WO2010080283A1 - Polyethylene polymerization processes - Google Patents

Polyethylene polymerization processes Download PDF

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Publication number
WO2010080283A1
WO2010080283A1 PCT/US2009/067019 US2009067019W WO2010080283A1 WO 2010080283 A1 WO2010080283 A1 WO 2010080283A1 US 2009067019 W US2009067019 W US 2009067019W WO 2010080283 A1 WO2010080283 A1 WO 2010080283A1
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Prior art keywords
article
prepared
pohmer
polymer
ihe
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PCT/US2009/067019
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French (fr)
Inventor
John Ashbaugh
Brian Cole
David Rauscher
Gerhard Guenther
Michael Mcleod
Ruby Curtis
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Fina Technology, Inc.
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Priority to CN2009801519130A priority Critical patent/CN102257013A/en
Priority to EA201170797A priority patent/EA201170797A1/en
Priority to EP09837823A priority patent/EP2358764A4/en
Priority to JP2011542233A priority patent/JP2012512941A/en
Publication of WO2010080283A1 publication Critical patent/WO2010080283A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

  • Fi F.I. ⁇ ) j ⁇ OOl ) Fmhnlimenss of ihc present imention general! relate to anieics formed with poh-dlv- lene.
  • embodiments oi the present imentior* ⁇ encralh relate so arncles IbroicJ with nucleated Nroodal poh elh> krse.
  • n refer to subject matte* jecited in one or more, bul not neee?sarii> all, of the claims.
  • Kico of the im'euiioiis v ⁇ ill 5LiH be described in s ⁇ retner detail lvlc>v ⁇ , inciuding specific embodiments, x er ⁇ oas and example?, but the ⁇ me ⁇ »i ⁇ i ⁇ s aie itot Hnuied to these embodiments, s crsions or example?, included ⁇ o enabk- ⁇ person bas ing ⁇ >rdi ⁇ ary skill in ihc an to snake and ose the n>x enilon- v-hen the infoimatton in thi? patent is combined xvith asailable information and technolog y .
  • CataMj wsteui? useSul for poh meriting olefin monomers include an> MiitaNc catalyst s ⁇ st ⁇ n, Fur example, the catalyst ssstem ma ⁇ include ehrom ⁇ -m based c.uul ⁇ st system,- si us.- Ie site transition metal eatah si sy stems including metailuecne eaulyst sterns, /ieeJer-Naita catalyst S ⁇ sicms or combinations thereof, for example.
  • the eauih srs may be ⁇ ethatcd tvs subsequent puh $ ⁇ o ⁇ /,n$on and ma ⁇ or may noi be associated with a support materiaK (or example. in-ended to linnt me Ncope of the un ention to such eatah sts.
  • catalysts mas be ehar ⁇ eteri/c ⁇ i generally a ⁇ eoordiu ⁇ jtion eo ⁇ po ⁇ ntJ ⁇ i-Korpntatm ⁇ vs ⁇ e or more es e!opentadien> l (Cp) groups ( 5 AhLh nuo be MibcJUtuied or uoAiV ⁇ imevi e.icb s hsiiuuiiju being the same or different) coordinated i ⁇ b a fneas ⁇ iuu metal ;'v bonding.
  • I he suhMJtucnt ⁇ ?oupt> on Cp may be linear, branched or es ch-s. h> d ⁇ oearbyi rudieak ⁇ ⁇ or example
  • Im emion examples include meiaHoeene catalyst ⁇ ⁇ enus meiudmg ia ⁇ euy i h ⁇ ,mds.
  • the metaSloceue caudx st systems may snciudc ictr ⁇ lt>dro indcnyl H ⁇ a ⁇ Js ih ⁇ y nn-riiii ⁇ wn Fro4.-esse?>
  • cat ⁇ h st s> stems are used to fonu poKolelm compositions.
  • O ⁇ ee J!i ⁇ eatuix st system is prepared, as described abo ⁇ e and > ⁇ a,s kno ⁇ n to one sU lied ht she art, a ⁇ - .met> of processes ma> be carried out usmy that eosnpusition. fbe equipment process conditions, ronetanis.
  • addUives and other materials nsed iu polymerization processes vulS in u gh en process, depending on (he desired composition :m ⁇ properties ⁇ > ⁇ the poK tnof Hehw formed, Mich processes may include solution phase, gas phase slum paa-v, bulk phase high pressure processes or combinations thereof, for example u ⁇ . . I ⁇ Patent No. 5,5 ⁇ 5/. " S: WS Patent No. 6.421) ⁇ 8 ⁇ L S, Patent No. 6.3S0.52S: r S Paten? ⁇ * » ⁇ ..>5 ⁇ 072 r.S P.iU. « ⁇ « NO o ⁇ »> ⁇ ⁇ iHK4 ⁇ o; r.S.
  • the olefin ⁇ nonoiners include tene, f jop> ienc. buienc, peniene, meih> 1peiUer!e, hexeae.
  • polss ⁇ er sna> include homopvsh me ⁇ , copolymers or lerj ⁇ nMuer ⁇ . for example.
  • phase processes yt-ssei ⁇ lh include forming u suspension of v>l ⁇ >1 p ⁇ nii ui ⁇ k* po)> ⁇ net
  • the reactors can include am reactors or eojnhhu ⁇ ion of reactors, as described ahote.
  • the same uucth -J is utiii/t'd in both a-act ⁇ >rs rbe high niok-ruiar v%ei ⁇ h ⁇ fraction a ⁇ v.1
  • the low molecular weight iraction can be prepared in au> order in ihe ⁇ s g
  • the vvcight fraction may be fo ⁇ ucd in the f ⁇ s v t reaeto? and the high moiecuhr wcigin fraction in the second reactor, or ⁇ ise versa for evampk-.
  • the polynit-r ma> be ⁇ as,seti ⁇ o a poHmer fee ⁇ »ser> ⁇ V Mem for Courtsher such addition oS addltn es and or extrusi,-n.
  • embodiments of thr insention include blending the poh mer wstb a modiller ⁇ u , ⁇ 'snudifkation”) n to one skilled isi ihe art.
  • modifier 1 refers ⁇ O an additis c thai effeeiix cl ⁇ acceleraie ⁇ inci uncasured b> cry st'ilh/auon ⁇ ⁇ a ⁇ ik ⁇ s and combinations thereof,
  • nus include nucleator known Io out: skdied in the ail for modih ing olefin ba ⁇ ed pohnier*.
  • non-limiti ⁇ u examples of nnelcUors may include b>dratcs, organic derh aiives* of dibenzylidene sorbitol, sorbitol acetuK organopbo ⁇ pbatc ⁇ aUs and fombitvuiuns ihereol. In one emhudijneni.
  • the uiicleators are selected froir Anifme Na- I i and Na- ⁇ L eoumiercialh av ailable from ⁇ mllne Chemical and I K perform 11PN ⁇ 8 and MillaU ⁇ '- ⁇ 8, commerciall) av ailable from Milliken (.lic ⁇ cal. h ⁇ >n ⁇ specific embodiment, "die modisicr me links ! l> ⁇ c ⁇ fortn HFN-20K, commerciall) a ⁇ ailable from Miihken Cactnical.
  • i ' hc modifser is blended with the polymer in a concentration sufficient :o aceeicrate the phase change os ' the polymer.
  • more tlie polymers include eth>L-uc based poh mers.
  • V used hereai, the Jcut.- poKmef or ") «>K ethylene " ⁇ md reiers to a polymer having at iea ⁇ i about ⁇ O ot "s». ot at lea'?; about Iv ss t.' "1 -. or at k-asi about 75 wt ⁇ V or at least about 80 vst . ⁇ o, ⁇ ? ⁇ t least about 85 or ai least about iJ 0 va.° « pol> ethylene reLitise to the total weight of pohmer for example.
  • ba ⁇ ed polymers ma> lia ⁇ e a dcnsitv an- measured by ' ⁇ S1M D- ' ⁇ -fZ) of is on? about O.fe g ⁇ .e t ⁇ > about O.$ ⁇ > g,cc. or from about 0.88 gee to about i>. ⁇ ⁇ ⁇ e or i ⁇ >m aiwut 0. ⁇ (> c ee to about 0 ⁇ ⁇ ? g ee or i rom about 0> ⁇ .? ⁇ g/ce to about O ⁇ 1 ? g ee, Uv example.
  • the terra "IO' ⁇ densh ⁇ poh ethy lene” refers to etln iene joer « kn uie, a vie-iMl) ⁇ f from aivnt Ie ⁇ - than about 0 Q 2 g ec, io>- example.
  • the pointers include medium dcnsin poUerh> Last-. ⁇ ?
  • she ierm “medium dentin polvctliylcnc” 1 refers to eth y lene KH «1 po! ⁇ uv.-r,s kux isss,' a dcnsUs of froif) ahoui i ! q 2 g ' cc to about 0, ⁇ 4 ⁇ /cc or mini about 0 ⁇ >2 ⁇ g cc to about ( ! .”M g cc,
  • ⁇ TM ⁇ include ⁇ J high snoieeuku- ⁇ % eight iraetion uxi ⁇ a k>Vv i ⁇ oleeular weigjit fraetion.
  • Hie lu ' gli molecular wciglu fraciion cxhibib a molecular ⁇ weigm h creaier than tile molecular may bane a mokvuiai weight of from about 50,000 to about 10,000,000, or irorn uhout ⁇ 0,00 ⁇ to about 5 JHHKOOu -u ixx ' iii about o5,000 ⁇ > ⁇ jb ⁇ >ut I .OOCf.OOO. for example.
  • ⁇ ise b)U"Ri-,hi polymers raa> have a ratio ⁇ u high inoleculur w eight ⁇ r,action to usoleeul ⁇ r v-vighi fV ⁇ ction -ai ' frons aboui 80:20 to ahoiu 20'8O, or from about 70- U ) to about
  • Mime include bknvn, onemed o* 1 east films loaned o> extrusion or co-extrusion or by lamination useml as ⁇ hnnk j$hn.
  • l-irvrs inv.ude sut-isims monofilament, melt spinning, solution spinning and melt bk>x ⁇ -n ilher aporanou ⁇ ⁇ >r is ⁇ c m ⁇ un en or non-s> ⁇ «.n form io tuake sacks, k ⁇ .
  • One or niufv of site imenikm include uuh/ing the po ⁇ ymcr ⁇ to lorn- pipe articles, as pipe, i ⁇ hmg. nmkkxl fitiing.s, pipe coatings and eorjbmadon.s fbercoL io? e ⁇ mpie i Iv pipe ardcle.s nu ⁇ he utilized m industrial chcmieul processes. nihmh.> ⁇ pcrauon ⁇ -, gas disfdhuiion. poi.-tbk- waier distribution ga.s and v>il production, tibe?
  • Bubble instahilu> e ⁇ jn inchkle ⁇ n ⁇ ui ⁇ ⁇ Mienon ⁇ ena, such as draw resonance ⁇ l)R), general! ebaraeieri/ed .i penodic of ihe bubble diameter, hehcoula! instabiiitx eeneralh charge ⁇ erl/ed bv a heheoniii ⁇ io ⁇ on ⁇ % bubble around its axial direc ⁇ orh frost line heljihi iFl lh y i>eneraU> , -- ⁇ hkr is analogous to H 1! with sarxmg stalk height.
  • the invention are capabk of formine blow n films with impnocd bubble sUibilUx.
  • the blown film processes exhibit at least about 5%, - 5 r a? least abtast IOV or ⁇ ⁇ s v V os at least ahooi in bubble st ⁇ bilil) compared to identical processes, absent the tooJille; for exanvole
  • embodiments ⁇ - i ' the imcution are capable u! fornnuj: bkwMt fihns cNliil 'SUUg ti(m gauge distribution.
  • the impRwement in gauge distributor produces bcttcf him appeasancc and funiN can be do ⁇ vny.eiiyd in u>c ⁇ 0.iMTi ⁇ 10'»,.
  • ⁇ ⁇ ".
  • nuvxfxv.od results ⁇ s U ⁇ u-5oioa.se Hx U ⁇ . * eas; ⁇ bou ⁇ - ⁇ U ⁇ v o; a?
  • Sample 21 nsclt hkndiii:; pnuiueed using an Alpine ixhn line w ⁇ b a fiat tempei at ⁇ » • •,. nr- ⁇ k v of 40 ⁇ ' V 1 lit- tli ⁇ i subHUy quaiuified by producing biowrj lllm ai three neck heights -; ⁇ ere reixmliny at each iieek heights whh the iris ssuusc ⁇ eai t>f 4 i.s ⁇ ic highest Ni'J ⁇ hi ⁇ ⁇ here there arc no vertical stabiin> s ⁇ sucs (breathing ⁇ >v hnhble (lancing ⁇ unking of 3 indicates sligin breathing and dancing $J C " ⁇ r ' UlU ⁇ " deviation hom ccracf !
  • ⁇ ranking of ?. indicates the bubble is breathing or dancing greatci than 1 " frosn center A ranking of 1 is use ! ⁇ csr ranking ⁇ here the bubble ⁇ c ⁇ hibiung signifieani breathing and or helical votanon all the vun to the open iris.
  • a fmai stability number is calcuh ⁇ cd h> inulbplxinv; the d.ua from mv ibrce closed ranking? and the three open ranking? and normaUrmg using ihe Kn; scale, 1 he s ⁇ ale for the tcs ⁇ ng is tjberei ' ore 0 to 3.61 , with 5.M being the most stabk ranking I'nexpeetedU .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

Polymer articles and processes of forming the same are described herein. The processes generally include providing a bimodal ethylene based polymer, blending the bimodal ethylene based polymer with a nucleator to form modified polyethylene and forming the modified polyethylene into a polymer article, wherein the polymer article is selected from pipe articles and blown films.

Description

POLYETl IY LKNK POIΛ MERlZATiON PR< K 'KSSKS
Fi F.I. ϊ) jθOOl ) Fmhnlimenss of ihc present imention general!) relate to anieics formed with poh-dlv- lene. In particular, embodiments oi the present imentior* ^encralh relate so arncles IbroicJ with nucleated Nroodal poh elh> krse.
KΛCK<;KOI M> jβlM£j Λs reflected in the patent literature, propy lene pohrners h:o» t boon 5 me Seated ior a
Figure imgf000003_0002
,-auI
Figure imgf000003_0001
Susie Mfcichmg procvSvSCs. for example, ■vsilli vicmonsiratcd impnn'emenb in
Figure imgf000003_0003
a?κ1 the
Figure imgf000003_0004
i.;uitτalh noi expck'iu-cd
Figure imgf000003_0005
\ high sniύai cr>?tal wπnM.h πae. Prior alterapis 10 nucle<iie pohveth> lciie have therefore been focused OU the ntOtAUioπ >)i
Figure imgf000003_0006
(as measured by increasing
Figure imgf000003_0008
has been achieved with linear
Figure imgf000003_0007
den,sk> fκ>heih> lene, the aNht> 10 nudeαtc other pols ethylenes.
Figure imgf000003_0009
pohetfc) lene base oot iveπ denionsirated.
[HiHB] hi addition, pipe arheie-s. ihemiolomu-d ariicles. cormgnied sheei <snd other proilie extuision axiielecs formed v>ήh ethylene based puKiners ma> e><hibii a Ie^s ihan desired say
Figure imgf000003_0010
hi^h muleenlar >veighi, hi
Figure imgf000003_0011
exhibit bubble mstahilits αuπnμ
Figure imgf000003_0013
rcsuUisui In blown fύtns
Figure imgf000003_0012
ing JefeeLs aud or processiny difileuhkss I OiHMj fherek^, ,ι need exists to develop eth) ienc based poi> tners and pro^esse^ exhibiting
Figure imgf000003_0014
|$HM)5] i-inbodimcnts of the present invention inehule pmeesses of fornting jvl>jncr urtieks. •Isc genctaU) iuelude providing <ι bimodal ethylene hαoe-J poiune*. hkuUiαg thv. Hniodαl etbx iene ha^ed pohiner with a αndeator to ibrm modified, pυiyetln tone and fonnnsy the nuiddied poh eibxlene ϊnuι u pohiuer article, wherein the poiuner aruele is Λeleeteα i?c>m ripe anieie? and blown nuns. fOOΘδ) lYnbodirnoms of' the imentkm further Include pipe articles and bk-wn nim^ formed t>\ iho processes eiesoπbed herein.
BkI FO)K-SCkI f 1IC>y OP DRAWINGS
|IH)07J Figure 1 illustrate? the sag resistance obtained ai \
Figure imgf000004_0001
arvm£ take up -φeeds of pipe samples
|(KI08| He,uιv ~ ϊϋnMratvs tbc gauge
Figure imgf000004_0002
ύϊm sampler
(CKMrøf Figure o illustrates the gauge pro tiles \arious film samples.
10010}
Figure imgf000004_0003
of \ arioυs ilJm samples.
|CMIΪ ϊ |
Figure imgf000004_0004
rates tbc ha/e of sarious iϋm samples.
i>KTΛ« FP I)ESCRiO K KN hitroductiou a«d Dcfjiiitioϊis*-
[00Ϊ2J Λ -JctaiicJ dest.'πρtlon v\ ill now be provided. I-aeh ol'tht- appended obinii> dcibies '\ st'pαraic un omion t hiols fox irdπn^enient purptwes it> reeuuni/ed as aieludiϊu.- equivalents to the various c!eτnt.-ut# or limitations specified us the claims. Depending <κ\ tfie eoutext. ail α-ferences below κ> tl\e "an en lion " πias iir some eases refer to certain specific embodiments on H . hi otber cases n refer to subject matte* jecited in one or more, bul not neee?sarii> all, of the claims. Kico of the im'euiioiis v\ ill 5LiH be described in sϊretner detail lvlc>v\ , inciuding specific embodiments, x er^oas and example?, but the ϊmeτ»iυiιs aie itot Hnuied to these embodiments, s crsions or example?,
Figure imgf000004_0006
included ϊo enabk- α person bas ing ^>rdiπary skill in ihc an to snake and ose the n>x enilon- v-hen the infoimatton in thi? patent is combined xvith asailable information and technology . |0013j
Figure imgf000004_0008
herein are
Figure imgf000004_0007
belo« . 1 o the ex'teni «ι tern? used in. a claiiVx i * not defnivrd ϊvkm , it should be given the broadest definition peri-v-ns in the per?iu*.-ut art h>n c that term is reOected in primed publications and issued patents ;a me time Os ilhng Further, unless othenvise speeilied, all compounds described herein mrsv be suhstύnsed -M and the lismig of compounds includes
Figure imgf000004_0009
thereof
10014} Kmher N< ;irions ranges and or numerical limitations m<n ht-
Figure imgf000004_0011
stated
Figure imgf000004_0010
U be κvc>unl-ed tha? unless stated otherwise, it is intended Hmt endpυuns uie to be JUL'rchangeable. -,-ujthe- , an> ranges ineiude iterative ranges of like magnitude Ulimg ^x ithm the e.xpresbh suited iαi!j.vs ^r Untitations. Catalyst Sv^ierøs
|1HH5| CataMj wsteui? useSul for poh meriting olefin monomers include an> MiitaNc catalyst s} støn, Fur example, the catalyst ssstem ma} include ehromα-m based c.uul} st system,- si us.- Ie site transition metal eatah si sy stems including metailuecne eaulyst sterns, /ieeJer-Naita catalyst S}sicms or combinations thereof, for example. The eauih srs may be αethatcd tvs subsequent puh $αoπ/,n$on and ma\ or may noi be associated with a support materiaK (or example.
Figure imgf000005_0001
in-ended to linnt me Ncope of the un ention to such eatah sts.
|001(»| Fur /iegler-NaUu oataiw systems arc generally fonut'vi fπnn the
Figure imgf000005_0002
vompi mettle sικh a^ u ealal^ si support, a eoeutaij^t and 'or one ^r moiv eiectτon donors, for example.
|iHM 7| One or moiv embodiments of the nn entum inekxie /iegkr-Naua oafaiw NN SICO^ geneial!} formed ^> eonUeting an alky l rnagnesiuni compound with <ai <ϋeoboi to soπu a magnoMum dιaikoxi<le eoτπp>jmκi :mά then euntaeting the ϊnagnesiuni dialkoxide compound wit|\
*acees?iveiy rfiror^er ehiorinjting agents. (.Vf, V. S. Fat. No. 0.734, t ?4 t\nύ V. S. Pat. No. vsj
Figure imgf000005_0003
are incorporated herein b> res'eivnce.)
{OOIS] Meuilioecns. catalysts mas be ehar<ιeteri/c<i generally a^ eoordiu<jtion eoπ^po\ntJ^ i-Korpntatm^ vs\e or more es e!opentadien> l (Cp) groups (5AhLh nuo be MibcJUtuied or uoAiVάimevi e.icb s hsiiuuiiju being the same or different) coordinated
Figure imgf000005_0004
iιb a fneasϋiuu metal ;'v bonding. I he suhMJtucnt μ?oupt> on Cp may be linear, branched or es ch-s. h> dιoearbyi rudieakλ ϊor example The eselic hydroeαrbyl radicals
Figure imgf000005_0005
αne, jaruertnvs ineludiuj.> indenvL a/ulens l and flaorenyl groups, for example, i bc-se eommuoui- riisg
Figure imgf000005_0006
iu i
Figure imgf000005_0007
1 rruIieaLv tor example.
|00l*>| Oue or moje embodiments of the Im emion include meiaHoeene catalyst ^ ^enus meiudmg iaαeuy i hμ,mds. For example, the metaSloceue caudx st systems may snciudc ictrα lt>dro indcnyl H^aπJs ihύy nn-riiiiϊwn Fro4.-esse?>
(0020 J V^ indicated elsewhere herein, catαh st s> stems are used to fonu poKolelm compositions. Oπee J!iκ eatuix st system is prepared, as described abo^ e and >τ a,s kno^n to one sU lied ht she art, a <- .met> of processes ma> be carried out usmy that eosnpusition. fbe equipment process conditions, ronetanis. addUives and other materials nsed iu polymerization processes vulS in u gh en process, depending on (he desired composition :mΔ properties ι>ϊ the poK tnof Hehw formed, Mich processes may include solution phase, gas phase slum paa-v, bulk phase high pressure processes or combinations thereof, for example u\\. . I Λ Patent No. 5,5^5/."S: WS Patent No. 6.421)^8^ L S, Patent No. 6.3S0.52S: r S Paten? \*» ^..>5^072 r.S P.iU.«ι« NO o
Figure imgf000006_0001
\»> ^ ^iHK4 ^o; r.S. Pαicni Xo '«,274,684; 5 '.S. Patcm No. (>J7 L.C 3; 1 '.S. Fatem No
Figure imgf000006_0002
Patent No. Oj -PJ "\\ v^bsch are incorporated h> reference herein.)
|002l{ In cenain embodiments, the processes described
Figure imgf000006_0003
jiencraUs int ijde polsnieri/ing one OE more olefin monomers (o ionn poh mers. The olefin ϊnonoiners
Figure imgf000006_0004
include
Figure imgf000006_0005
tene, f jop> ienc. buienc, peniene, meih> 1peiUer!e, hexeae. octene and deeene u for
Figure imgf000006_0006
I Ue rrsonomers ΠI:Ϊ> inchide oieilnic unsaturated monomer^ C; to V^ diuicftns, conjugated or ihMiCiMisugateU diene.s, ρ<.«l) cnes,
Figure imgf000006_0007
e>\ lie olefins for example. Non-ϋnnπui? exαiαpies of other ?m>n>>nιere m>s> include norKjrueue, nobornadiesie. i.sohut> leno. 5--Λprerκ\
Figure imgf000006_0008
ss Irene, alkv l substiuued stsrene. ethyϋdeπe uorborncne Jk^ elopcnta-.ϋene .-aϋ e> ek>pen(ene, for evample. i"b.c ioniKvi polss^er sna> include homopvsh me^, copolymers or lerj^nMuer^. for example.
[0022} i xantpleo m .solution processes are described in V. S. Patent N-1 ^, N~ i .(*ou, I ,s. Patent No. 5.0θ1 ,:«κ. I .S. Patent No. 5.?3o.^X and I .S. Patent No 5 5^l* 555. ^hich atx incorporated by reference herein.
J0Θ23J (,>ne cxampk' vf a
Figure imgf000006_0009
~item- therein a ex eling eas .stream
Figure imgf000006_0010
as a recycle hireusn o> ftuKii/iue
Figure imgf000006_0011
from Ute cv elinj; >UN sltvant in aϋoilier part of the e>e!e by a cooling sχ ?teπ^ externa* to the ieaetor ) he e\ ding
Figure imgf000006_0012
mas be eoDtinuotbh e> ekd through a iluiui/ed ivd tn (he presence oJ a
Figure imgf000006_0013
ustder reaetKe conditions. The c} cHug p.αs streant ϋ> e,enofa)lx Λx iiluirrm n fri«iu fue tlutds/ed hed and back into ihe reaetos. Simuhant-onsiv . poK nκr pπxiuet ωa> he ^ uluirawn from the reactor and fresh inonomet mrπ be rukieil to jepiaee the poi> meri/ed nsojtomer. The reaeroϊ pressure in a gas phase process tnαx VΛYS from <iK>ut 100 psϊg k> about ^Hs psu;, >.>v from aboui JOO p.sig tu about 400 pstg e>. from aboiα 2"k* pMg ".o ahoos
Figure imgf000007_0001
t\ous about U^ C to about IJ^V, or ftvm about <χs°C to about U 5°( \ or fiom about ?0 I v> about 1 • (> «. Vr from about ?ιr t. t> aK>at °5 si \
Figure imgf000007_0002
fur example, t&v. for I ,S, Patent \o. ^ Λ-Ϊ O4*'\ i ^ >\uort Nt. 4,588/M\ i N Putont Mo. 5.028,o?0; U 5» Patom \τo \^ ".0 ϊκ r s )»ateιrt No. 5.551"4^, S ,S, I'^icnt No. 5,4θ5,!^:; 1 Λ, Patent Ko 5.4>.?04: WS Patent No. :vb<vs? t i .S. Pau-nt No 5.^O^>; I .> Fateni No. 5,(>) 6.oϋ l ; ! '.S. Paiem No. 5^ 7J<4:, r.S Vatr.it No,
Figure imgf000007_0003
which arc iαcorpoπreJ h> reibi cncc hereni "*
|0ft24] phase processes yt-sseiαlh include forming u suspension of v>lι>1 pαnii uiαk* po)>τnet In J bqsϋd
Figure imgf000007_0004
aion^ wUU k.-auis> ?u t«e adUvd l he suspension
Figure imgf000007_0005
»»-
Figure imgf000007_0006
*V»^u ;be pols tner ,mύ joevcL-cL optsoralh alter α Jϊsiiilaliou, to the svaeh^ i he liv|ueiκd usiueni ernpKΛ i'J in ihe ρol> weπΛVϋon medium mas incknie a ( N so T - alkutK (s' xj . l;es.atic «^ ssv'bntαnel tor
Figure imgf000007_0008
employed is generαH) ikp.ud under iϋc
Figure imgf000007_0007
of ρoi> lαers/aih-n and relativ e!) inert. A bulk phase process is similar to ύut o! ri siuiπ proems w dh the exeepiion
Figure imgf000007_0009
^v . u>outπuer> ;n a buϊk piuse pT'oces.s * km e<. O^ i pU'Ccss mα> be a bull process, a slum process or a bulk <>!urn process. t\»r evatipie
[0025J In a spev. -t\c tmboJiment a slurπ process Qt a ouik p^oces^ $ra> Iv eαπied out eoniiiuϊonsis
Figure imgf000007_0010
ponder, nn> '">e injected reguuu'h to the reactor loop, winch can itself be ύlK-ά ^Uh ersenlαfu-.e, siuu> of growmg poK snet parfieic? us a diiυenL for example
Figure imgf000007_0011
oia> t"-: added to the fro^ev*. such a^ for mokvulat weight cor.troi of the rouUunt pohtnes i hf leop react* SΪ ou> tv nvunsαiπed at α pressure of from about 2"' bar to aKπu ςυ Kn or fron. ahout ,;-' l\u io about 15 bar and a temperature <n from about 3S^C to about \ .? 1 °i\ KM c\a.nρ!e Re. u U> -n lie.it nu) K- s thi«.>iϊgh the loop vwVli Ma αu> suitable method, such as ua a ooutne- :<u
Figure imgf000007_0012
be .u exchanger for example
(0026] Aberoatn cU , eihci ι> ρes of mentation proee.sst-? ma> Iv used, such as
Figure imgf000007_0013
ϊvaeξor.s m -CtICs, pas a! Li or combinations thereof, for sample, m >>ne or more eosbodsinems, tb«-
Figure imgf000007_0014
proee.ss includes the production of multi-modal ooK olefins Fos exanipk-. one or more -embodiments max inelnde passing a slurry through at k&st isvo reaction /ones u i> . u rmϋtϊ-nvxtal process}, A-; used heroin, the term "ixsuiu-niodal process ' iefers io a poh mers/atson process including a plurality of reaction zones
Figure imgf000008_0001
t^ o ieaetson ?one.->l thai pjoduee a poh ioe? exhibiting a multi-modal molecular weight distribution, tor example* a single composition Including at least ^ne identifiable high molecular weigh, fraction and at least one sdemifiable low moWcuiar weiszh} fraction is considered a "bύnodal" puh olefin. |0027| 1 he mulu-ntovSai poholefros ma> be formed \ ι& any suitable method, ?uch a ^ \ u u pluralii> of reactor in series. The reactors can include am reactors or eojnhhuαion of reactors, as described ahote. In out or more embodiments, the same uucth -J is utiii/t'd in both a-act^>rs rbe high niok-ruiar v%ei^h} fraction aτv.1 the low molecular weight iraction can be prepared in au> order in ihe <s g , the
Figure imgf000008_0002
vvcight fraction may be foπucd in the fιsvt reaeto? and the high moiecuhr wcigin fraction in the second reactor, or \ ise versa for evampk-. ||M)2S) Upon remov al from the reactor, the polynit-r ma> be ρas,seti \o a poHmer fee<»ser> ΛV Mem for ihrsher
Figure imgf000008_0003
such
Figure imgf000008_0004
addition oS addltn es and or extrusi,-n. }os example, in }κniic\ιlar, embodiments of thr insention include blending the poh mer wstb a modiller < u , ■'snudifkation")
Figure imgf000008_0005
n to one skilled isi ihe art. Λs used herein, the term "modifier"1 refers ΪO an additis c thai effeeiix cl^ acceleraieό
Figure imgf000008_0006
inci uncasured b> cry st'ilh/auon
Figure imgf000008_0007
\ ϊaπikτs and combinations thereof,
|U02*>! i nc nuekaion? nus include
Figure imgf000008_0008
nucleator known Io out: skdied in the ail for modih ing olefin ba^ed pohnier*. lor example, non-limitiπu examples of nnelcUors may include
Figure imgf000008_0009
b>dratcs, organic derh aiives* of dibenzylidene sorbitol, sorbitol acetuK organopbo^pbatc ^aUs and fombitvuiuns ihereol. In one emhudijneni. the uiicleators are selected froir Anifme Na- I i and Na- ^ L eoumiercialh av ailable from Λmllne Chemical and I K perform 11PN^8 and MillaU ^'-^8, commerciall) av ailable from Milliken (.licπύcal. h\ >nκ specific embodiment, "die modisicr me links ! l> ρcτfortn HFN-20K, commerciall) a\ ailable from Miihken Cactnical. |(IO3O| i'hc modifser is blended with the polymer in a concentration sufficient :o aceeicrate the phase change os' the polymer. In one or more embodiments, the modifies nia> he used in concentrations of irom about O.oi vU.% to about 5
Figure imgf000008_0010
or from about ^,{»1 Wt.'-1 *., to ahoiu ^ ^ t v\>. fr- m<m about
Figure imgf000009_0001
wes^ir of trie polymer, for e\ ample.
(003 Ij I IK* modifies ma> he blended with the pohmer in any marine? kno^t to one skilled in ihf <irt. h» example, one or more embodiments oi the invention iru.iu.de" mels blending the eth> iene kiseJ poϊxmer ^iili ihe modifier,
|IHM2| (i is thai the modifies may be formed into a -"masterhaterT u s> , eomblned ifh
Figure imgf000009_0002
oi masierbateh pohmer, either tlse c>aτne or JlfiertMit uoni the foKmer
Figure imgf000009_0004
\xv',h the poKmer.
Figure imgf000009_0003
cl}, it is- c«.»ute5npiated thai lix
Figure imgf000009_0005
^iih the polymer.
Poh mer Product
{#$$$} the
Figure imgf000009_0006
ii^lαde, but v*rt s>ot hniucd ι<\ linear low ciensit) ρol> eihylcnt , clistomen-;, phi Mongers high densir> pαbvih) leiκ>. lo^ de?isύ> pol>vth>knes. medium density polsethvlene?-. poKpropvlene
;uiJ μoh propylene for example. jθUi4j Vnless
Figure imgf000009_0007
signated herein, all testing methods are ihe enrren. mesbo-js ;u the iiiυe of tiling.
{0035} In one <.*? more
Figure imgf000009_0008
tlie polymers include eth>L-uc based poh mers. V used hereai, the
Figure imgf000009_0009
Jcut.- poKmef or ")«>K ethylene" <md reiers to a polymer having at iea^i about ^O ot "s». ot at lea'?; about Iv ss t.'"1-. or at k-asi about 75 wtΛV or at least about 80 vst
Figure imgf000009_0010
.^o, <■? <ιt least about 85 or ai least about iJ0 va.°« pol> ethylene reLitise to the total weight of pohmer for example. jθ$B6J 1 lie eι)i>lene ba^ed polymers ma> liaΛe a dcnsitv an- measured by '\S1M D-'^-fZ) of is on? about O.fe g ^.e tκ> about O.$ϊ> g,cc. or from about 0.88 gee to about i>.^~ ^ ^e or iτ<>m aiwut 0.^(> c ee to about 0Λ}? g ee or i'rom about 0>}.?Λ g/ce to about OΛ1? g ee, Uv example.
|(KB?f The elsylenc based polymers ma> ha\e a melt index tMΪ > tαs nuMsnred b> \S1 M
O-l.l'S'ϊ of srom aboui tlOl d^πύn to about lOo vig'røiπ., or iron) iih^m 00) dg nun to aKnn 2^
Figure imgf000009_0011
HOin aKs-ut 0Λι? dg'mύi-, to about 15 -Jg miu. or iron) about 005 -Jg irnπ. to abon? 10 dμ. mm, tor example |ι>038] hi vna
Figure imgf000010_0001
iK-ϊvin. the terra "IO'Λ densh} poh ethy lene" refers to etln iene
Figure imgf000010_0002
joer« kn uie, a vie-iMl) υf from aivnt Ie^- than about 0 Q2 g ec, io>- example. j UO-Wj In one or more embodiments, the pointers include medium dcnsin poUerh> Last-. Λ? used herein, she ierm "medium dentin polvctliylcnc"1 refers to ethy lene KH«1 po!} uv.-r,s kux isss,' a dcnsUs of froif) ahoui i! q2 g 'cc to about 0,^4 μ/cc or mini about 0Λ>2^ g cc to about (!."M g cc,
Figure imgf000010_0003
|iHM0) la one or
Figure imgf000010_0004
iene Λs n^cJ herein, iUc lerrn 'Isigh den.sύj puhcihs lcnc" refer? to ethylene based μeh mors h.n sng a dens t> ^C ij osn abom u,*)4 y ce to uhfUt V^" g'oc. for es.arøplc.
{0041 ] in one oi more erøixKknk'nh-, the polymers inehak high nh>L-eulsτ ^ci^ht
}K)h t.1b} iene. AN used herein, the term "high molecular weight poiy^hyiene" ri lcr^ io ethy lene ivuveu pv>i>
Figure imgf000010_0005
\(W41\ In ^sS-,- or niuiv embodiment, the eihykac bused pol> nϊθϊ> ma> exnibii IninoJcJ molecular weight distribution-- Su1 . the> ;ire bunodal polymers). For example, :\ ^ragk* composition
Figure imgf000010_0006
jnolecului" weight peaks using si/e exelusiou chronsuiograpL i SiiO ) io eonv:dofe>? io be a "bhnodal" poh oleiln. For example, the !ooiecul;u weight iVaetion--
■TM} include <J high snoieeuku- \% eight iraetion uxiύ a k>Vv iπoleeular weigjit fraetion.
{#043] Hie lu'gli molecular wciglu fraciion cxhibib a molecular ■weigm
Figure imgf000010_0007
h creaier than tile molecular
Figure imgf000010_0008
may bane a mokvuiai weight of from about 50,000 to about 10,000,000, or irorn uhout ό0,00^ to about 5 JHHKOOu -u ixx'iii about o5,000 κ> <jbι>ut I .OOCf.OOO. for example. In contrail, tiu* K-w mokvuias height iraeuon nut>
Figure imgf000010_0009
or ft ojti about 5^> io abu>a 40,0ou oi from about 000 to about Λ5.0ΓΌ. tl>r example.
{0044] ϊise b)U"Ri-,hi polymers raa> have a ratio <u high inoleculur w eight ιr,action to
Figure imgf000010_0010
usoleeulαr v-vighi fVαction -ai' frons aboui 80:20 to ahoiu 20'8O, or from about 70- U) to about
3θ:'"0 oi from about o0;αθ io aK-ut 4θ:(H), for example.
Protio€i ApplicatJ««i
(0045 J I he poh mers ;«ul bkud.N thereof are useful in
Figure imgf000010_0011
to one .skilled in the art. such
Figure imgf000010_0012
as vu'l! as NuVv moLIins:, iniection molding and rυtan molding). Mime include bknvn, onemed o*1 east films loaned o> extrusion or co-extrusion or by lamination useml as ^hnnk j$hn. ehm; illm, stretch film, seaung πirns, oriented illras, snack packaging, lieav} dun hags, c-{ocor> sacks, baked and ikven lood packaging, medical packaging, industrial Hner«, and membranes, iot example, in tevd-^ntae* and non-food contact application. l-irvrs inv.ude sut-isims, monofilament, melt spinning, solution spinning and melt bk>x<-n ilher aporanou^ κ>r is^c m \un en or non-s>ιΛ «.n form io tuake sacks, k^. rope, m ine, eriψet backing, earpet > αru^, fskα-;?, vtiuper iahru'β, oie-.Ueal
Figure imgf000011_0001
for exanipic. 1- χιruded articles include medical tahiiig,
Figure imgf000011_0002
for evursple
Figure imgf000011_0003
iu the tbrsn uf Katies. Uiuks, large hυilow .n tielcs rigid
Figure imgf000011_0004
(0046} One or niufv
Figure imgf000011_0005
of site imenikm include uuh/ing the poϊymcrό to lorn- pipe articles, as pipe, iπhmg. nmkkxl fitiing.s, pipe coatings and eorjbmadon.s fbercoL io? eλΛmpie i Iv pipe ardcle.s nuι\ he utilized m industrial chcmieul processes. nihmh.> ^pcrauon^-, gas disfdhuiion. poi.-tbk- waier distribution ga.s and v>il production, tibe? opiju condiuu scwcr ^s stems .ind pipe relinήig, lor example. \n one or move embodiment, die pipe ardeks nιa> hr.vc α ihickiiCcss at least about 1 inch, or at k<a?i about 1.25 inches or at least about 1 5 inches, for example. In αruftber embotiimem. iUc polymers arc utilized to form tltennohmntd auieles o? corrugated sb.-eis. for evample
(0047) Nag Ro!c«iauv.e is an important perionnanee characteristic of pipe aπUes
Figure imgf000011_0006
ai?o be inipouαtit ιl>r thcπnofoπned arύclcs and or corrugated sheets.
Figure imgf000011_0007
vUiicies -iecroasc pipe pejfonnance s e g., thuiiicr section^ are weaker), resulting in processiju; and o? hήϋering the llnid How thereihrouglu for example Prior attetnpis to hnpnΛ e sag fjsisuuue in pipe articles
Figure imgf000011_0008
can cease adJiύonal problems,
Figure imgf000011_0009
as processing difliculiics and or docre.ising siou crack growsh resϊ.s* UKC in pspe walls, lor exanψie
[Θ(M8| bncxpcctedb, , entbiKihneuts of the im ention arc eapahlc of t\<nuin^ fife arύvles exhibiting improved κ\ssstance to sag. For example, ihe pipe articles ina> exhibi! an increase in sag resistance oS at least about 5° -λ or at least about 10?c, or at least ^ bout 2(^'\ or .it least about 30{> <> compared to. pipe articles loaned from an identical process abstnt du? modiiicr, for example. \s used bejein, "sag resistance" is quantified by mea^suring the sag o! an extruded M rand ai diffcreni taie up speeds J0049] <,)no i.-r mote embodiments ul ihc imentlon include unli/ing the pointers to form bu>wn fiinu βuch .is sadL? and liners. Bioun ilhus ma> be formed h) iorcmg molten polymer through a circular die. which i? then blown and the molten poh-rner is then inflated tυ losm a bubble 1 he vesukant bubble i.s then flattened and cut into strips, thai when roiled, produces roll:* of tlaS J)Un Si'ttK- blown film processes, ^neh a.s those that ntϊή/c the ^peeifie polymers described herein n\e: hi^h nimeeular weight, high densits poKeihslcneK hkm die ithfϊ wttii ;J stalk {tUc melt e\it^: the blown ύhπ die as an annulus and h h carried up ards pnos m iιu1athMi>, foπidnj; a buhhk- s
Figure imgf000012_0001
cύmiluf to a wine gk^s, for evunpie. In one or uu>u- ernhxiinK'nlβv ilie siuil bαs a height of ;a least ahoui 4 die d^αmeierx or at least about 5 die diameters or αl iea^i about o die
Figure imgf000012_0002
than blown iihn ρtvxx>-\'S absent a sblk
10050 j
Figure imgf000012_0004
hiuwn tlhn
Figure imgf000012_0005
ma> experience bubble
Figure imgf000012_0003
. Bubble instahilu> e<jn inchkle τn<ui\ ϊMienonαena, such as draw resonance ιl)R), general!) ebaraeieri/ed .i penodic of ihe bubble diameter, hehcoula! instabiiitx eeneralh charge ιerl/ed bv a heheoniii πioϋon Ή% bubble around its axial direcπorh frost line heljihi iFl lh
Figure imgf000012_0006
y i>eneraU>
Figure imgf000012_0007
, --\hkr is analogous to H 1!
Figure imgf000012_0008
with sarxmg stalk height.
|tJ05l| Hubble ins* ability v.an lead to a iess consistent formed
Figure imgf000012_0009
JifhcuUie^, for exaniplc hs addition, Ii the bubble iπstabilltx h net re\ersed, Uie bubble may break, ret>ohiuy m ohui
Figure imgf000012_0010
of the processing line.
111052 J Prior auempts to inipnwe bubble
Figure imgf000012_0011
^ueh a,s ealeiam carbonate and sluoroelastouiers, for example. !
Figure imgf000012_0012
desnon-'trotevi eon.sjsteni iusprinenicrst in bubble stability and therefore have Ihisiied suv.ιes-5 depending opoϋ tiie t>ρe of ρoh merntiii/cd.
[0053] i fne\peetedlv , embodiments <■>{ the invention are capabk of formine blow n films with impnocd bubble sUibilUx. In one or more embodiments, the blown film processes exhibit at least about 5%, -5r a? least abtast IOV or <ύ
Figure imgf000012_0013
\svV os at least ahooi
Figure imgf000012_0014
in bubble stπbilil) compared to identical processes, absent the tooJille; for exanvole
[0054] hi addition, embodiments ^ - i' the imcution are capable u! fornnuj: bkwMt fihns cNliil 'SUUg ti(m gauge distribution. The impRwement in gauge distributor, produces bcttcf him appeasancc and
Figure imgf000012_0015
funiN can be doΛvny.eiiyd in u>c{0.iMTiή
Figure imgf000013_0001
10'»,. ^ α". Last now V'< ui at kast aboui
Figure imgf000013_0002
ahm 40*1 v.omj>au\t v ^ienuesl p^vosses a.xsem Uv '.nodifϊej.
} 0055] Oιhe> nuvxfxv.od results
Figure imgf000013_0003
\s U\\ u-5oioa.se Hx U
Figure imgf000013_0004
<^ .* eas; αbou
Figure imgf000013_0005
ΛΪ-^U ^ v o; a? !cα- 1 aK>ut 60
Figure imgf000013_0007
ai ieαsi about 70° o eoπipared to au ide?uκal ftoΛSs ahseni lho
Figure imgf000013_0006
i;s ac.dU:oπ, ύ^ uhn jn<xs exhibit a decrease j\ l^ve U' ^y , at least abou "■• '« o: ei o.is; aK>Uv 1'»° .> o: Λi
Figure imgf000013_0008
^v
Figure imgf000013_0009
.n α<«t mφaet :esistαnee.
[U056] !
Figure imgf000013_0010
Figure imgf000013_0011
how cxtmJed samples at dittojent puϋer speecs \ i>τ--.hs.us5C> extiudei vcιπpp>.v)
Figure imgf000013_0012
I:κ» UΓ-
Figure imgf000013_0013
<um X I ){>N (a buKodα" folseiξnlcne kαxuig α dcnoH) of 09486 gu and an Mk o^ r 2~ Uc nun \ convu.;cuiil> as.« abk
Figure imgf000013_0014
i<>»r.o>i b) mol} h
Figure imgf000013_0015
UF\~ ?or ns !
Figure imgf000013_0017
C ^as
Figure imgf000013_0016
an evΛeπrerU'
Figure imgf000013_0018
HXs 0 v)
Figure imgf000013_0019
U ^aft 5 NΛ; °O iH
Figure imgf000013_0020
a$yu£' c,o spoeJs, the scM'h.N -u
Figure imgf000013_0021
5 ate ohov*n in lanle '
1 able 1
Figure imgf000013_0022
niocalealion
»<> D ;fe ins;!
.'7
, -, 44bλ t i Λ--) 44;; ;'3 ss 66
^
1 7700_
*sv 66oo I sSoO
— &ύ
MO J0Θ57J I
Figure imgf000014_0001
ΗrVs a?
Figure imgf000014_0002
H\ jθϋSSj Exanir!e_2. Blown ύhw> 'Acre lbrmed from \aiying polymer sampk-*. Sample
2 \ wac* formed uom BDMi 05-11 <<ι Ziegler-Natta formed bimodal poh ethylene haung a debits <u 0 <■>>!<; y ..-c <md au ML of 0.27 dgmin), produced by 1OT \l PFl IUV lib MICA! V
Figure imgf000014_0003
blending Sample 1Λ wnh 5 wΛi Ul Λ-4, a nueleutor ina^tcibatcb e^nunning !1F\-?ΛH' in I DPI:, commcrciatiy a\aiiαb!e iV-ni Mi! liken CltejniefJ-*.
Figure imgf000014_0004
ba^ ing a dcuc'sty vi 09?.
Figure imgf000014_0006
alhii>ie h<nn
Figure imgf000014_0005
Cbcnύcal, MA S.-αupie 2Λ. Sample 2O WHS ioπned irom 2285 (a /iegicr-Naua ibrmed bunodal p->l>dh}!ene liavuK a density of 0 ()5! g'cc and αu Mk of 0.32 d^ mri.K conmiv'rciaϊK asaihfDle πom k>r\l PV!BOCHFMIΓAI N, ΓSΛ. Inc. Sample 21:
Figure imgf000014_0007
nsclt hkndiii:;
Figure imgf000014_0008
Figure imgf000014_0009
pnuiueed using an Alpine ixhn line wύb a fiat tempei at ■»••,. nr-ύkv of 40υ'V 1 lit- tliαi subHUy
Figure imgf000014_0011
quaiuified by producing biowrj lllm ai three neck heights -;
Figure imgf000014_0010
Figure imgf000014_0012
^ ere reixmliny at each iieek heights whh the iris
Figure imgf000014_0014
ssuuscπeai
Figure imgf000014_0013
t>f 4 i.s ϋic highest Ni'Jπhi} ^ here there arc no vertical stabiin> s^sucs (breathing^ >v hnhble (lancing \ unking of 3 indicates sligin breathing and dancing $JC"^ r'UlU ^" deviation hom ccracf ! \ ranking of ?. indicates the bubble is breathing or dancing greatci than 1 " frosn center A ranking of 1 is use !<^csr ranking ^ here the bubble ^ cλhibiung signifieani breathing and or helical votanon all the vun to the open iris. A fmai stability number is calcuhϊcd h> inulbplxinv; the d.ua from mv ibrce closed ranking? and the three open ranking? and normaUrmg using ihe Kn; scale, 1 he s^ale for the tcsύng is tjberei'ore 0 to 3.61 , with 5.M being the most stabk ranking I'nexpeetedU . the nucleated samples resulted in improved bubble stability vxliiie bubble was general!) observed With the non-nneicated samples, in parucuiai. Sample .?B scdultcd in about Λ>n« huprovenscnt in bubble stability over Sample ZΛ.
|00<>y| 1 he
Figure imgf000014_0015
milne uce of the nueleator adJHion. While making blown fiim unh Satnpie 2,V there was evidence of port il>« with both flattened areas on the bubble <uul
Figure imgf000014_0016
tihu i-iiHstrared m
Figure imgf000014_0017
Sample 2B dramatical!) impaned port flow issues such UKU nenher
Figure imgf000015_0001
present whh the nucleated Nend. Tfe rsπproved yauge distribution aliox^d ior more doxcngaαging oi'ihe film.
(00611 1 lie eHeu of downgauging ύ £ , increasing the take-off speed during film
Figure imgf000015_0002
was αiso unalx/eci during processing of the sample?. Doxsngaυgma was
Figure imgf000015_0003
us skis example hs .soshng ihe
Figure imgf000015_0004
speed to 75 rpm at a eonsiaπt nip roll --peed vi 7o ;n sntn a?κi thcji sknsi} uκNϊc;u>ijiu' the
Figure imgf000015_0005
Sample J!> sigsnficant breathing hegau to occur at a nip ,s|ved of "(> m mm, Ihe bubble hroko due io insiabuii} on inoraμo at *->8 nπmn. ghing a liaai yaiyc uf
Figure imgf000015_0006
U.,? mύ.
Figure imgf000015_0007
No bswJhuψ \s. 'us pteseni at >ai> put ut in the ie t and a nip speed oi 140 m mm \xα* aehieu\l } iehbny ,\ ύual yuu^ ks.s Uuin V. I mil tOΛM mil) before the bubble (n-uke. (0062| Iu addiiiotu the ^pueal properties of \urious .sample? v<ere nieα^nred :mΛ <ox' nlusuufcd iu I'igutv^ ^ run) 4 Λs shnwu iu i-i^ure ^. Sample 2B UekWα a ?5 t<^ ^^ percent jtTipmx eπ^eni >π μU^-; uxer S<impie 2 \, depending on ibe neck height \ reduction «u haze oϊ I^ Iv M ρeκNen? W:LS uHo
Figure imgf000015_0008
ed. ΛΪ> shcmn hi Figure 4, ihe difiVrt-uee >u L>ks?.s waa exeti ^ivaier ior
Figure imgf000015_0009
) a rcdueύon in ha/c oi ?>% |00(>3| Further a,^ illusirmed in Figuje 5. Sample 2B unexpectedly evrubued α reduction m maw bine direehou ^\H>"! tear Mfongth over Saraplc 2Λ. but uu significant change in transversa Sx !T>}
Figure imgf000015_0010
the curx'e ui tlie right due to the increased iear raUo I knxeses. n
Figure imgf000015_0011
a .sundur shift m tear ratio.
Figure imgf000015_0012
. the addition of the nuekator
Figure imgf000015_0013
causes a <>oρ in MH hwr ciirenoHi.
|00fe4j While ihe foregoing is di reeled to embodiments of the pre^eni isneniion. othe- and farther embodiment* of she invention
Figure imgf000015_0014
be dexised without departing iioin ilκ basic scope thereof and fhe SC>HV dsereof LS determined by the elaini$ thai folloxs

Claims

Wha: is eUjmied ?v
\ . \ process of ibπmng a pol> mer article comprising: iding a Hmodal cili> lene based polymer; bicnJin^ the bimodal etmlene (wed pohirser with a nodeator to iorm m^vilued pohvilnicne; h>rnsnψ ibo
Figure imgf000016_0001
^ sekvicd fπ«ns pspo
Figure imgf000016_0002
illms.
2, 1 iiv
Figure imgf000016_0003
a /L-g.es-NutUϊ
Figure imgf000016_0004
^!eir; Ls fonnCil b> conhwtrag •m a!k>! tnrumeMum
Figure imgf000016_0005
an alcohol to iorm a magnesium dkύkoxidc Ci-nipound and coniacting the
Figure imgf000016_0006
ageu^
Λ Che process of claim L wherein the puhnier arucle i$ a nipt ankle ,aκ» exhibits at icαβi αlxnst 5s'v grcitcr
Figure imgf000016_0008
p^oce^s
Figure imgf000016_0007
me nυckaior,
4, Hie process v>f eiahn ". wherein the poluner article is prepared in th*. ah^enec of
Figure imgf000016_0009
5. ll\e process o\ eiaini >, wherein the pipe article exhibits at le<ust ab»>uι U^o ^i eater ^ re^iswnce than a poKmcf article prepared \kι an identical process absent the mieleator.
Ϊ\ The precox >*s elabn 1. \s herein the polymer article iv< a Mown iilm and exhibiis en iea>a aboui lU°>i iuereαNC in bubble tUabiiii) than a polymer article prepared ^Ja ua ύk-ntic.'il pr<>et-os aKciii ihe nucleates
7. The
Figure imgf000016_0010
0.^1 wi °c 10 ubott! ^ \M.°O nuckatcir.
u
8. I he proecλs of claim 1 , wherein the pohmer article exhibit^ J baze that i.s at least about 10% less than α pohmer article prepared via an identical process aksent the nucLator,
v. The pnxvβs of claim 1. vs herein ihe ethylene leased pohmer exhibit a density oi at ku^ siKfUt 0 °40 - \ o
10 i he process oi Uaim L wherein the eihslene bused
Figure imgf000017_0001
e^ht
0 f at Ie ^St ;*!vm ^u.Ouo.
1 1. 1 he proce^ of claim L wherein the binioUal ethy lene ba^eα j-oh mci exhibits a hi^h n-olecusas fj action
Figure imgf000017_0002
v»eight of from αhoui 50ΛHKS» to jfvut
Figure imgf000017_0003
»>i from ;UH«nt
1.? The P-OCΛ>N of vt.mii 1 L *Λ herein the eth> !cjic based polymer cxbiriis a ratio of hk-h niolt'cuiar xvei^bt iraαion to lou moiecubi \x eight fraction of from ahoui 8<f;.x'> to aboui J^vgO.
13, Λ poHrαi.-r article formed irorn the process of ekήm 1.
) -*. \ pipe fonned from tht.* process of claim 3.
15. A n ϊnni fonucd from the process of claim U
H>. The procCN-' oi v kutn 1,
Figure imgf000017_0004
the pohmer article eUubits a ^k».^^ thai is ^t ieuU about ^y1O higlier man a polsracs urtiele prepared \ ia a« klentieal proce^^ αbsenf the nncloatof,
17, The Mown film of ehim 15. wherein the blown film exhΦits at least <ιb<uu ^ l^' - iuereasc io an abiiit> to dowiiμaiige than a poh mer article prepared \ia an κle;uical pr>HX-^s absent the mwieator.
PCT/US2009/067019 2008-12-18 2009-12-07 Polyethylene polymerization processes WO2010080283A1 (en)

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