of each other; M is a group IV metal, preferably Zr or 5 Hf, most preferably Zr; and R is an alkylene group or silanediyl group used to crosslink Cp 1 and Cp 2 ).
  • inte ⁇ olymers which possess at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in WO 98/09999.
  • These inte ⁇ olymers contain additional signals with intensities greater than three times 0 the peak to peak noise. These signals appear in the chemical shift range 43.75-44.25 ppm and 38.0-38.5 ppm. Specifically, major peaks are observed at 44.1, 43.9 and 38.2 ppm.
  • a proton test NMR experiment indicates that the signals in the chemical shift region 43.75-44.25 ppm are methine carbons and the signals in the region 38.0-38.5 ppm are methylene carbons.
  • these new signals are due to sequences involving two head-to- tail vinyl aromatic monomer preceded and followed by at least one ⁇ -olefminsertion, 5 for example an ethylene/styrene/styrene/ethylene tetradwherein the styrene monomer insertions of said tetrads occur exclusively in a 1 ,2 (head to tail) manner.
  • each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to about 30 preferably from 1 to 20, more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
  • Particularly preferred catalysts include, for example, racemic-
  • the random copolymers of ethylene and styrene as disclosed in Polymer Preprints Vol. 39, No. 1, March 1998 by Tom Aria et al. can also be employed as blend components for the present invention.
  • the polymerization may be carried out in solution, slurry, or gas phase polymerization reactions. Further, the polymerization may be carried out as a batchwise or a continuous polymerization process. In a continuous process, ethylene, vinyl or vinylidene aromatic monomer or hindered aliphatic vinyl or vinylidene monomer, and solvent and the optional propylene or alternate third monomer are continuously supplied to the reaction zone and polymer product continuously removed therefrom.
  • the substantially random inte ⁇ olymer may be polymerized at conditions for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, reactor pressures ranging from atmospheric to 3500 atmospheres (355 MPa).
  • the reactor temperature will typically be from -30°C to 200°C.
  • the reactor 5 temperature will be greater than 50°C, typically from 70°C to 200°C, and preferably from 80°C to 150°C, with temperatures at the higher end of the range, that is, temperatures greater than 100°C favoring the formation of lower molecular weight polymers.
  • Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in the o formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • the substantially random inte ⁇ olymer may be prepared using the catalysts as described above as supported in an inert support, such as silica.
  • an inert support such as silica.
  • slurry polymerizations take place s in liquid diluents in which the polymer product is substantially insoluble.
  • the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent.
  • the ⁇ -olefin monomer or a mixture of different ⁇ -olefin monomers may be used in whole or in part as the diluent.
  • the diluent comprises, in at least a major part, the monomer or monomers to be polymerized.
  • the substantially random inte ⁇ olymer may be blended with additional polymers, according to the needs of the particular formulator, to form a useful blended polymer composition.
  • the inte ⁇ olymers of the present invention may 5 be blended with other polymers to form various types of blends.
  • Types of blends that are useful in the compositions disclosed herein include mechanical blends, in which the polymers are mixed at temperatures above the T g or T m for the amo ⁇ hous or crystalline polymers respectively.
  • mechanochemical blends in which the polymers are mixed at shear rates high enough to cause degradation. When using o mechanochemical blends, care must be taken to control combination of resultant free radicals, which form complex mixtures including graft and block compositions.
  • Solution-cast blends and latex blends are also useful according to the present invention; as are a variety of inte ⁇ enetrating polymer network blends.
  • the polymer blends of the present invention can be prepared by any conventional compounding operation, such as for example single and twin screw extruders, Banbury mixers, Brabender mixers, Farrel continuous mixers, and two roll mills.
  • the order of mixing and the form of the blend components to be mixed is not critical; but rather, it may vary depending on the particular requirements or needs of the individual compounder.
  • the mixing temperatures are preferably such that an intimate blend is obtained of the components. Typical temperatures are above the softening or melting points of at least one of the components, and more preferably above the softening or melting points of all the components.
  • the claimed compositions also contain an organic acid.
  • the organic acid is added in an amount sufficient to lower the torque required in the mixing equipment, or to lower the viscosity of the remainder of the composition, or to otherwise improve the flow of the composition during processing and fabrication, or both.
  • the addition of as little as 0.3 weight percent stearic acid may decrease the torque by up to 50 percent or more on the mixing rotors.
  • the extreme torque peak seen upon addition of filler to the composition may also be decreased relative to the case with no acid.
  • the acid may have other functional effects.
  • the organic acid may serve as a dispersant, allowing the filler component to be more evenly distributed throughout the composition.
  • the acid may be added at any point in the production process or it may be added in stages. Alternatively or additionally, it may be added as a coating to other additives to the composition, such as the filler. When such a coated filler is used, the filler is generally coated with the acid prior to its mixture with the other components of the composition.
  • Organic acids over a wide range of saturated acid types from C 6 monobasic saturated carboxylic acids such as caproic to long-chain types such as C 22 (behenic) fatty acids, are highly effective in enhancing elongation and in increasing melt index.
  • a concomitant decrease in blend stiffness is generally also attained.
  • addition of organic acid promotes dispersion of the filler, or other additives, throughout the composition.
  • monomeric organic acids the so-called 'dimer' and 'trimer' acids
  • Saturated polybasic acids are also effective, as are mono- or polyunsaturated organic acids, including the Cj to C 20 mono- and dicarboxylic acids, and, in particular, oleic acid (mono-unsaturated C ⁇ 8 -type fatty acid) are also highly effective.
  • Cyclic organic acid 'analogs' of the fatty acids are also effective for practicing this invention. Both alicyclic (saturated) and aromatic (unsaturated, benzene-related ring structures with carboxylic group) may be used. The various attributes of all these acids, known to those skilled in the art, are considered when chosing an acid for use in the compositions of the present invention.
  • Mono-, di- and trivalent metal salts of organic acids are very effective in carrying out the pu ⁇ oses of this invention.
  • Esters and amides of the organic acids are also effective.
  • the number of organic acids in existence is enormous; the examples named above can be replaced by other close analogs, as known by those of skill in the art, with good results and without departing from the spirit of this invention.
  • the preferred organic acids are selected from the group consisting of saturated mono-, di- and tricarboxylic acids having from 6 to 54 carbon atoms; unsaturated mono- and dicarboxylic acids having from 12 to 20 carbon atoms; and calcium, magnesium and zinc salts of said acids.
  • the most preferred organic acids are selected from the group consisting of palmitic, stearic and oleic acids, dimers and trimers thereof, and mixtures of these acids.
  • the preferable amount is from 0.01 to 5 percent by weight, and preferably from 0.05 to 2 percent. Most preferably, when using a fatty acid which is particularly effective, the amount is from 0.1 to 1.0 percent by weight.
  • the substantially random inte ⁇ olymer comprises from 4.9 to
  • One of the advantages of the disclosed compositions is their ability to maintain desirable fabrication characteristics with very high filler levels.
  • formulating cost efficient compositions is also aided by the use of fillers.
  • the attainment of filler loadings of approximately 50 percent by volume, and above, while maintaining adequate mechanical properties is favorable to the formulation of economical compositions, and results in compositions particularly useful for sound management applications.
  • Addition of an organic acid improves dispersion of a filler in the composition, and thus further facilitates achieving preferable filler loading levels in an economical manner.
  • Points of novelty in the presently disclosed compositions include their capacity to be highly filled and for the filler to be evenly dispersed via the use of an organic acid.
  • An additional advantage of the claimed compositions, and another example of where they provide an improvement over the prior art, is their ability to maintain desirable mechanical properties over a wide range of filler levels.
  • the addition of moderate levels of filler to the claimed novel compositions can provide an excellent feel to the final article.
  • the capacity of the disclosed compositions to sustain addition of high levels of filler makes them particularly useful in the manufacture of sound management materials.
  • the percentage of filler that can be included in the composition of the present invention on a weight basis is primarily a function of the density of the filler. Particle size and shape of the filler also will effect the properties of the composition. For example, ultra fine particle size fillers (less than 1 micron average particle size) generally have a tendency to result in higher blend viscosities and are also more expensive. Preferred fillers are calcium carbonate and barium sulfate, or a combination thereof.
  • the amount of filler present in the composition of the present invention is from 0.01 to 95 percent by weight, of the composition. Preferably, the filler represents from 5 to 90 percent by weight. Most preferably, when using a filler of medium density, such as calcium carbonate, the amount of filler is from 30 to 85 percent by weight.
  • the amount of filler is preferably from 30 to 95 percent by weight.
  • the level of filler in a blend composition may be described by weight or volume.
  • the volume percent of the filler may be estimated by the equation:
  • vol percent F [(wt percent F /p F )xl00 percent]/[(wt percent F /p F ) + ⁇ (wt percent j/p ,)]
  • vol percent F is equal to the volume percent of the filler in the final composition
  • wt percent F is equal to the weight percent of the filler
  • p F is the density of the filler measured in grams per cubic centimeter (g/cm 3 )
  • wt percent) is the weight percent of the i l component
  • p. is the density of the i' component measured in grams per cubic centimeter (g/cm 3 ).
  • fillers or combination thereof is, of course, possible without altering the fundamentals taught in this patent.
  • inclusion of alumina trihydrate (ATH, Al O 3 ' 3H 2 O) is highly desirable when flame-retardant or low-smoke-tendency blends are desired.
  • Heavy fillers, such as powdered iron or lead, or oxides or shavings of them, can be employed when ultra-dense blends are desired.
  • minerals having low density such as magnesium carbonate, magnesium oxide, magnesium hydroxide, calcium sulfate, silica, fly ash, and cement dust, or organic fillers such as yarns, wood flour, nut shells, rice hulls, cornmeal, clay, can be employed when light-density blends are preferable.
  • fillers with varied aspect ratios such as talc, mica, from highly acicular (wollastonite, for example) to round (glass beads, for example,) can also be employed to alter relationships such as tensile strength or elongation.
  • compositions comprising an inte ⁇ olymer, non-ignition resistant filler, coupling agent, and optionally an initiator. Similar compositions comprising ignition-resistant fillers are described in the patent application entitled “Compositions Having Improved Ignition Resistance,” filed on the same day as the instant application and naming S.R. Betso et al., as inventors.
  • the amount of coupling agent and/or initiator of the invention may vary according to the end-use application in which the composition is to be employed. However, if present, the amount of coupling agent and/or initiator generally comprises from 0.1 to 10 weight percent of the composition.
  • the coupling agent and/or initiator also may vary according to the end-use application in which the composition is to be employed.
  • the coupling agent 5 and/or initiator is selected from organic peroxides, silanes, titanates, zirconates, multifunctional vinyl compounds, organic azides, and mixtures thereof. While not wishing to be bound to any theory, it is believed that, under some conditions, the filler may become coupled, that is, grafted, to the inte ⁇ olymer or another polymer of the composition capable of such grafting. Similarly, the filler may become coupled, (that 0 is, grafted) to at least one filler. Thus, the filler often serves as a coupling agent, which may couple the following components:
  • the inte ⁇ olymer is typically grafted onto the coupling agent via a vinyl group while an active polar group on the coupling agent usually binds the coupling agent to the filler.
  • the extent of coupling varies depending on the amount and types of o ingredients and the conditions to which the ingredients are subjected.
  • the amount, types of ingredients and conditions are such that at least a portion of at least one filler is coupled to at least a potion of at least one inte ⁇ olymer or any other polymer component which may be present in the composition.
  • the above-mentioned inte ⁇ olymer(s) suitable in the composition of the present 5 invention are usually thermoplastic, that is, the inte ⁇ olymer may be molded or otherwise shaped and reprocessed at temperatures above their melting or softening point. However, when a coupling agent is present in the composition, the inte ⁇ olymer may undergo some crosslinking. Thus, if a thermoplastic composition is desired then, the amount of coupling agent should be at least the amount necessary to generate the o desired amount of coupling or grafting but not so much that the thermoplastic nature of the composition is jeopardized.
  • thermoplastics are generally preferable if a non-thermoplastic composition is desired then a crosslinking process can be carried out by standard practices or by the addition of an amount of filler such that the composition, when cured, is not thermoplastic.
  • the coupling agent may be grafted to the inte ⁇ olymer by any conventional method.
  • Such methods and agents are described in, for example, K. Kircher, 5 "Chemical Reactions in Polymer Processing", pp. 62-63, Hanser Press, 1987, and G.
  • Such methods typically include the presence of a free radical initiator such as a peroxide or an azo compound or ionizing radiation.
  • a free radical initiator such as a peroxide or an azo compound or ionizing radiation.
  • Organic initiators especially 0 peroxide initiators, are preferred.
  • peroxide initiators include dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2, 5-dimethyl-2, 5- di (t-butyl peroxy)hexane, aluryl peroxide, di (t-butyl peroxy) 3, 3, 5- trimethylcyclohexane, and t-butyl peracetate.
  • Suitable azo compounds include those 5 such as azo-bis-isobutyl nitrite.
  • the coupling agent may be coated on one or more of the fillers and the vinyl groups replaced with a group, which is compatible with the inte ⁇ olymer.
  • Suitable coupling agents include any agent, which can be grafted to the inte ⁇ olymer.
  • Such coupling agents include, for example, silanes, titanates, zirconates, o multifunctional vinyl compounds, and mixtures thereof.
  • Typical titanates and zirconates are described in, for example, Ken-React Reference Manual, Kenrich
  • Preferable coupling agents include silanes, vinyl alkoxy titanates, zirconates, or vinyl substituted alkoxy or arlyoxy titanates or zirconates.
  • silanes include those of the general formula:
  • CH 2 CR'— (C(O)-O) x (C n H 2n ) y SiR 3 0 in which R' is a hydrogen atom or methyl group; x and y are 0 or 1 with the proviso that when x is 1, y is 1 ; n is an integer from 1 to 12 inclusive, preferably 1 to 4, and each R independently is a hydrolyzable organic group such as substituted or unsubstituted Cl-12 alkoxy groups (for example, methoxy, ethoxy, butoxy, etc.), substituted or unsubstituted aryloxy groups (for example, phenoxy, etc.), substituted or unsubstituted aralkoxy groups (for example, benzyloxy, etc.), substituted or unsubstituted C-.- 12 aliphatic acyloxy groups (for example, formyloxy, acetyloxy, propanoyloxy, etc.), amino or amino groups substituted with a suitable substituent such as
  • Silanes are also useful which have ketoximino hydroly sable groups, such as vinyl tris(methylethylketoamino) silane.
  • Particularly useful silanes include unsaturated silanes comprising an ethylenically unsaturated hydrocarboxyl group, such as vinyl, ally, isopropyl, butyl, cyclohexenyl or gamma-(meth)acryloxy allyl group, and a hydrolyzable group, such as, for example, a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group.
  • hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino group.
  • Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the inte ⁇ olymer such as vinyl trimethoxy silane, vinyl triethoxy silane, gamma-(meth)acryloxy propyl trimethoxy silane, and mixtures thereof.
  • at least a portion of the inte ⁇ olymer may be coupled to at least a portion of the filler without the express inclusion of a coupling agent.
  • compositions of the present invention may further contain any one or a combination of a variety of processing agents.
  • processing agents are those substances that function as a tackifier, an oil, a plasticizer, and antioxidant or a combination thereof. Such substances are selected for use depending upon the needs of the formulator, and the desired characteristics of the final composition.
  • Various additional other components may also be added to the disclosed compositions, as needed to suit the needs of the formulator.
  • processing agents When processing agents are employed in the present invention, they may be used alone, or in combination with other processing agents, to synergistically achieve similar properties, or to achieve different resultant properties in the end composition.
  • Effective amounts of processing agents in the present invention range from 0.25 to 50 percent of the composition, by weight, depending upon the particular processing agent and its role in the composition developed by an individual formulator. More preferable processing agent amounts range from 0.3 to 35; and, most preferably, from 0.5 to 25 percent by weight.
  • composition comprises a processing agent and/or filler and one or more substantially random inte ⁇ olymer and one or more further polymers
  • said inte ⁇ olymer comprises from 25 to 95 weight percent
  • said further polymer represents from 5 to 75 weight percent (based on the weight of said inte ⁇ olymer and said further polymer).
  • Tackifiers that are useful in the present invention can be any number of substances, including those that are commercially available and well-known by those of skill in the art, such as those listed in United States Patent No. 3,484,405. Generally, natural or synthetic resin materials, and rosin materials, work well. Prefered amounts of tackifier range from 1 to 50 weight percent of the composition. More preferable concentrations range from 5 to 25 percent, and most preferable concentrations range from 10 to 20 percent, by weight, of the composition.
  • the resins that can be employed according to the present invention are liquid, semi-solid to solid, complex amo ⁇ hous materials generally in the form of mixtures of organic compounds having no definite melting point and no tendency to crystallize.
  • Such resins are insoluble in water and can be of vegetable or animal origin, or can be synthetic resins.
  • the resins employed function to provide substantial and improved tackiness of the composition.
  • Suitable tackifiers include, but are not necessarily limited to the resins discussed below.
  • a class of resin components that can be employed as the tackifier composition hereof are the coumarone-indene resins, such as the para coumarone-indene resins.
  • the coumarone-indene resins which can be employed have a molecular weight which ranges from 500 to 5,000. Examples of resins of this type which are available commercially include those materials marketed as 'Picco'-25 and 'Picco'-lOO.
  • te ⁇ ene resins including also styrenated te ⁇ enes. These te ⁇ ene resins can have a molecular weight range from 600 to 6,000. Typical commercially available resins of this type are marketed as 'Piccolyte' S-100, as 'Staybelite Ester' #10, which is a glycerol ester of hydrogenated rosin, and as 'Wingtack' 95 which is a polyte ⁇ ene resin.
  • butadiene-styrene resins having a molecular weight ranging from 500 to 5,000 may be used as the tackifier.
  • a typical commercial product of this type is marketed as 'Buton' 100, a liquid butadiene-styrene copolymer resin having a molecular weight of about 2,500.
  • a fourth class of resins which can be employed as the tackifier hereof are the polybutadiene resins having a molecular weight ranging from 500 to 5,000.
  • a commercially available product of this type is that marketed as 'Buton' 150, a o liquid polybutadiene resin having a molecular weight of 2,000 to 2,500.
  • Another useful class of resins which can be employed as the tackifier are the so-called hydrocarbon resins produced by catalytic polymerization of selected fractions obtained in the refining of petroleum, and having a molecular weight range of 500 to 5,000. Examples of such resins are those marketed as 'Piccopale'-100, and as 'Amoco' s and Nelsicol' resins. Similarly, polybutenes obtained from the polymerization of isobutylene may be included as a tackifier.
  • the tackifier may also include rosin materials, low molecular weight styrene hard resins such as the material marketed as 'Piccolastic' A-75, disproportionated pentaerythritol esters, and copolymers of aromatic and aliphatic monomer systems of 0 the type marketed as Nelsicol' WX-1232.
  • the rosin that may be employed in the present invention may be gum, wood or tall oil rosin but preferably is tall oil rosin.
  • the rosin material may be a modified rosin such as dimerized rosin, hydrogenated rosin, disproportionated rosin, or esters of rosin.
  • Esters can be prepared by esterifying the rosin with polyhydric alcohols containing 2-6 alcohol groups.
  • Useful tackifiers include aromatic hydrocarbon resins, including those with low softening points such as Piccovar ; and aliphatic, low molecular weight hydrocarbon resins such as PiccopaleTM, and those with high softening points such as PiccotacTM.
  • Additional useful tackifiers include synthetic polyte ⁇ ene resins such as WingtackTM, and hydrogenated rosin, glycerol ester resins such as Foral . These must be regarded o only as typical examples, as literally hundreds of logical candidates exist.
  • the compounder In use, the compounder generally will want to select an ethylene-based copolymer and a tackifier resin, which will be mutually compatible; chemical similarities, which will indicate compatibility, can be used for guidance. The compounder may also elect to use incompatible systems. Finally, the reverse effect may be sought. For example, where an unusually slippery surface is desired, inco ⁇ oration of small amounts of a slip aid such as Armid O may prove beneficial.
  • plasticizers in ⁇ - olefin/vinyl or vinylidene substantially random inte ⁇ olymers are known in the art.
  • United States Patent No. 5,739,200 explains the use of plasticizers in ⁇ - olefin/vinyl or vinylidene inte ⁇ olymers, and lists those plasticizing agents that are particularly useful in compositions containing ⁇ -olefm/vinyl or vinylidene inte ⁇ olymers.
  • Preferred concentrations of plasticizers range from 0.25 to 50 percent, by weight. More preferred concentrations range from 0.3 to 35 percent by weight, with most preferred concentrations ranging from 0.5 to 25 percent, by weight.
  • Suitable plasticizers which can be employed herein include at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters (including adipates azelates and sebacates), epoxy compounds, phosphate esters, glutarates, polymeric plasticizers (polyesters of glycols and aliphatic dicarboxylic acids) and oils.
  • Particularly suitable phthalate esters include, for example, dialkyl C -C ⁇ 8 phthalate esters such as diethyl, dibutyl phthalate, diisobutyl phthalate, butyl 2- ethylhexyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, mixed aliphatic esters such as heptyl nonyl phthalate, di-(n-hexyl, n-octyl, n-decyl) phthalate (P610), di(n-octyl, n-decyl) phthalate (P810), and aromatic phthalate esters such as diphenyl phthalate ester, or mixed aliphatic-aromatic esters such as
  • trimellitate esters include, for example, tri-(2-ethylhexyl) trimellitate, tri-(heptyl, nonyl) trimellitate, tri isooctyl trimellitate, tri isodecyl trimellitate, tri-(octyl, decyl) trimellitate.
  • Particularly suitable benzoates include, for example, diethylene glycol dibenzoate and dipropylene glycol dibenzoate.
  • Particularly suitable epoxy compounds include, for example, epoxidised vegetable oils such as epoxidised soyabean oil and epoxidised linseed oil.
  • Particularly suitable phosphate esters include, for example, triaryl, trialkyl, mixed alkyl aryl phosphates such as tributyl phosphate, trioctyl phosphate, tri-(2- ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, isopropylphenyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, 2- ethylhexyl diphenyl phosphate and isodecyl diphenyl phosphate.
  • triaryl, trialkyl, mixed alkyl aryl phosphates such as tributyl phosphate, trioctyl phosphate, tri-(2- ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate,
  • Oils may also be used in the compositions of the present invention to manipulate the characteristics of the composition.
  • Commercial oils generally contain a range of components where the composition of the oil is reported as a percentage of napthenic, parafmic and aromatic oil.
  • Suitable oils include virtually any known oil, including naphthenic, parafmic and aromatic oils, further including, for example, mineral oils and natural oils. Oils are generally characterized by their flashpoint and composition. According to their classification and flash point, one skilled in the art can select the oil or combination of oils that will best achieve the desired characteristics in the compositions of the present invention.
  • Preferred oils include those commercialized under the names ShellflexTM 6371, ShellflexTM 6702, and ShellflexTM 2680.
  • plasticizer and processing oil may also be used to effectively achieve the desired properties in the resultant composition according to the present invention.
  • any processing oil may be combined with an epoxidized oil, a poly ether, or a polyester to manipulate the characteristics of the composition.
  • using a combination of plasticizers and oils may achieve more desirable properties than using either in isolation, depending upon the constituent parts of the inte ⁇ olymer or polymer blend component of the composition.
  • antioxidants for example, hindered phenols such as, for example, IrganoxTM 1010 a registered trademark of Ciba Geigy
  • phosphites for example, IrgafosTM 168 a registered trademark of Ciba Geigy
  • U. V. stabilizers for example. PIB
  • antiblock additives for example. PIB
  • slip agents for example, colorants, pigments blowing agents, ignition- resistant additives
  • Tinuvin, polyisobutylene, titanium dioxide, iron oxide pigments can also be included in the compositions of the present invention.
  • the additives are employed in functional amounts known to those skilled in the art.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during processing, storage, and ultimate end use of the polymers. By preventing oxidation, aging of the product is retarded.
  • antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or organic component of the composition.
  • the amounts of any of the other enumerated components, as well as additives are the functional amounts such as the amount to render the polymer or o polymer blend antiblocking, to produce the desired amount of filler loading to produce the desired result, to provide the desired color from the colorant or pigment.
  • additives in particular, can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35 more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend. 5
  • the order of mixing the components is usually not critical. The preferred order of mixing involves the polymer component as a starting point, to which an oil may be added.
  • the organic acid or other coupling agent or initiator is added, and then the filler and other processing agents or additives, such as plasticizers, tackifiers, and/or additional oils.
  • the filler and other processing agents or additives such as plasticizers, tackifiers, and/or additional oils.
  • the organic acid of the present invention may be advantageously added to the composition prior to addition of the inorganic components.
  • it may be added as a coating to any filler that is added.
  • guidance 0 may be found in United States Patent No. 4,263,196, which provides details of the effects of particle size of filler on the properties of polymer blends.
  • the disclosed ⁇ -olefin/vinyl or vinylidene inte ⁇ olymer containing compositions can be used in a variety of sound management or other insulating applications.
  • the disclosed compositions can simultaneously and/or independently block sound waves and damp vibrating sources that cause sound waves.
  • This invention also shows that the disclosed compositions will damp vibration across a wide and useful temperature range, and that they can be formulated to block and/or 5 absorb sound waves.
  • the disclosed compositions also can be filled with inert fillers, such as barium sulfate and/or calcium carbonate, to high levels which raise the resultant compound density to levels which will block sound.
  • compositions can be readily formed into useful articles by a variety of fabrication techniques such as, for example, rotational molding, conventional plastic forming techniques, including sheet 0 formation, profile extrusion, thermoforming, injection molding.
  • fabrication techniques such as, for example, rotational molding, conventional plastic forming techniques, including sheet 0 formation, profile extrusion, thermoforming, injection molding.
  • T g of the inte ⁇ olymer or inte ⁇ olymer-polymer blend component of the composition largely determine the desirable T g of the inte ⁇ olymer or inte ⁇ olymer- polymer blend component of the composition.
  • T g the desirable T g of the inte ⁇ olymer or inte ⁇ olymer-polymer blend component of the composition.
  • the compositions presently disclosed have T g at approximately room temperature, which tends to impart to the material an inherent sound-dampening capacity.
  • T g modifiers include phthalate ester plasticizers such as 0 dioctyl phthalate (DOP). Additional factors important in sound damping applications include the tensile strength, compressibility, and flex modulus as well as the geometry of the inte ⁇ olymer component of the final article. Further, as sound-damping articles must be in close contact with the item producing the sound, sound-damping articles must have a high adhesion and thermoformability. Goal parameters for sound- dampening articles include having a composite loss factor as high as possible, with a goal ratio ( ⁇ c ) of resonant energy to incident energy of approximately 0.1, or greater. In sound absorbing applications, the geometry or the form of the inte ⁇ olymer or blend component of the composition is more important, with those having increased surface areas being preferred. Such preferable properties may also be expressed in terms of "pore size" of the composition.
  • DOP dioctyl phthalate
  • Characteristic properties that are preferred in sound wave blocking applications include articles with a density of greater that 0.15 g/cm 3 .
  • Preferred densities for effective sound blocking articles range from approximately 1.5 to about 2.6 g/cm 3 .
  • the modulus of the composition again related to temperature at which the article is fabricated, is also important.
  • sound blocking articles are preferably made from compositions that are compoundable, processable and moldable. A noted advantage of the disclosed compositions is that they can support high filler loading and still retain a favorable balance of properties. Further, as filler is more economical, and increases final composition density (greater than 1.5 g/cm 3 ), the thickness of the material needed to block the sound is minimized.
  • the presently disclosed compositions When fabricated into sheets, the presently disclosed compositions effectively manage sounds at sheet thicknesses as thin as 0.05 inches, with a particularly useful sheet thickness obtained at about 0.13 inches.
  • the disclosed compositions are particularly amenable to fabrication.
  • the damping layers of articles based on the disclosed compositions have remarkable properties at the intermediate temperatures typical of thermoforming, where they hold their shape better than previous heavy layers, so that they can be draped over the thermoforming tool by automated machinery. This is despite the extreme filler levels which these compounds can be formulated to contain.
  • Specific mechanical properties that are desireably maintained by the disclosed compositions, even at high filler levels, include elongation characteristics that are desireable at both shaping or forming termperatures as well as use temperatures.
  • the damping layers or sheets are generally softer than traditional EVA heavy layers. Increasingly, vehicle manufacturers are demanding softer barrier layers, which are better at managing sound and vibration.
  • EngageTM or EVA or EngageTM/EVA heavy layers undergo a sharp drop in mechanical properties at between 52 and 55 volume percent filler. Above this level, the elongation to break at 80°C is below the 100 percent required for thermoforming and the sheet will break or pinhole.
  • the disclosed compositions can be filled to 65 volume percent before the properties, especially the elongational properties, degrade to an unacceptable level.
  • the filler level above which previous materials' mechanical properties degrade has been found by experience to be generally about 52 volume percent, and when using unusually high-quality fillers, may be as high as 56 volume percent.
  • the disclosed compositions are able to bind 65 volume percent and above, of economic fillers before the mechanical properties degrade.
  • articles made from the disclosed compositions are also remarkably soft with excellent drape.
  • compositions are advantageously amenable to a wide range of fabricating techniques for the production of economic sound management articles. They may be manipulated, by adjusting the amounts and types of components, such that they are easily molded.
  • the compositions disclosed according to the present invention can be fabricated into films, including blown films, sheets, moldings, foam sheet, foam plank, expandable and foamable particles, moldable foam beads, and injection molded articles by conventional processes.
  • the compositions can also be used in the manufacture of fibers, foams and lattices, as well as adhesive and sealant formulations
  • compositions of the present invention may be formed into articles by any suitable means known in the art and may be employed in any application in which the desired properties are useful. Included in the available means for forming the compositions disclosed herein are virtually any types of molding, extruding, calendering or casting. Specific examples of useful fabrication methods include compression and injection molding, including reaction injection molding and rreinforced reaction injection molding; calendering; extrusion coating; sheet laminating; and sheet thermoforming. Additional available fabrication methods include dry blending in a pelletized form in the desired proportions followed by melt blending in a screw extruder, an internal batch mixer (for example, a Banbury mixer), a calender or a roll mill, or the like.
  • An article may be prepared in a one-step process or a two-step process.
  • a one-step process the mixing and blending steps are combined and continuously performed on an apparatus having adequate mixing capability.
  • the two-step process the blend is first prepared in a granular form by a suitable mixing and pelletizing means, and then subjected to a conventional fabrication process.
  • Sheet articles are typically extruded in one step and often subjected to thermoforming, such as for example described in U.S. Pat. No. 4,386,187.
  • Film articles can be prepared by extrusion and thermoforming, but also by casting or film blowing. Blown films require the inte ⁇ olymer by itself, or a relatively homogeneously mixed inte ⁇ olymer-polymer blend for the polymer component of the composition, which preferably is prepared in a separate step.
  • the disclosed compositions are useful as binders for highly filled sound dampening compounds for automotive and other applications. It has been found that the level of filler that these compounds can bind without unacceptable degradation of the physical properties is significantly higher than many other polymers, which are not substantially random.
  • compositions of the present invention when employed in sound barrier layer applications are generally used in conjunction with a decoupling layer of foam or fibrous felt.
  • the high density of the compositions of the present invention itself acts as a barrier to the transmission of sound vibrations.
  • use of a decoupling layer in conjunction with said high density barrier layer) prevents the direct transmission of sound vibrations from the substrate through the barrier layer (which would occur if the sound barrier layer were directly affixed to the substrate).
  • the sound barrier layer usually has a density of between 1.5 and 2.6 g/cm 3 .
  • the barrier layer compound is usually calendered or extruded into a sheet, prior to thermoforming, to fit the contours of the vehicle, appliance or other structure to which it is applied.
  • the barrier layer may then be "laminated" with the foam or fiber layer, and is often also layered with a ca ⁇ et or other decorative layer.
  • the substrate is the material of construction of the article for which sound management is required and typically comprises metal, plastic, glass, natural fibers, synthetic fibers, and wood.
  • Such dense thermoplastic ethylene and/or ⁇ -olefin/vinyl or vinylidene inte ⁇ olymer containing compositions have many sound management uses including, but not limited to, extruded sheet to be used as a moldable sound barrier in sound deadening applications including transport systems such as automobiles, motor cycles, buses, tractors, trains trams, aeroplanes, automotive door and truck liners, rear seat strainers, wheel well covers, ca ⁇ et under layments, molded dash insulators, dash mats, construction, wallpapers/coverings, and paper/textiles industries, small and large appliances, including dishwashers, refrigerators, air conditioners, household items like blender housings, power tools, lawn and garden items like leaf blowers, snow blowers, small engines like outboard motors, jet ski's, and the like.
  • Additional applications include devices for modifying the sound of a drum, loudspeaker systems, composite sound walls, acoustically damped disc drive systems, mufflers, thermoformable acoustical mat compositions, sound damping units for vacuum cleaning machines, systems for reducing drag and noise of underwater vehicles, automotive headliners having improved sound management characteristics, sound damped automotive enclosures such as oil pans, high heat, sound damping metal-polymer laminates, molded ca ⁇ et assemblies with sound deadening backing, vibration-damping constrained-layer constructions, conveyor belts and material transfer systems, sound insulation moldable ca ⁇ ets, non-squeal disc brake pads, and the like. Further applications include coatings for wires and cables in a variety of electronic, telecommunications and similar areas in which cable or wire coatings are desirable.
  • the molecular weight of the polymer compositions used in the present invention is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formally known as "Condition (E)” and also known as I2).
  • Another useful method to indicate or determine the melt flow properties of the substantially random inte ⁇ olymers used in the present invention is the Gottfert melt index (G#, cm 3 /10 min) which is obtained in a similar fashion as for melt index (I ) using the ASTM D1238 procedure for automated plastometers, with the melt density set to 0.7632, the melt density of polyethylene at 190°C.
  • melt density to styrene content for ethylene-styrene inte ⁇ olymers was measured, as a function of total styrene content, at 190°C for a range of 29.8 percent to 81.8 percent by weight styrene inte ⁇ olymer. Atactic polystyrene levels in these samples were typically 10 percent or less. The influence of the atactic polystyrene was assumed to be minimal because of the low levels. Also, the melt density of atactic polystyrene and the melt densities of the samples with high total styrene content are very similar.
  • the method used to determine the melt density employed a Gottfert melt index machine with a melt density parameter set to 0.7632, and the collection of melt strands as a function of time while the 12 weight was in force. The weight and time for each melt strand was recorded and normalized to yield the mass in grams per 10 minutes. The instrument's calculated I2 melt index value was also recorded. The equation used to calculate the actual melt density is; ⁇
  • the density of the substantially random inte ⁇ olymers used in the present invention was determined in accordance with ASTM D-792. The samples are annealed at ambient conditions for 24 hours before the measurement is taken. Inte ⁇ olymer styrene content and atactic polystyrene concentration were determined using proton nuclear magnetic resonance ( ! H N.M.R). All proton NMR samples were prepared in 1, 1, 2, 2-tetrachloroethane-d 2 (TCE-d ). The resulting solutions were 1.6 - 3.2 percent polymer by weight. Melt index (I 2 ) was used as a guide for determining sample concentration.
  • I 2 was greater than 2 g/10 min, 40 mg of inte ⁇ olymer was used; with an I 2 between 1.5 and 2 g/10 min, 30 mg of inte ⁇ olymer was used; and when the I was less than 1.5 g/10 min, 20 mg of inte ⁇ olymer was used.
  • the inte ⁇ olymers were weighed directly into 5 mm sample tubes. A 0.75 mL aliquot of TCE-d 2 was added by syringe and the tube was capped with a tight-fitting polyethylene cap. The samples were heated in a water bath at 85°C to soften the inte ⁇ olymer. To provide mixing, the capped samples were occasionally brought to reflux using a heat gun.
  • Sweep Width 5000 Hz Acquisition Time, 3.002 sec Pulse Width, 8 ⁇ sec Frequency, 300 MHz Delay, 1 sec
  • Integrals were measured around the protons labeled above; the 'A' designates aPS. Integral A 7 1 (aromatic, around 7.1 ppm) is believed to be the three ortho/para protons; and integral A (aromatic, around 6.6 ppm) the two meta protons.
  • the two aliphatic protons labeled ⁇ resonate at 1.5 ppm; and the single proton labeled b is at 1.9 ppm.
  • the aliphatic region was integrated from 0.8 to 2.5 ppm and is referred to as A a. .
  • the theoretical ratio for A 7 1: A 6 : Aai is 3: 2: 3, or 1.5: 1 : 1.5, and correlated very well with the observed ratios for the StyronTM 680 sample for several delay times of 1 second.
  • the ratio calculations used to check the integration and verify peak assignments were performed by dividing the appropriate integral by the integral A Ratio A r is A 7 1 / A 6 6 .
  • Region A 66 was assigned the value of 1.
  • Ratio Al is integral A a ⁇ / A 66 . All spectra collected have the expected 1.5: 1 : 1.5 integration ratio of (o+p) ' m: ( ⁇ +b). The ratio of aromatic to aliphatic protons is 5 to 3. An aliphatic ratio of 2 to 1 is predicted based on the protons labeled ⁇ and b respectively in Figure 1. This ratio was also observed when the two aliphatic peaks were integrated separately.
  • the 1H NMR spectra using a delay time of one second had integrals C 7 1 , C 6 , and C a ⁇ defined, such that the integration of the peak at 7.1 ppm included all the aromatic protons of the copolymer as well as the o & p protons of aPS.
  • integration of the aliphatic region C a ⁇ in the spectrum of the inte ⁇ olymers included aliphatic protons from both the aPS and the inte ⁇ olymer with no clear baseline resolved signal from either polymer.
  • s c and e c are styrene and ethylene proton fractions in the inte ⁇ olymer, respectively, and S c and E are mole fractions of styrene monomer and ethylene monomer in the inte ⁇ olymer, respectively.
  • the total styrene content was also determined by quantitative Fourier Transform Infrared spectroscopy (FTIR).
  • FTIR quantitative Fourier Transform Infrared spectroscopy
  • the residue was slurried in 60 ml of mixed hexanes at about 20 °C for approximately 16 hours. The mixture was cooled to about -25 °C for about 1 hour. The solids were collected on a glass frit by vacuum filtration and dried under reduced pressure. The dried solid was placed in a glass fiber thimble and solid extracted continuously with hexanes using a Soxhlet extractor. After 6 hours a crystalline solid was observed in the boiling pot. The mixture was cooled to about -20 °C, isolated by filtration from the cold mixture and dried under reduced pressure to give 1.62 g of a dark crystalline solid. The filtrate was discarded. The solids in the extractor were stirred and the extraction continued with an additional quantity of mixed hexanes to give an additional 0.46 g of the desired product as a dark crystalline solid.
  • ESI 1 was prepared in a continuously operating loop reactor (36.8 gal, 139L).
  • An Ingersoll-Dresser twin screw pump provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa) with a residence time of approximately 25 minutes.
  • Raw materials and catalyst/cocatalyst flows were fed into the suction of the twin screw pump through injectors and Kenics static mixers.
  • the twin screw pump discharged into a 2 inch (5.1 cm) diameter line which supplied two Chemineer-Kenics 10-68 Type BEM Multi-Tube heat exchangers in series.
  • the tubes of these exchangers contained twisted tapes to increase heat transfer.
  • Recycle solvent was mixed with uninhibited styrene monomer on the suction side of five 8480-5-E Pulsafeeder diaphragm pumps in parallel. These five Pulsafeeder pumps supplied solvent and styrene to the reactor at 650 psig (4,583 kPa).
  • Fresh styrene flow was measured by a MicroMotion flowmeter, and total recycle solvent/styrene flow was measured by a separate MicroMotion flowmeter.
  • Ethylene was supplied to the reactor at 687 psig (4,838 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flowmeter.
  • a Brooks flowmeter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture combined with the solvent/styrene stream at ambient temperature. The temperature of the entire feed stream as it entered the reactor loop was lowered to 2°C by an exchanger with -10°C glycol on the jacket.
  • Preparation of the three catalyst components took place in three separate tanks: fresh solvent and concentrated catalyst/cocatalyst premix were added and mixed into their respective run tanks and fed into the reactor via variable speed 680-S-AEN7 Pulsafeeder diaphragm pumps.
  • the three component catalyst system entered the reactor loop through an injector and static mixer into the suction side of the twin screw pump.
  • the raw material feed stream was also fed into the reactor loop through an injector and static mixer downstream of the catalyst injection point but upstream of the twin screw pump suction.
  • This flashed polymer entered the first of two hot oil jacketed devolatilizers.
  • the volatiles flashing from the first devolatizer were condensed with a glycol jacketed exchanger, passed through the suction of a vacuum pump, and were discharged to the s solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of this vessel as recycle solvent while ethylene exhausted from the top.
  • the ethylene stream was measured with a MicroMotion mass flowmeter. The measurement of vented ethylene plus a calculation of the dissolved gases in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer and remaining o solvent separated in the devolatilizer was pumped with a gear pump to a second devolatizer.
  • the pressure in the second devolatizer was operated at 5 mm Hg (0.7 kPa) absolute pressure to flash the remaining solvent.
  • This solvent was condensed in a glycol heat exchanger, pumped through another vacuum pump, and exported to a waste tank for disposal.
  • the dry polymer ( ⁇ 1000 ppm total volatiles) was pumped with a 5 gear pump to an underwater pelletizer with 6-hole die, pelletized, spin-dried, and collected in 1000 lb (453 kg) boxes.
  • ESI #'s 2 and 3 were prepared in a 6 gallon (22.7 L), oil jacketed, Autoclave continuously stirred tank reactor (CSTR).
  • CSTR Autoclave continuously stirred tank reactor
  • a magnetically coupled agitator with Lightning A-320 impellers provided the mixing.
  • the reactor ran liquid full at 475 psig o (3,275 kPa).
  • Process flow was in at the bottom and out of the top.
  • Heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction.
  • At the exit of the reactor was a micromotion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.
  • Toluene solvent was supplied to the reactor at 30 psig (207 kPa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • the feed to the reactor was measured by a Micro-Motion mass flow meter. 0 A variable speed diaphragm pump controlled the feed rate. The styrene stream was mixed with the remaining solvent stream.
  • Ethylene was supplied to the reactor at 600 psig (4,137 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow. A Brooks flow meter/controller was used to deliver hydrogen s into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature.
  • the temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with -5°C glycol on the jacket. This stream entered the bottom of the reactor. o
  • the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream.
  • Preparation of the catalyst components took place in an inert atmosphere glove box.
  • the diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured 5 up with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst flush solvent just prior to entry through a single injection line into the reactor.
  • the stream was condensed with a glycol jacketed exchanger and entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top.
  • the ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer separated in the devolatilizer was pumped out with a gear pump to a ZSK-30 devolatilizing vacuum extruder. The dry polymer exits the extruder as a single strand. This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper.
  • Catalyst A ⁇ s (lH-cyclopenta[l]phenanthrene-2-yl)d ⁇ methyl(t-butylam ⁇ do)-s ⁇ lanet ⁇ t-m ⁇ um 1 4-d ⁇ phenylbutad ⁇ ene)
  • Catalyst b is (t-butylam ⁇ do)d ⁇ methyl(tetramethylcyclopentad ⁇ enyl)s ⁇ lane-t ⁇ tan ⁇ um (II) 1,3-pentad ⁇ ene prepared as in U S Patent # 5,556,928, Ex 17 c
  • Cocatalyst C is t ⁇ s(pentafluorophenyl)borane, (CAS# 001 109-15-5), d a modified methylalummoxane commercially available from Akzo Nobel as MMAO-3A (CAS# 146905-79-5)
  • compositions were prepared by adding 7.77 weight percent of ESI #1 and
  • the filler was added in stages to prevent an excessively high torque and the breakage of the shear pins.
  • the mixer was allowed to reach a steady state and a torque of 140Nm at 45 ⁇ m was recorded (Comparative Example 2).
  • the addition of 0.28 weight percent (0.55 volume percent) of stearic acid was added to the mixer and the torque dropped rapidly to 79Nm (Example 2).
  • Example 3 the filler and stearic acid were added together, and the torque peak was much more moderate ( ⁇ 90Nm) and never spiked during processing, thus presenting no danger to the integrity of the mixer.
  • the filler was added at one time if stearic acid was added prior to the addition of filler.
  • the mixtures were prepared by adding 11.1 weight percent of ESI # 1 to a lab- scale internal mixer pre-heated to 150°C. After the polymer was molten, 6.5 weight percent of Shellflex 371 paraffinic oil was added, followed by 82 weight percent of a 15 ⁇ m particle size calcite (CalcicoU W15 from Alpha Calcite, Germany), together with 0.3 weight percent stearic acid and 0.5 weight percent carbon black.
  • the presence of a sufficient amount of oil (greater than 50 percent of the amount of polymer, that is an oi polymer ratio of >0.5) and the stearic acid facilitate production of a damping sheet with desireable properties.
  • the ingredients were mixed for 4 minutes after which time the mass had reached 150-156°C.
  • the viscosity, measured by the torque generated on the mixer blades was not high, being only 20 percent higher than a typical EVA-based formulation under the same conditions.
  • the hot mass was passed once through a cold roll mill to make a 2mm thick sheet that was then laid flat on a table to cool.
  • EngageTM product and trademark of DuPont Dow Elastomers
  • ExactTM product and trademark of Exxon
  • ElvaxTM EVA product and trademark of E.I. DuPont de Nemours
  • ClearflexTM product and trademark of Enichem
  • the torque on the mixer is proportional to the viscosity of the components, the stickiness of the EVA is a physico-chemical property of the EVA, as is the small increase in hardness in the EVA containing formulation.
  • Composite Loss Factor is a measure of the ability of the material to stop vibration that causes noise. The higher the Composite Loss Factor, the better the ability to stop vibration.
  • the resonant frequency and half the power bandwidth (frequency difference between 3 dB down points from the resonant peak) of each mode needed for composite loss factor ( ⁇ c ) computation were read directly from a dual channel signal analyzer (B&K Type 2032).
  • the test samples were bonded on to the steel Oberst bar by compression molding.
  • the Oberst bar was placed in the center of a chase and loose polymer was laid on the metal bar.
  • the chase was covered on both sides with Mylar and placed in a compression molder.
  • the heating cycle conforms to ASTM standard D1325. Excess polymer was cut away from the Oberst by using a razor blade.
  • the dimensions of the bar were: total length 225 mm, free length 200 mm, thickness 0.8 mm, and width 12.7 mm. Test procedures were in accordance with SAE Recommended Practice J1637, Laboratory Measurement of the Composite Vibration Damping Properties of Materials on a Supporting Steel Bar with certain exceptions (see Figure 1).
  • Table 6 shows the Resonance Frequency (Hz) and resultant Composite Loss Factor ( ⁇ c ) for Comparative 4 and ESI #2, and ESI #3 all tested at 25 °C.
  • the results show that ESI #2 has comparable Composite Loss Factor to Comparative 4, which is the industry standard.
  • ESI #3 is shown to have superior Composite Loss Factor to Comparative 4.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Soundproofing, Sound Blocking, And Sound Damping (AREA)

Abstract

L'invention concerne de nouvelles compositions d'interpolymères d'éthylène et/ou α-oléfine/vinyle ou vinylidène ainsi qu'un acide organique et une charge. L'invention concerne également des compositions contenant des interpolymères d'éthylène et/ou α-oléfine/vinyle ou vinylidène, un acide organique, divers agents de traitement, des agents de couplage ainsi qu'une charge. Les compositions de l'invention sont particulièrement utiles dans des applications de gestion du son ou en temps qu'isolants.
EP00936469A 1999-06-18 2000-06-01 Compositions interpolymeres utilisees dans la gestion du son Withdrawn EP1203053A1 (fr)

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US13999999P 1999-06-18 1999-06-18
US139999P 1999-06-18
US374096 1999-08-12
US09/374,096 US6319969B1 (en) 1997-06-26 1999-08-12 Interpolymer compositions for use in sound management
PCT/US2000/015232 WO2000078860A1 (fr) 1999-06-18 2000-06-01 Compositions interpolymeres utilisees dans la gestion du son

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US8476360B2 (en) 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
US20050038160A1 (en) * 2003-08-15 2005-02-17 Hall Matthew Scott Ethylene copolymers with hollow fillers
DE102005046817A1 (de) * 2005-09-29 2007-04-05 Basf Ag Schalldämmplatte aus Füllstoff-haltigen, thermoplastischen Elastomeren auf Basis von Styrol
CN101448882A (zh) * 2006-04-06 2009-06-03 陶氏环球技术公司 可膨胀聚烯烃组合物和含有膨胀聚烯烃组合物的隔绝车辆部件
WO2009063809A1 (fr) * 2007-11-13 2009-05-22 Nitto Boseki Co., Ltd. Feuille de résine renforcée de fibres transparente et ininflammable et procédé pour la produire
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CN107223148A (zh) * 2015-02-11 2017-09-29 普立万公司 声音阻尼热塑性弹性体制品
US10814593B2 (en) 2016-07-25 2020-10-27 Avient Corporation Super-vibration damping thermoplastic elastomer blends and articles made therewith
CN109689772B (zh) 2016-09-09 2021-07-30 莱尼电缆有限公司 具有高柔韧性和阻燃性的聚合物组合物
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AR032741A1 (es) 2003-11-26
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