EP1381647A1 - Melanges d'interpolymeres sensiblement statistiques a performances thermiques accrues - Google Patents

Melanges d'interpolymeres sensiblement statistiques a performances thermiques accrues

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Publication number
EP1381647A1
EP1381647A1 EP02721027A EP02721027A EP1381647A1 EP 1381647 A1 EP1381647 A1 EP 1381647A1 EP 02721027 A EP02721027 A EP 02721027A EP 02721027 A EP02721027 A EP 02721027A EP 1381647 A1 EP1381647 A1 EP 1381647A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
blend
interpolymer
substantially random
vinyl aromatic
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Withdrawn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
EP02721027A
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German (de)
English (en)
Inventor
Yunwa W. Cheung
Samuel Ethiopia
Martin J. Guest
Pak-Wing S. Chum
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP1381647A1 publication Critical patent/EP1381647A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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 immiscible blends of two or more ⁇ - olefin/vinyl aromatic monomer interpolymers, the blend having at least one interpplymer component which comprises 2 to 7 mole percent vinyl aromatic monomer content, and uses for such blends.
  • the blend components are selected to provide superior processability and/or performance, such as upper use temperature, in the blend compositions and in their end use applications.
  • ⁇ -olefin/vinyl aromatic monomer interpolymers and especially ethylene/styrene interpolymers (ESI)
  • ESE ethylene/styrene interpolymers
  • They offer a range of material structures and properties which makes them useful for varied applications, such as compatibilizers for blends of polyethylene and polystyrene as described in US 5,460,818.
  • compatibilizers for blends of polyethylene and polystyrene as described in US 5,460,818.
  • Industry is constantly seeking to improve the applicability of these interpolymers.
  • Such enhancements may be accomplished via additives or the like, but it is desirable to develop technologies such as blend systems to provide improvements in processability and/or performance without the addition of additives.
  • Blends comprising two or more substantially random interpolymers are generally known in the art.
  • WO 98/10018 The Dow Chemical Company
  • WO 98/10018 describes blends of interpolymers in which individual interpolymer blend components have differences (> 0.5 mol percent ) in copolymer vinyl aromatic comonomer content, and/or molecular weight.
  • These blends can exhibit miscible behavior as indicated by their having a single glass transition temp, (Tg) which falls between the Tg's of the ESI blend components, or the blends can exhibit immiscible behavior as indicated by multiple Tg's.
  • Patent EP0869146 Al (Mitsui Chemicals) describes blends of copolymers of ethylene with an aromatic vinyl compound and/or an ⁇ - olef ⁇ n for which the copolymer blend components each have crystallinity of at least 10 percent and wherein the ratio of degree of crystallinity of the blend components is less than 1. Examples are given for blends of ethylene/styrene copolymers having 0.5, 2.0, 2.7 and 2.9 mol percent styrene comonomer.
  • Patent JP 2000- 129043 A (Denki Kagaku K.K.) describes blends containing two or more a- olefin/vinyl aromatic monomer copolymers, said copolymers being considered to be of different types with one copolymer having, for example, isotactic diad sequences. Examples are given for blends of ethylene/styrene copolymers wherein the component copolymers have greater than 10 mole percent styrene comonomer content.
  • This invention utilizes specific interpolymer blend components having from 2 to 7 mole percent vinyl aromatic monomer. These interpolymers have been found in independent studies of structure/property relationships to have a desirable balance of mechanical properties such as intrinsic tear properties, compatibility and processability. As such they are identified as preferred interpolymer blend components.
  • the present invention pertains to an immiscible blend of two or more substantially random interpolymers comprising 5 to 95 weight percent of at least one substantially random inte ⁇ olymer having an overall crystallinity (as measured by differential scanning calorimetry) of at least 20 wt percent , said interpolymer comprising: a) from 2 to 7 mole percent of one or more vinyl aromatic monomers and b) the balance comprising ethylene; or a combination of ethylene and at least one or more C 3 to C 20 ⁇ -olefin monomers, and optionally one or more additional olef ⁇ n monomers.
  • the above-identified interpolymer blend component is utilized in combination with:
  • the blends find utility in a wide range of fabricated articles such as calendered sheet, blown or cast films, compression or injection-molded articles, rotomolded or thermoformed parts.
  • the blends can be used in the manufacture of fibers, foams and latexes, and be utilized in adhesive and sealant formulations.
  • Blends fabricated under high shear melt processing conditions, (for example, where the shear rate is greater than 30 sec "1 ) can be used to produce for example film, foamed or injection molded parts for a range of applications,
  • 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 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • immiscible refers to individual blend components which are immiscible in each other.
  • polymers are considered to be immiscible when, in a blend of the two or more polymers, the individual blend components can still be identified by electron microscopy as discrete domains, or by their characteristic thermal transitions (such as the glass transition, Tg) which can still be discerned.
  • substantially random interpolymer in the substantially random interpolymer comprising polymer units derived from ethylene or ethylene in combination with one or more ⁇ -olef ⁇ n monomers with one or more vinyl aromatic monomers as used herein means that the distribution of the monomers of said interpolymer 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.
  • substantially random interpolymers do not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of vinyl aromatic monomer of more than 3 units.
  • the substantially random interpolymers used as blend components in the present invention are prepared by polymerizing i) ethylene, or ethylene in combination with one or more 3 to C 0 ⁇ -olefin monomers and ii) one or more vinyl aromatic monomers, and optionally iii) other polymerizable ethylenically unsaturated monomer (s).
  • Suitable ⁇ -olefins include for example, ⁇ -olefms containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1, 4-methyl-l- pentene,-hexene-l or octene-1. These ⁇ -olef ⁇ ns do not contain an aromatic moiety.
  • Suitable vinyl aromatic monomers which can be employed to prepare the interpolymers, 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 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 ⁇ - 4 -alkyl, and and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds.
  • Particularly suitable "such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C ⁇ - 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 monomer is styrene.
  • ethylenically unsaturated monomer(s) include norbornene and Cno alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary interpolymer being ethylene/styrene/norbornene.
  • the most preferred substantially random interpolymers are the ethylene/styrene, ethylene/propylene/styrene, ethylene/styrene/norbornene, and interpolymers.
  • the substantially random interpolymers include the pseudo-random interpolymers as described in EP-A-0,416,815 Bl and EP-A-0,765,888 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers.
  • the substantially random interpolymers also include the interpolymers of ethylene, olefinic monomers and vinyl aromatic monomers as described in US Patent No. 5,872,201 by Yunwa W. Cheung et al.
  • the substantially random interpolymers can be prepared by polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -30°C to 200°C as described in US Patent Nos 6,048,909 and 6,231,795 Bl. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp2 R2 where Cp 1 and Cp 2 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 Hf, most preferably Zr; and R 3 is an alkylene group or silanediyl group used to crosslink Cp 1 and Cp 2 .
  • the substantially random ⁇ -olefin vinyl aromatic interpolymers 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 interpolymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in U. S. Patent No. 6,191,245 Bl by Francis J. Timmers et al. These interpolymers contain additional signals in their carbon- 13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 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 43.70 - 44.25 ppm are methine carbons and the signals in the region 38.0 - 38.5 ppm are methylene carbons.
  • Copolymers of ethylene and styrene produced by bridged metallocene catalysts have been described by Arai, Toshiaki and Suzuki (Polymer Preprints. Am. Chem. Soc. Div. Polvm. Chem. Volume 38, pages 349, 350 [1997]) and in DE 197 11 339 Al and U.S. Patent No. 5,883,213 to Denki Kagaku Kogyo KK.
  • the manufacture of ⁇ - olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996, issued to Mitsui Petrochemical Industries Ltd.
  • an amount of atactic vinyl aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures.
  • the presence of vinyl aromatic homopolymer is in general not detrimental for the purposes of the present invention and can be tolerated.
  • the vinyl aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinyl aromatic homopolymer.
  • one or more of the interpolymer components may be modified by various cross-linking processes.
  • Such cross-linking processes include, but are not limited to, peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems.
  • a full description of the various cross-linking technologies is described in copending U.S. Patent No's 5,869,591 and 5,977,271, the entire contents of both of which are herein incorporated by reference.
  • Dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. Dual cure systems are disclosed and claimed in U. S. Patent Nos. 5,911,940 and 6, 124,370, the entire contents of both of which are incorporated herein by reference. For instance, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc.
  • the polymer compositions may also be modified by various cross-linking processes including, but not limited to the incorporation of a diene component as an additional monomer in the interpolymers and subsequent cross linking by the aforementioned methods and further methods including vulcanization via the vinyl group using sulfur for example as the cross linking agent.
  • the immiscible blend compositions comprise two or more substantially random ⁇ -olefin/vinyl aromatic monomer interpolymers, having as one component (A) from 5 to 95, preferably from 15 to 80, more preferably from 30 to 70 weight percent of one or more interpolymer blend components comprising from 2 to 7 mole percent, preferably from 2.5 to 6 mole percent and more preferably from 3 to 5.5 mole percent of one or more vinyl aromatic monomers and from 93 to 98 mole percent, preferably from 94 to 97.5 mole percent and more preferably from 94.5 to 97 mole percent) of one or more C 2 to C 20 ⁇ -olef ⁇ n monomers.
  • component (A) from 5 to 95, preferably from 15 to 80, more preferably from 30 to 70 weight percent of one or more interpolymer blend components comprising from 2 to 7 mole percent, preferably from 2.5 to 6 mole percent and more preferably from 3 to 5.5 mole percent of one or more vinyl aromatic monomers and from 93 to 98 mole percent,
  • the preferred ⁇ -olefin monomers are ethylene; or a combination of ethylene and at least one of propylene, 4- methyl-1-pentene, butene-1, hexene-l,octene-l or norbornene.
  • This interpolymer blend component has an overall polyethylene equivalent crystallinity as measured by differential scanning calorimetry of at least 20 wt.%, preferably at least 25 wt%.
  • the specific interpolymer blend components having 2 to 7 mole percent vinyl aromatic monomer have been found to have a desirable balance of mechanical properties such as intrinsic tear properties, compatibility and processability. As such they are identified as preferred interpolymer blend components.
  • This interpolymer blend component (A) is utilized in combination with:
  • the amount of vinyl aromatic comonomer in the interpolymer blend component (A) differs from that in the second interpolymer component (B) by an amount which results in an immiscible blend system.
  • the interpolymer is an ethylene/styrene interpolymer
  • an immiscible blend typically results when there is a copolymer styrene difference of at least 10 weight percent.
  • the immiscible nature of blends can be manifested and identified in the blends in that each component retains its characteristic thermal transition behavior such as Tg or crystalline melting transitions, or by the respective blend components being identifiable by microscopic techniques, including atomic force microscopy.
  • blends of ethylene styrene interpolymers are characterized by having an overall styrene content in the range 20 to 50 wt. percent styrene, and are designed to provide superior performance/ processability compared to a single interpolymer of the-same copolymer styrene content.
  • These blends have significantly enhanced TMA softening points either compared to the performance of a single component interpolymer of similar styrene content, or compared to the weighted average of the TMA softening points of the individual blend components.
  • the blend will contain three or more components that when combined together meet the overall requirements of immiscibility, but with the proviso that the third or additional component may be immiscible or miscible with either component (A) or component (B) or component (C) above.
  • the blends of the present invention may be prepared known methods including, but not limited to, solution blending, or dry blending the interpolymer , blend components in a pelletized form in the desired proportions followed by melt blending in an extruder, Banbury mixer or the like.
  • the dry blended pellets may be directly melt processed into a final solid state article by, for example, injection molding.
  • the blends may be made by direct polymerization, without isolation of the blend components, using for example two or more catalysts in one reactor, or by using a single catalyst and two or more reactors in series or parallel.
  • the blends of the present invention show performance advantages including, but not limited to, increased heat resistance, tensile strength, tear strength and heat seal capability.
  • the blends further show improved processability such as lower cycle times and improved set up/demolding during injection molding.
  • the blends can be utilized to produce a wide range of fabricated articles such as calendered sheet, blown or cast films, injection-molded articles (for example, toys), rotomolded or thermoformed parts.
  • the blends can be used in wire and cable applications and to produce extrusion profiles such as gaskets.
  • the blends can be used in the manufacture of fibers, foams and latexes, and be utilized in adhesive and sealant formulations.
  • Blends fabricated under high shear melt processing conditions, (for example, where the shear rate is greater than 30 sec "1 ) to produce for example film, foamed or injection molded parts may have significantly different properties resulting from flow induced morphology compared to low shear processing such as compression molding.
  • fabricated articles and films prepared from an interpolymer blend may have improved optical properties such as low haze or transparency.
  • polymer compositions used in the present invention are various organic and inorganic fillers, the identity of which depends upon the type of application for which the composition is to be utilized.
  • fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B O 3 , nickel powder or chalk.
  • organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica
  • organic or inorganic, fiber or mineral, fillers include carbonates such as barium, calcium or magnesium carbonate; fluorides such as calcium or sodium aluminum fluoride; hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystalsAlso included are the various classes of fillers that act as anti-microbial agents. Mixtures of more than one such filler may be used as well.
  • Additives such as antioxidants (for example, hindered phenols such as, for example, IrganoxTM 1010), phosphites (for example, IrgafosTM 168) both trademarks of, and commercially available from, Ciba Geigy Corporation), U. V. stabilizers, cling additives (for example, polyisobutylene), antiblock additives, colorants, pigments, fillers, tackifiers are optionally also included in the substantially random interpolymers, either in the component interpolymers and/or the overall blend compositions of the present invention, to the extent that they do not interfere with the enhanced properties discovered by Applicants.
  • antioxidants for example, hindered phenols such as, for example, IrganoxTM 1010)
  • phosphites for example, IrgafosTM 168
  • additives for example, polyisobutylene
  • antiblock additives for example, polyisobutylene
  • colorants for example, pigments, fillers,
  • the additives are advantageously employed in functionally equivalent 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 storage and ultimate use of the polymers.
  • Such amount of 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 polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or 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.
  • Such additives are advantageously 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.
  • Processing aids which are also referred to herein as plasticizers, can also be included in the substantially random interpolymerblend components and/or the overall blend compositions of the present invention.
  • phthalates such as dioctyl phthalate and diisobutyl phthalate
  • natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feedstocks.
  • Exemplary classes of oils useful as processing aids include white mineral oil (such as KaydolTM oil (available from and a registered trademark of Witco), and ShellflexTM 371 naphthenic oil (available from and a registered trademark of Shell Oil Company).
  • Another suitable oil is TufloTM oil (available from and a registered trademark of Lyondell).
  • the interpolymers were prepared in a continuously operating loop reactor .
  • An Ingersoll-Dresser twin screw pump provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa) .
  • Raw materials and catalyst/cocatalyst flows were fed into the reactor through injectors and Kenics static mixers in the loop reactor piping. From the discharge of the loop pump, the process flow goes through two shell and tube heat exchangers before returning to the suction of the loop pump.. Upon exiting the last exchanger, loop flow returned through the injectors and static mixers to the suction of the pump. A second monomer/feed injector and mixer was used if available. Heat transfer oil or tempered water was circulated through the exchangers' jacket to control the loop temperature. The exit stream of the loop reactor was taken off between the two exchangers. The flow and solution density of the exit stream was measured by a Micro-MotionTM mass flow meter.
  • Solvent was injected to the reactor primarily as part of the feed flow to keep the ethylene in solution. A split stream from the pressurization pumps prior to ethylene injection was taken to provide a flush flow for the loop reactor pump seals. Additional solvent was added as a diluent for the catalyst Feed solvent was mixed with uninhibited styrene monomer on the suction side of the pressurization pump. The pressurization pump supplied solvent and styrene to the reactor at approximately 650 psig (4,583 kPa). Fresh styrene flow was measured by a Micro- MotionTM mass flow meter, and total solvent/styrene flow was measured by a separate Micro-MotionTM mass flow meter.
  • Ethylene was supplied to the reactor at approximately 690 psig (4,865 kPa).
  • the ethylene stream was measured by a Micro- MotionTM mass flow meter.
  • a flow meter /controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture was at ambient temperature when it was combined with the solvent/styrene stream.
  • the temperature of the entire feed stream as it entered the reactor loop was lowered to approximately 2°C by a glycol cooled exchanger.
  • Preparation of the three catalyst components took place in three separate tanks. Fresh solvent and concentrated catalyst/cocatalyst/secondary co-catlayst premix were added and mixed into their respective run tanks and fed into the reactor via a variable speed PulsafeederTM 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 upstream of the catalyst injection point or through a feed injector/mixer between the two exchangers, if available.
  • This flashed polymer entered the devolatilization section of the process.
  • the volatiles flashing from the devolatilization were condensed with a glycol jacketed exchanger, passed through vacuum pump, and were discharged to vapor/liquid separation vessel.
  • solvent/styrene were removed from the bottom of this vessel as recycle solvent while unreacted ethylene exhausted from the top.
  • the ethylene stream was measured with a Micro-MotionTM mass flow meter.
  • 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 solvent was pumped with a gear pump to a final devolatilizer.
  • the pressure in the second devolatilizer was operated at approximately 10 mmHg (1.4 kPa) absolute pressure to flash the remaining solvent.
  • the dry polymer ( ⁇ 1000 ppm total volatiles) was pumped with a gear pump to an underwater pelletizer with spin- dried, and collected.
  • the preparation conditions for each sample were summarized in Table 1. Test Methods.
  • TMA Thermal Mechanical Analysis
  • DSC-910 was used to measure the thermal transition temperatures and heat of transition for the samples run under nitrogen. In order to eliminate previous thermal history, samples were first heated to about 200 °C. Heating and cooling curves were recorded at 10 °C/mm. Melting (from second heat) and crystallization temperatures were recorded from the peak temperatures of the endotherm and exotherm, respectively. Dynamic Mechanical Spectroscopy (DMS)
  • Dynamic mechanical properties of compression molded samples were monitored using a Rheometrics 800E mechanical spectrometer. Samples were run in solid state torsional rectangular geometry and purged under nitrogen to prevent thermal degradation. Generally, the sample was cooled to -100 °C and a strain of 0.05 % was applied. Oscillation frequency was fixed at 10 rad/sec and the temperature was ramped in 5°C increments. Mechanical Testing
  • Shore A hardness was measured at room temperature based on ASTM-D240. Intrinsic Tear was determined using Elmendorf Type A method based on ASTM- D1922. Flex modulus was evaluated in the Polyolefms Testing Lab according to ASTM-D790. ASTM-D1708 samples were tested at a strain rate of 5 rr ⁇ r 1 . Average of four tensile measurements is reported in this study. Melt Rheolo y
  • Dynamic data were taken on a Rheometrics RMS-800 with a nitrogen purge. Frequency/temperature sweeps were performed at 190, 170, and 150 °C with 25 mm parallel plates and a strain within the linear viscoelastic regime. Additionally, the melt strength was determined using the Instron Capillary Rheometer. The samples were extruded at 190°C with piston speed of 1 in/min. The data were collected on a Goettfert Rheotens.
  • the blends were produced by dry blending the component interpolymer pellets in defined weight ratios and subsequent melt compounding for 11 minutes in a Haake mixer operating at 180°C and 30 r.p.m. Test parts were produced from the melt compounded blends by compression molding at 190°C for 3 minutes at 20,000 psi pressure and subsequent quenching to 25°C.
  • an ethylene /styrene interpolymer having 15.9 wt percent copolymer styrene, 0.1 wt percent atactic polystyrene, and a melt flow rate (I 2 ) of 5.27 and identified as Component A in Table 2 was selected as one of the blend components.
  • a 40/60 wt ratio blend of A and Component C having 40 weight percent copolymer styrene and a melt flow rate I 2 of 1.0 was prepared as described above. This blend has an overall copolymer styrene content of 30 wt. percent.
  • Blends have been designed and produced having 25, 30, 35 and 40 wt percent overall total copolymer styrene.
  • ES25 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 25 weight percent and an ethylene content of 75 weight percent.
  • ES30 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 30 weight percent and an ethylene content of 70 weight percent.
  • ES35 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g 10 min, a styrene content of 35 weight percent and an ethylene content of 65 weight percent.
  • ES40 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 40 weight percent and an ethylene content of 60 weight percent.
  • ES9 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 9 weight percent and an ethylene content of 91 weight percent.
  • ESI 5 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 15 weight percent and an ethylene content of 85 weight percent.
  • ES22 is an ethylene styrene interpolymer having a melt index (I 2 ) of 1.0 g/10 min, a styrene content of 22 weight percent and an ethylene content of 78 weight percent.
  • I 2 melt index
  • styrene content 22 weight percent
  • ethylene content 78 weight percent.
  • Table 4 Interpolymer Blends .-Mechanical Properties ( Tensile, Modulus, Intrinsic Tear)

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Abstract

L'invention a trait à des mélanges non miscibles de deux ou davantage d'interpolymères d'α-oléfine/monomère aromatique vinylique, ces mélanges comprenant au moins un constituant interpolymère qui renferme de 2 à 7 pour cent molaire de monomère aromatique vinylique ; et à des applications de ces mélanges. Les constituants des mélanges sont sélectionnés en vue d'obtenir une aptitude supérieure au traitement et/ou des performances supérieures, p. ex. température d'utilisation supérieure, des compositions de mélange et de leurs applications finales.
EP02721027A 2001-03-09 2002-02-19 Melanges d'interpolymeres sensiblement statistiques a performances thermiques accrues Withdrawn EP1381647A1 (fr)

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US274790P 2002-10-21

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US6803422B2 (en) 1999-09-13 2004-10-12 Denki Kagaku Kogyo Kabushiki Kaisha Cross-copolymerized olefin/aromatic vinyl compound/diene copolymer and process for its production
JP3979995B2 (ja) 2001-05-15 2007-09-19 電気化学工業株式会社 オレフィン−芳香族ビニル化合物共重合体の製造方法
WO2024090868A1 (fr) * 2022-10-27 2024-05-02 주식회사 엘지화학 Résine de polyéthylène ayant une excellente résistance à la chaleur
WO2024090867A1 (fr) * 2022-10-27 2024-05-02 주식회사 엘지화학 Résine de polyéthylène ayant une excellente résistance thermique

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TW408155B (en) * 1989-08-31 2000-10-11 Dow Chemical Co Blends of <alpha>-olefin/vinylidene aromatic monomer or hindered aliphatic vinylidene monomer interpolymers with polymers of vinylidene aromatic monomers
ZA977908B (en) * 1996-09-04 1999-03-03 Dow Chemical Co Blends of alpha-olefin/vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
ID20058A (id) * 1996-10-23 1998-09-17 Mitsui Chemicals Inc Komposisi kopolimer berbasis etilena dan produk hasil bentukannya

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JP2004528428A (ja) 2004-09-16

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