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WO1997044391A1 - Granules d'elastomere polymere a base d'isobutylene - Google Patents

Granules d'elastomere polymere a base d'isobutylene Download PDF

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Publication number
WO1997044391A1
WO1997044391A1 PCT/US1997/008251 US9708251W WO9744391A1 WO 1997044391 A1 WO1997044391 A1 WO 1997044391A1 US 9708251 W US9708251 W US 9708251W WO 9744391 A1 WO9744391 A1 WO 9744391A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
isobutylene
composition
pellets
copolymer
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.)
Ceased
Application number
PCT/US1997/008251
Other languages
English (en)
Inventor
Hsien-Chang Wang
Richard Cheng-Ming Yeh
Dongming Li
Thomas Chen-Chi Yu
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.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of WO1997044391A1 publication Critical patent/WO1997044391A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/283—Iso-olefin halogenated homopolymers or copolymers

Definitions

  • This invention relates to elastomeric isobutylene copolymer compositions that may be processed into the form of non-agglomerating pellets. More particularly, this invention relates to an article of manufacture which comprises pellets which are stable and relatively free flowing with respect to each other and composed of 60 wt% or greater of an elastomeric component comprising at least 51 weight percent of an isobutylene based elastomer
  • Isobutylene based elastomers such as butyl rubbers, which are isobutylene- isoprene copolymers, and halogenated derivatives of butyl rubbers, such as bromobutyl rubber and chlorobutyl rubber, are utilized in the manufacture of a wide variety of useful articles, particularly in the manufacture of the inner liner, carcass, sidewall and tread of pneumatic tires and in other applications such as medical stoppers, hoses and the like. More recently an elastomeric isobutylene- paraalkylstyrene copolymer has been developed, as described in commonly owned U.S. Patent No. 5,162,445, which also can be advantageously used in tire applications.
  • an elastomeric isobutylene copolymer could readily be loaded into or discharged from storage bags and/or hopper cars in controllable predetermined quantities, and in this form could readily be transported from the copolymer production site and used at the final article manufacturing site.
  • an elastomeric isobutylene copolymer is a particularly self-adhering
  • 4,822,545 itself describes an elaborate method of co-blending an elastomer with a semi- crystalline plastic having a melting point at least 10°C greater than the softening point of the elastomer followed by extrusion of the blend through a die having a specifically controlled temperature gradient to form a strand that may be cut to pellets which are stable and free flowing because they carry a skin of the semi- crystalline plastic.
  • pelletizing efforts may have with respect to other types of elastomers such as silicone, ethylene-propylene, ethylene-propylene-diene, polybutadiene, styrene-butadiene rubbers, and the like, they have not proved particularly practical of application to isobutylene based rubbers.
  • An isobutylene based rubber is a particularly sticky elastomer which presents unique problems with respect to its initial formation into non- agglomerating pellets. Further an isobutylene based rubber generally exhibits cold flow properties such that pellets of such a material that may as initially formed be non-agglomerating undergo cold flow deformation with time during storage to form a highly agglomerated and/or a fused mass, i.e. such pellets lack stability
  • This invention provides for an isobutylene based rubber composition that may be processed by standard pelletization procedures to produce stable, relatively free flowing pellets having an isobutylene rubber content of at least about 30 wt% and a total elastomer content of at least about 60 wt% and a thermoplastic content not exceeding 40wt% of the total composition.
  • the produced pellets are dusted with a non-tack dusting agent
  • the dusted pellets are stable, i e , will remain free flowing during a quiescent period of storage until they are processed
  • This invention is applicable to the production of stable, free flowing pellets composed of isobutylene based rubbers such as butyl rubbers, halobutyl rubbers such a bromobutyl rubbers, and most particularly to isobutylene-paraalkylstyrene copolymer elastomers such as isobutylene-paramethylstyrene copolymer elastomers and halogenated derivatives thereof such as isobutylene-paramethylstyrene- parabromomethylstyrene terpolymer elastomers and functionalized derivatives of these halogenated derivatives as described in commonly owned U.S Patent No 5,162,445
  • compositions of an isobutylene based rubber which are suitable to practice of this invention comprise from about 60 to about 90 wt% of an elastomer component which comprises at least about 51 wt% of a butylene based rubber and from 0 to about 49 wt% of another type of elastomer and from about 10 to about 40 wt% of a thermoplastic
  • the composition is produced as a homogeneous mass by high shear blending of the respective polymeric components, such as by a Banbury mixer, at a temperature above the melting point of the polyolefinic thermoplastic component.
  • the composition may be pelletized by standard means, such as by a single-screw extruder with an under- water pelletizer or by a twin-screw extruder and a strand- cut pelletizer, to produce relatively stable free flowing pellets
  • a non-tacking powdered agent Any organic, inorganic or quasi organic material can be employed as a dusting agent: the dusting agent may comprise a non sticky plastic organic material such as powders of a low or high density polyethylene (LDPE, HDPE), polypropylene (PP), nylon or other non sticky polymeric materials; non sticky inorganic materials such as powders of talc, clay, ZnO, Ti 2 0 3 , Si0 2 and the like, non sticky quasi organic materials such as powders of a metal (Ca, Zn, etc.) stearate, carbon black, waxes and the like
  • LDPE low or high density polyethylene
  • PP polypropylene
  • non sticky inorganic materials such as powders of talc, clay, Zn
  • the pellets may be treated to a dusting treatment level of about 0 1 to 3 0, and preferably from about 0 5 to 2 0%, of the pellet weight
  • Pellets produced of such compositions comprise from about 60 to about 90 wt% of an elastomer which comprises a butylene based rubber from the group consisting of polyisobutylene, butyl rubber, halobutyl rubber, isobutylene-paramethystyrene copolymer rubber, isobutylene-paramethystyrene-parabromomethystyrene terpolymer rubber and functionalized derivatives of such rubbers and from 0 to about 49 wt% of this elastomer may comprise a second rubber from the group consisting of a polyolefinic rubber such as an ethylene-propylene copolymer rubber, an ethylene- propylene-diene te ⁇ olymer rubber or the like; from about 10 to about 40 wt% of a polyo
  • This invention is particularly suited to application to those elastomers which in their solid state are tacky and/or exhibit cold flow.
  • the elastomer compositions in which isobutylene is the predominate monomeric repeating unit, to the extent of at least about 60 wt% of the elastomer content, are particularly benefitted by this invention.
  • Such isobutylene based rubbers include polyisobutylene elastomers; isobutylene-isoprene copolymers (i.e., butyl rubber); isobutylene-paraalkystyrene copolymers; halogenated derivatives of such isobutylene based copolymers such as bromobutyl rubber and brominated isobutylene-paraalkylstyrene copolymers and functionalized derivatives of such isobutylene based copolymers.
  • this invention is particularly applicable to the production of stable, free flowing, elastomer rich pellets of butyl rubber, bromobutyl rubber, isobutylene- paraalkylstyrene copolymers, brominated isobutylene-paraalkylstyrene copolymers and functionalized derivatives of brominated isobutylene-paraalkylstyrene copolymers.
  • the brominated and/or functionalized counterparts of an isobutylene- paraalkylstyrene copolymer, particularly those of an isobutylene-paramethylstyrene copolymer are of the greatest interest as an elastomer for use in this invention.
  • the isobutylene-paraalkylstyrene copolymers and derivatives of these copolymers that are suitable for practice of this invention are those as described in U.S. Patent No. 5,162,445, the disclosure of which is hereby incorporated by reference as if fully set forth and described herein.
  • Those copolymers of particular interest are those of isobutylene (IB) and paramethylstyrene (PMS), which may hereafter be referred to as an IB-PMS copolymer, and halogenated or functionalized derivatives of these copolymers.
  • those that exhibit elastomeric properties generally have a weight percent content of LB monomeric units of from about 99.5 to about 60 and a PMS monomeric content of from about 0.5 to about 40 weight percent.
  • PMS copolymers have an isobutylene content of from about 80 to 96 weight percent (about 89 to 98 mole %) and a paramethystyrene content of about 20 to 4 weight percent (about 11-2 mole %).
  • the elastomeric LB-PMS copolymers have a number average molecular weight (M n ) of 500 or greater, preferably of 25,000 or greater, ranging up to about 2,000,000 and their molecular weight distribution (weight average molecular weight divided by number average molecular weight) is less than 6.0, preferably less than 4.0, and most preferably less than 2.5.
  • M n number average molecular weight
  • these IB-PMS copolymer elastomers may be brominated to inco ⁇ orate bromine therein to the degree desired without disrupting the elastomeric nature or the superior microstructural properties of the precursor copolymer, and the brominated LB-PMS copolymer elastomer, and derivatives of this, are particularly preferred elastomers for use.
  • thermoplastics such as low or high density polyethylenes such as LDPE and HDPE and ethylene based copolymeric thermoplastics such as LLDPE, VLDPE, plastomers, polypropylenes, etc.; polyamide thermoplastics such as nylons; polyurethanes; polyester; polycarbonate and polyether such as polyphenylene ether; and other high polymer substances which soften with heat but return to their original condition at ambient temperature such as polyvinyl chloride, polystyrene, cellulosic and acrylic resins and the like.
  • thermoplastic material are the polyolefinic thermoplastics.
  • the pellet forming blend composition may comprise as its polymeric components only the isobutylene based rubber and the thermoplastic, or it may also, and beneficially so, contain as a third polymeric component a quantity up to about 45 wt% of the blend of an elastomeric polymer which is other than an isobutylene based rubber.
  • elastomers suitable for this purpose include any elastomer having a Tg less than 0°C, such as general rubbers; polyolefinic elastomers such as ethylene-propylene copolymer elastomers (EPR), ethylenc- propylene-diene terpolymer elastomers (EPDM), and the like; styrene-butadiene copoymer rubber; polybutadiene rubber; polychloroprene (neoprene) rubber; nitrite rubber; polysulfide rubber; polyisoprene rubber; silicon rubber; polyurethane rubber; natural rubber and the like. Of these polyolefinic elastomers are preferred.
  • an isobutylene based rubber is blended with a polyolefinic thermoplastic as the only other polymeric component, generally it is necessary to use the polyolefinic thermoplastic in an amount of from about 10 to about 40 wt% of the blend, and preferably as at least about 15 wt% of the blend.
  • the isobutylene based rubber thus comprises from about 90-60 wt% and the polyolefinic thermoplastic comprises from about 10-40 wt% of the blend.
  • the quantity of polyolefinic thermoplastic may be reduced to as low as that of about 10 wt% to provide a blend wherein the isobutylene based rubber and other elastomer comprises about 90 wt% of the blend with the isobutylene based rubber comprising at least about 51 wt% of the total elastomer.
  • the isobutylene based rubber comprises from about 30 to about 89 wt%
  • the other elastomer comprises from about 1 to about 45 wt%
  • the polyolefinic thermoplastic comprises from about 10 to 40 wt% of the polymer content of the prepelletizable blend.
  • the blend composition Prior to pelletization the blend composition is rendered into the state of being a homogeneous mass by mixing its respective components together under high shear conditions while at a temperature greater than that of the melting point of the polyolefinic thermoplastic component of the blend
  • This may be readily accomplished by mixing the blend components in a Banbury or similar shearing mixer at a temperature from about 330 to about 475°F, preferably from about 340- 370°F
  • the homogeneous mass in its molten state may be fed to a pelletization procedure, such as a single screw or a twin screw extruder
  • the pellets produced from the blend composition may be, and preferably are, dusted with a non-tacking powdered agent
  • Such dusting may be accomplished by gravitationally dropping the dust onto the pellets as they are being moved by a vibrating or screw conveyor
  • Dusting may also be accomplished by spraying of a dust-water slurry onto the pellets Alternatively, dust may be applied to the pellets as they are moved thorugh
  • the BrLB PMS had a paramethylstyrene content of 7.5 wt%, a bromine content of 0.7 wt% and a Moony Viscosity of about 45 (1+8, 125°C).
  • the PP had a melt flow rate (MFR) of 35
  • the EPR used in recipe X had a Moony Viscosity of about 46 (1+4, 125°C) and an ethylene content of about 78wt% and in recipe Y had a Mooney Viscosity of about 26 (1+4, 125°C) and an ethylene content of about 57wt%.
  • the IB PMS used in recipe Z had a paramethylstyrene content of 5.0wt%, a bromine content of 0.0wt% and a moony viscosity of about 35 (1+8, 125°C) and the HDPE in recipe E had a melt index (MI) of 19 at 190°C and a density of 0.9525.
  • HDPE dusts were added and then the pellets were pneumatically conveyed to a storage bin. Under the large bin, the pellets were bagged into 50 pound bags. The blends were mixed in the Banbury and dumped at 350-370°F. The pelletizing extruder was steam heated to about 350°F. After dusting with HDPE powder, and pneumatically mixed and conveyed, the pellets were free flowing enough to be bagged.
  • Recipes V, W, X and Z were respectively processed into pellets on a pelletizing line comprising a 122 pound Banbury, a 10 inch single screw pelletizer with a ram feeder, screen pack, and an underwater pelletizer.
  • the pelletizing die has 50 holes of 1/8 inch diameter with a six-blade cutter.
  • pellet Lube Pellet Lube suspension was added to the pellet cooling water and the water temperature was kept at 100°F. Coming out of the spin dryer, the pellets were conveyed by an auger screw conveyor, where LDPE dusts were added. The pellets then fell into a ribbon blender before they were bagged. The pellets were bagged in a 50 pound plastic bag and encased in a supported cardboard box.
  • Example 12 The pelletization procedure of Examples 4-1 1 was applied to recipe V to produce pellets which in one case (Example 12) were dusted with a HDPE powder rather than with LDPE powder, and in the other case (Example 13) were dusted with PP powder rather than with LDPE powder. Otherwise, the pelletization, dusting and bagging procedures applied were the same as described in Examples
  • Pellets as produced in Examples 1-13 were evaluated for stability after storage for three days at a temperature of 50°C, both with and without pressure loading.
  • the elastomeric pellets produced in accordance with this invention although of a high content of a butylene based rubber, were found to be stable and relatively free flowing.
  • Such elastomeric pellets may be readily loaded into or discharged from storage bags and/or hopper cars and are convenient for transport to and use at an article manufacturing site. When ready for manufacturing use the elastomeric pellets may readily be mixed with a desired amount of curing agents and other desirable additives and/or polymer components, shaped to form of a desired article and the elastomer may then be cured or vulcanized.

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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)
  • General Chemical & Material Sciences (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions copolymères élastomères à base d'isobutylène pouvant être traitées sous la forme de granules non agglomérés qui sont stables et s'écoulent relativement librement les uns par rapport aux autres, et qui sont constitués de 60 % en poids ou plus d'un composant élastomère comprenant au moins 51 % en poids d'un élastomère à base d'isobutylène.
PCT/US1997/008251 1996-05-17 1997-05-15 Granules d'elastomere polymere a base d'isobutylene Ceased WO1997044391A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64955196A 1996-05-17 1996-05-17
US08/649,551 1996-05-17

Publications (1)

Publication Number Publication Date
WO1997044391A1 true WO1997044391A1 (fr) 1997-11-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8013069B2 (en) 2005-01-31 2011-09-06 Exxonmobil Chemical Patents Inc. Polymer blends and pellets and methods of producing same
US8530581B2 (en) 2011-12-12 2013-09-10 Exxonmobil Chemical Patents Inc. Powder, compositions thereof, processes for making the same, and articles made therefrom
DE102013202114A1 (de) * 2013-02-08 2014-08-14 Robert Bosch Gmbh EP(D)M-NOR/TOR/PIB/CR/IIR/CIIR/BIIR-Wischgummi

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287282A1 (fr) * 1987-04-07 1988-10-19 Tonen Chemical Corporation Composition élastomère thermoplastique
EP0419155A2 (fr) * 1989-09-18 1991-03-27 Tonen Chemical Corporation Composition thermoplastique élastomère résistant à l'huile
WO1994003542A1 (fr) * 1992-07-31 1994-02-17 Exxon Chemical Patents Inc. Modification de la resistance aux chocs concernant des polyamides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287282A1 (fr) * 1987-04-07 1988-10-19 Tonen Chemical Corporation Composition élastomère thermoplastique
EP0419155A2 (fr) * 1989-09-18 1991-03-27 Tonen Chemical Corporation Composition thermoplastique élastomère résistant à l'huile
WO1994003542A1 (fr) * 1992-07-31 1994-02-17 Exxon Chemical Patents Inc. Modification de la resistance aux chocs concernant des polyamides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8013069B2 (en) 2005-01-31 2011-09-06 Exxonmobil Chemical Patents Inc. Polymer blends and pellets and methods of producing same
US8530581B2 (en) 2011-12-12 2013-09-10 Exxonmobil Chemical Patents Inc. Powder, compositions thereof, processes for making the same, and articles made therefrom
DE102013202114A1 (de) * 2013-02-08 2014-08-14 Robert Bosch Gmbh EP(D)M-NOR/TOR/PIB/CR/IIR/CIIR/BIIR-Wischgummi

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