WO2019036085A1 - Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation - Google Patents

Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation Download PDF

Info

Publication number
WO2019036085A1
WO2019036085A1 PCT/US2018/035305 US2018035305W WO2019036085A1 WO 2019036085 A1 WO2019036085 A1 WO 2019036085A1 US 2018035305 W US2018035305 W US 2018035305W WO 2019036085 A1 WO2019036085 A1 WO 2019036085A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
isobutylene
mole
butyl
content
Prior art date
Application number
PCT/US2018/035305
Other languages
English (en)
Inventor
Sujith Nair
Ranjan Tripathy
Sunny Jacob
Yuan-Ju Chen
Original Assignee
Exxonmobil 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 Exxonmobil Chemical Patents Inc filed Critical Exxonmobil Chemical Patents Inc
Priority to EP18731345.7A priority Critical patent/EP3668923A1/fr
Priority to CN202211283875.8A priority patent/CN115466466A/zh
Priority to US16/634,389 priority patent/US10982081B2/en
Priority to CN201880053521.XA priority patent/CN110997797B/zh
Publication of WO2019036085A1 publication Critical patent/WO2019036085A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • 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 ; Homo- 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 compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C09J123/283—Halogenated homo- or copolymers of iso-olefines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present disclosure relates to butyl based compositions having a low transition glass temperature, and more particularly relates to hydrocarbon resins for butyl based compositions with low transition glass temperature to improve low temperature fatigue resistance without an increase in permeability.
  • Aliphatic-aromatic based hydrocarbon resins are used in isobutylene based compositions to impart suitable filler dispersion and modify the range of mechanical and fatigue resistant properties of the composition without affecting the permeability characteristics.
  • certain butyl based compositions comprise one or more polymers having a high softening point ("SP") and a high glass transition temperature (“Tg”). Therefore, adding such polymers increases the butyl based composition Tg, and the potential for cold cracking and decreasing cold temperature resistance in various applications.
  • SP softening point
  • Tg high glass transition temperature
  • isobutylene-isoprene based compositions are prone to crack at severe low temperature conditions (i.e., -35°C to -40°C) under tension-compression cyclic loadings.
  • additives can be added the butyl based composition to decrease the overall Tg, often an additive will increase the permeability coefficient of the composition, which is undesirable, especially for applications such as tire inner liners.
  • a secondary polymer such as natural rubber, ethylene propylene rubbers or ethylene propylene diene monomer (“EPDM)
  • EPDM ethylene propylene diene monomer
  • Tg as well as the low temperature brittle point
  • LTB low temperature brittle point
  • relative large amount of oils in the isobutylene based composition can increase the free volume of the polymer chains and cause a suppression of the Tg and LTB.
  • additives such as low molecular weight plasticizers can result in an increase in permeability coefficient, especially for applications such as tire inner liners.
  • a bromobutyl-natural rubber blend composition can result in more rapid air loss in a tire when compared to a 100% bromobutyl polymer blend based composition.
  • some isoprene based polymers such as isobutylene co-para- methylstyrene based polymers, have improved permeability characteristics but also have higher glass transition temperatures than conventional isobutylene-isoprene based compositions. Therefore, these polymers pose serious concerns with respect to low temperature performance. While co-monomers such as para-methyl styrene with functionality in the side group can help in efficient packing of the chains and reduce permeability, efficient packing reduces the free volume of the polymer, thereby increases Tg.
  • butyl based compositions with very low Tg and high cold temperature fatigue resistance are needed. Therefore, a need exists for reducing the Tg (and LTB) and improving cold temperature fatigue resistance of butyl based elastomer compositions without decreasing permeability or rheo-mechanical properties.
  • hydrocarbon resins comprising an aromatic H mole content between about 0% to about 10%; an olefin H mole content between about 0% to about 30%; and an aliphatic H content between about 70% to about 100%, and where the resin has a number average molecular weight between about 20 to about 500 g/mole, a weight average molecular weight between about 100 to about 2,000 g/mole, and a glass transition temperature between about 0°C to about -80°C.
  • Methods of making the hydrocarbon resin comprising the steps of providing a hydrocarbon reaction product having a reaction temperature is between about 0°C and about 30°C.
  • the reaction product comprises: (a) at least one of trans-pentadiene- 1,3, cyclopentene, cis-pentadiene, and mixtures thereof; (b) a cyclic pentadiene component selected from the group consisting of: cyclopentadiene, cyclopentadiene dimer, cyclopentadiene trimer, cyclopentadiene-C 4 codimer, cyclopentadiene-piperylene codimer, cyclopentadiene-methylcyclopentadiene codimer, methylcyclopentadiene, methylcyclopentadiene dimer, methylcyclopentadiene-C 4 codimer, methylcyclopentadiene- piperylene codimer, and mixtures thereof; and an aromatic component selected from the group consisting of s
  • the reaction product is quenched with an isopropanol and water mixture and an aqueous layer is separated from the mixture. Paraffins are removed from the aqueous layer to produce the hydrocarbon resin having: an aromatic H mole content between about 0% to about 10%; an olefin H mole content is between about 0% to about 30%; an aliphatic H content between about 70% to about 100%; a number average molecular weight between about 10 to about 1000; a weight average molecular weight between about 50 to about 5000; and a glass transition temperature between about 0°C to about -80°C.
  • the reaction product can be produced in a polymerization reactor with a Friedel- Crafts catalyst or Lewis Acid catalyst at a temperature between about 0°C and about 100°C.
  • the reaction product can comprise 10 to 20 wt. % of raffinate.
  • Figure 1A shows the effect of varying natural rubber content on the permeability of 2 isobutylene-isoprene copolymer compositions.
  • Figure IB shows the effect of varying natural rubber content on the Tg (and LTB) of 2 isobutylene-isoprene copolymer compositions.
  • Figure 2A shows the effect of varying napthalenic oil content on the permeability of 2 isobutylene-isoprene copolymer compositions
  • Figure 2B shows the effect of varying napthalenic oil content on the Tg (and LTB) of 2 isobutylene-isoprene copolymer compositions.
  • Figure 3A shows polymer Tg dependence on pMS level.
  • Figure 3B shows composition Tg dependence on pMS level.
  • Figures 4A and 4B show the effect of varying natural rubber content on inner liner compositions Tg and LTB.
  • Figure 5A depicts the effect of the Tg of oil on composition Tg.
  • Figure 5B depicts the effect of the Tg of resin on composition Tg.
  • the term “elastomer” may be used interchangeably with the term “rubber” and refers to any composition comprising at least one elastomer.
  • the term “rubber” refers to any polymer or composition of polymers consistent with the ASTM D1566 definition: "a material that is capable of recovering from large deformations, and can be, or already is, modified to a state in which it is essentially insoluble (but can swell) in boiling solvent. "a material that is capable of recovering from large deformations, and can be, or already is, modified to a state in which it is essentially insoluble (but can swell) in boiling solvent.
  • vulcanized rubber refers to a crosslinked elastic material compounded from an elastomer, susceptible to large deformations by a small force capable of rapid, forceful recovery to approximately its original dimensions and shape upon removal of the deforming force as defined by ASTM D1566.
  • hydrocarbon refers to molecules or segments of molecules containing primarily hydrogen and carbon atoms. In some molecules, hydrocarbon also includes halogenated versions of hydrocarbons and hydrocarbons containing heteroatoms.
  • inert hydrocarbons refers to piperylene, aromatic, styrenic, ameylene, cyclic pentadiene components, and the like, as saturated hydrocarbons or hydrocarbons which are otherwise essentially non-polymerizable in carbocationic polymerization systems, e.g., the inert compounds have a reactivity ratio relative to cyclopentadiene less than 0.01.
  • Aromatic, olefinic, and aliphatic hydrogen content of the hydrocarbon polymer modifiers were determined by proton nuclear magnetic resonance ("H-NMR").
  • phr refers to parts per hundred rubber and is a measure of the component of a composition relative to 100 parts by weight of the elastomer (rubber component) as measured relative to total elastomer.
  • the total phr (or parts for all rubber components, whether one, two, three, or more different rubber components) is always defined as 100 phr. All other non-rubber components are a ratio of the 100 parts of rubber and are expressed in phr.
  • polymer refers to homopolymers, copoloymers, interpolymers, terpolymers, etc.
  • a copolymer refers to a polymer comprising at least two monomers, optionally with other monomers.
  • copolymer refers to random polymers of C 4 to C 7 isoolefins derived units and alkylstyrene.
  • a copolymer can contain at least 85 wt. % of the isoolefin, about 8 to about 12% by weight alkylstyrene, and about 1.1 to about 1.5 wt % of a halogen.
  • a copolymer can be a random elastomeric copolymer of a C 4 to C 7 alpha -olefin and a methylstyrene containing at about 8 to about 12 wt. % methylstyrene, and 1.1 to 1.5 wt.
  • random copolymers of isobutylene and para-methylstyrene can contain from about 4 to about 10 mol % para-methylstyrene wherein up to 25 mol % of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, such as a bromine atom (para-(bromomethylstyrene)), as well as acid or ester functionalized versions thereof.
  • copolymers can be substantially free of ring halogen or halogen in the polymer backbone chain.
  • the random polymer is a copolymer of C 4 to C 7 isoolefin derived units (or isomonoolefin), para- methylstyrene derived units and para-(halomethylstyrene) derived units, wherein the para- (halomethylstyrene) units are present in the polymer from about 10 to about 22 mol % based on the total number of para-methylstyrene, and wherein the para-methylstyrene derived units are present from 8 to 12 wt % based on the total weight of the polymer or from 9 to 10.5 wt %.
  • para-(halomethylstyrene) can be para-(bromomethylstyrene).
  • alkyl refers to a paraffinic hydrocarbon group which may be derived from an alkane by dropping one or more hydrogens from the formula, such as, for example, a methyl group (CH3), or an ethyl group (CH3CH2).
  • aryl refers to a hydrocarbon group that forms a ring structure characteristic of aromatic compounds such as, for example, benzene, naphthalene, phenanthrene, anthracene, etc., and typically possess alternate double bonding ("unsaturation") within its structure.
  • An aryl group is thus a group derived from an aromatic compound by dropping one or more hydrogens from the formula such as, for example, phenyl, or C6H5.
  • isoolefin refers to a C 4 to C 7 compound and includes, but is not limited to, isobutylene, isobutene 2-methyl-l-butene, 3-methyl-l-butene, 2-methyl-2-butene, and 4- methyl-l-pentene.
  • the multiolefin is a C 4 to Ci 4 conjugated diene such as isoprene, butadiene, 2,3-dimethyl-l,3-butadiene, myrcene, 6,6-dimethyl-fulvene, cyclopentadiene, hexadiene and piperylene.
  • An exemplary polymer can be obtained by reacting 92 to 99.5 wt. % of isobutylene with 0.5 to 8 wt. % isoprene, or reacting 95 to 99.5 wt. % isobutylene with from 0.5 to 5.0 wt. % isoprene.
  • substituted refers to at least one hydrogen group being replaced by at least one substituent selected from, for example, halogen (chlorine, bromine, fluorine, or iodine), amino, nitro, sulfoxy (sulfonate or alkyl sulfonate), thiol, alkylthiol, and hydroxy; alkyl, straight or branched chain having 1 to 20 carbon atoms which includes methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, etc.; alkoxy, straight or branched chain alkoxy having 1 to 20 carbon atoms, and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, hept
  • substituent selected from, for example,
  • butyl based composition is also sometimes referred to herein "butyl based elastomer composition,” butyl based polymer composition,” “isobutylene based composition,” “isobutylene based elastomer composition” and/or “isobutylene based polymer composition.”
  • isobutylene based elastomer may be used to refer to elastomers or polymers comprising a plurality of repeat units from isobutylene.
  • isobutylene based elastomer or “isobutylene based polymer” refers to elastomers or polymers comprising at least 70 mole percent repeat units from isobutylene.
  • rubber includes, but is not limited to, at least one or more of brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched brominated butyl (polyisobutylene/isoprene copolymer) rubber; halogenated poly(isobutylene-co-p-methylstyrene), such as, for example, terpolymers of isobutylene derived units, p-methylstyrene derived units, and p-bromomethylstyrene derived units (BrIBMS), and the like halomethylated aromatic interpolymers as in U.S. Patent Nos.
  • halogenated isoprene and halogenated isobutylene copolymers 5,162,445, 4,074,035, and 4,395,506; halogenated isoprene and halogenated isobutylene copolymers, polychloroprene, and the like, and mixtures of any of the above.
  • Halogenated rubbers are also described in U.S. Patent Nos. 4,703,091 and 4,632,963.
  • halogenated butyl rubber refers to both butyl rubber and so- called “star-branched” butyl rubber, described below.
  • the halogenated rubber can be a halogenated copolymer of a C 4 (as noted sometimes as “C 4 ") to C 7 (also noted sometimes as “C 7 ”) isoolefin and a multiolefin.
  • the halogenated rubber component can be a blend of a polydiene or block copolymer, and a copolymer of a C 4 to C 7 isoolefin and a conjugated, or a "star-branched" butyl polymer.
  • the halogenated butyl polymer can be described as a halogenated elastomer comprising C 4 to C 7 isoolefin derived units, multi-olefin derived units, and halogenated multiolefin derived units, and includes both "halogenated butyl rubber” and so called “halogenated star-branched” butyl rubber.
  • rubber can be a halogenated rubber or halogenated butyl rubber such as brominated butyl rubber or chlorinated butyl rubber.
  • General properties and processing of halogenated butyl rubbers is described in THE VANDERBILT RUBBER HANDBOOK 105-122 (R. F. Ohm ed., R.T.
  • Halogenated butyl rubber can be produced from the halogenation of butyl rubber.
  • the olefin polymerization feeds employed in producing the halogenated butyl rubber of the invention are those olefinic compounds conventionally used in the preparation of butyl-type rubber polymers.
  • the butyl polymers are prepared by reacting a co-monomer mixture, the mixture having at least one (1) C 4 to C 7 isoolefin monomer component such as isobutylene with (2) a multiolefin, or conjugated diene, monomer component.
  • the isoolefin is in a range from 70 to 99.5 wt. % of the total comonomer mixture, or 85 to 99.5 wt.
  • the conjugated diene component is present in the comonomer mixture from 30 to 0.5 wt. % or from 15 to 0.5 wt. %. From 8 to 0.5 wt. % of the co-monomer mixture is conjugated diene.
  • Halogenated butyl rubber is produced by the halogenation of a butyl rubber product.
  • Halogenation can be carried out by any means, and the invention is not herein limited by the halogenation process.
  • Methods of halogenating polymers such as butyl polymers are disclosed in U.S. Patent Nos. 2,631,984, 3,099,644, 4,554,326, 4,681,921, 4,650,831, 4,384,072, 4,513,116 and 5,681,901.
  • the halogen can be in the so called II and III structures as discussed in, for example, RUBBER TECHNOLOGY at 298-299 (1995).
  • the butyl rubber can be halogenated in hexane diluent at from 40 to 60°C.
  • the halogenated butyl rubber has a Mooney viscosity of from 20 to 70 (ML 1+8 at 125°C), or from 25 to 55.
  • the halogen content is from 0.1 to 10 wt. % based in on the weight of the halogenated butyl rubber or from 0.5 to 5 wt. %.
  • the halogen wt. % of the halogenated butyl rubber is from 1 to 2.2 wt. %.
  • EXXPROTM refers to a brominated isobutylene- paramethylstyrene (BIMSM) rubber or isobutylene-co-para-methyl-styrene based elastomer, which is produced by catalytic polymerization of isobutylene and isoprene and manufactured by ExxonMobil and useful in a variety of consumer applications including tires and medical tube stoppers.
  • BIMSM brominated isobutylene- paramethylstyrene
  • isobutylene-co-para-methyl-styrene based elastomer which is produced by catalytic polymerization of isobutylene and isoprene and manufactured by ExxonMobil and useful in a variety of consumer applications including tires and medical tube stoppers.
  • EXXPROTM 3035 or EXXPRO 3035 refers to a brominated copolymer of isobutylene and paramethylstyrene having a specific gravity of 0.93, a Mooney Viscosity Target of 45 with minimum of 40 and maximum of 50, benzylic bromine, calcium, water and slow cure rate grade.
  • EXXPROTM 3433 or EXXPRO 3433 refers to a brominated copolymer of isobutylene and paramethylstyrene having a specific gravity of 0.93, a Mooney Viscosity Target of 35 with minimum of 30 and maximum of 40, benzylic bromine, calcium, water and regular cure rate grade.
  • EXXPROTM 3745 or EXXPRO 3745 refers to a brominated copolymer of isobutylene and paramethylstyrene having a specific gravity of 0.93, a Mooney Viscosity Target of 45 with minimum of 40 and maximum of 50, benzylic bromine, calcium, water and fast cure rate grade.
  • EXXPROTM Bromobutyl or Bromobutyl refers to brominated isobutylene- isoprene rubber or BUR manufactured by Exxon Mobil Chemical, a family of butyl rubbers used in a variety of consumer applications including tires and medical tube stoppers
  • Bromobutyl 6222 also known as SBB 6222, refers to a brominated copolymer of isobutylene and isoprene having a specific gravity of 0.94; a Mooney Viscosity target of 32, minimum of 27, and a maximum of 37; a bromine composition target of 2.4%, a minimum of 2.2%, and a maximum of 2.6%; and a calcium composition target of 0.165%, a minimum of 0.135%, and a maximum of 0.195%.
  • Bromobutyl 2222 also known as BUR 2222, refers to a brominated copolymer of isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 32, a minimum of 28, and a maximum of 36; a bromine composition target of 1.03%, a minimum of 0.93%, and a maximum of 1.13%; and a calcium composition target of 0.15%, a minimum of 0.12%, and a maximum of 0.18%.
  • Bromobutyl 2235 refers to a brominated copolymer of isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 39, a minimum of 35, and a maximum of 43; a bromine composition target of 1.03%, a minimum of 0.93%, and a maximum of 1.13%; a calcium composition target of 0.14%, a minimum of 0.11%, and a maximum of 0.17%, and regular cure rate grade.
  • Bromobutyl 2255 refers to a brominated copolymer of isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 46, a minimum of 41, and a maximum of 51; a bromine composition target of 1.03%, a minimum of 0.93%, and a maximum of 1.13%; a calcium composition target of 0.15%, a minimum of 0.12%, and a maximum of 0.18% and regular cure rate grade.
  • Bromobutyl 2211 is a brominated copolymer or isobutylene and isoprene having a specific gravity of 0.93; a Mooney Viscosity minimum of 28, and a maximum of 36; a bromine composition target of 1.08%, a minimum of 0.93%, and a maximum of 1.23%; a calcium composition target of 0.13%, a minimum of 0.09%, and a maximum of 0.17% and fast cure rate grade.
  • Bromobutyl 2244 is a brominated copolymer or isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 32, a minimum of 28, and a maximum of 36; a bromine composition target of 1.08%, a minimum of 0.93%, and a maximum of 1.23%; a calcium composition target of 0.13%, a minimum of 0.09%, and a maximum of 0.17% and fast cure grade.
  • Bromobutyl 7211 is a brominated copolymer or isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 32, a minimum of 28, and a maximum of 36; a bromine composition target of 1.08%, a minimum of 0.93%, and a maximum of 1.23%; a calcium composition target of 0.13%, a minimum of 0.10%, and a maximum of 0.16% and fast cure grade.
  • Bromobutyl 7244 is a brominated copolymer or isobutylene and isoprene having a specific gravity of 0.93; a Mooney viscosity target of 46, a minimum of 41, and a maximum of 51 ; a bromine composition target of 1.03%, a minimum of 0.93%, and a maximum of 1.13%; a calcium composition target of 0.17%, a minimum of 0.14%, and a maximum of 0.20% and slow cure grade.
  • EXXONTM Butyl refers to a copolymer of isobutylene and isoprene having a specific gravity of 0.92, and useful in a variety of consumer applications including tires and medical tube stoppers.
  • Butyl 065 refers to a copolymer of isobutylene and isoprene having a specific gravity of 0.92 and Mooney Viscosity Target of 32, Minimum of 29 and Maximum of 35, an antioxidant minimum of 0.03 and 0.3 wt. % of maximum volatiles.
  • Butyl 365 refers to a copolymer of isobutylene and isoprene having a specific gravity of 0.92 and Mooney Viscosity Target of 33 Minimum of 30 and Maximum of 36, an antioxidant minimum of 0.03 and 0.3 wt. % of maximum volatiles.
  • Butyl 068 refers to a copolymer of isobutylene and isoprene having a specific gravity of 0.92 and an antioxidant minimum of 0.03 and 0.3 wt. % of maximum volatiles.
  • Butyl 268 refers to a copolymer of isobutylene and isoprene having a specific gravity of 0.92, a Mooney Viscosity Target of 51, Minimum of 46 and Maximum of 46; an antioxidant minimum of 0.03 and 0.3 wt. % of maximum volatiles.
  • CHLOROBUTYL refers to chlorinated isobutylene-isoprene rubber or CIIR useful in a variety of consumer applications including tires and medical tube stoppers. CHLOROBUTYL is made from reacting butyl rubber with chlorine in a continuous process and provides an improved compression set and better resistance to heat, ozone, and flex fatigue. Other properties of CHLOROBUYTL include low permeability to air, gases, and moisture, vibration damping, low glass transition temperature, wide vulcanization versatility, fast cure rates, no nitrosamines or nitrosamines precursors, good adhesion and compatibility to other rubbers.
  • CHLOROBUTYL 1066 refers to an isobutylene-isoprene copolymer derived from reacting butyl rubber with chlorine in a continuous process having low permeability to gas, gases and moisture, vibration damping, low glass transition temperature, wide vulcanization versatility, good adhesion and compatibility to other rubbers.
  • ESCOREZTM refers to petroleum hydrocarbon tackifiers or tackifier resins.
  • the second family has major components that are polycyclodienes (C10-C12 Cyclodiene dimers plus dicyclopentadiene with or without Cs-Cio vinyl aromatics) (5000 series) that are thermally polymerized.
  • These resins can be used to enhance the tack properties of a variety of adhesive polymers. Applications for these resins include hot melt adhesives and pressure sensitive adhesives.
  • ESCOREZTM E5000 refers to a petroleum hydrocarbon tackifier resin having polycyclodienes (C10-C12 cyclodiene dimers plus dicyclopentadiene with or without Cs-Cio vinyl aromatics) as a major component which is thermally polymerized.
  • ESCOREZTM 1102 refers to an aliphatic hydrocarbon resin having a softening point of 100°C, a melt viscosity of 1650 cP, a molecular weight- number average (Mn) of 1300 g/mol and a molecular weight - weight average (Mw) of 2900 g/mol useful to increase tack and adhesive properties and modify mechanical and optical properties of polymer blends and thermally polymerized.
  • ESCOREZTM 2520 refers to a petroleum hydrocarbon tackifier resin having C5- C6 olefins and diolefins as major components and thermally polymerized.
  • SBC 5066 refers to a chlorinated copolymer of isobutylene and isoprene, including a styrene block copolymer branching agent useful in adhesives and sealants.
  • STRUKTOLTM 40 MS refers to a homogenizing agent by Struktol Company of America and a mixture of aromatic and aliphatic hydrocarbon resins designed to improve the homogeneity of elastomers and effective with elastomer blends which tend to crumble at the beginning of the mixing cycle. STRUKTOLTM 40 MS increases the greentack of some compounds, boosts the efficiency of other tackifying agents and has good solubility in aromatic and chlorinated hydrocarbon oils.
  • PROMIXTM 400 refers to a homogenizing resin of dark aliphatic, naphthenic, and aromatic hydrocarbon resins; an EVA copolymer; silicon dioxide; and magnesium silicate used to improve mold flow, extrusion characteristics, and the homogeneity of elastomers and fillers.
  • PROMIXTM 400 can reduce nerve, shrinkage, mixing cycle time, energy consumption, and viscosity and enhance green tack.
  • CONTINEXTM Carbon Black N660 refers to a furnace grade carbon black compound manufactured by Continental Carbon Company and is both tire grade and mechanical rubber grade. CONTINEXTM Carbon Black N660 has the following specifications: iodine adsorption of 36 g/kg; oil absorption 90 10-5 m 3 /kg; oil absorption compressed of 74 10-5m 3 /kg/NSA multipoint of 35 m 2 /g; STSA of 34 m 2 /g; pour density of 440 kg/m 3 ; and a delta stress at 300% elongation of 02.3 MPa or -330 psi and is useful in carcass and innerliner functions for tires, medium reinforcing for innertubes, cable insulation, and body mounts for mechanical rubber.
  • Calsol- 810 refers to a naphthenic oil manufactured by Calumet Specialty Products and is refined form a blend of naphthenic crudes using a multistage hydrogenation process, compatible with synthetic elastomers and their additives and designed to increase viscosity- gravity constants and aromatic s levels, and lower aniline points. It exhibits high VGC levels and low aniline points.
  • This compound can be used in a variety of compounds, including but not limited to adhesives, defoaming agents for paper and paperboard, defoaming agents used in coatings, textiles and textile fibers, resin bonded filers, animal glue defoamer, surface lubricants for the manufacture of metallic articles such as rolling foils and sheet stock, and rubber articles intended for repeated use.
  • the specifications of Calsol-810 include a viscosity at 40°C minimum of 18.70, maximum of 21.70; API gravity minimum of 23.5, maximum of 26.0; flash point minimum of 160°C; Pour point maximum of -34°C; aniline point minimum of 68.3°C and maximum of 76.7°C.
  • MAGLITETM K refers to a magnesium oxide compound manufactured by Hallstar designed to produce a lower activity product for applications where longer reaction time is required.
  • MAGLITETM K can be used in a wide variety of polymer applications including fluoroelastomers, butyl, chlorobutyl, chlorinated rubber, chlorosulfonated polyethylene, and nitrile.
  • MAGLITETM K The specifications of MAGLITETM K include a composition of 94.5% Magnesium Oxide, 1.0% calcium oxide, and 0.03% chloride; ignition loss of 4.0%; mean particle size of 2.0 microns; bulk density of 26 lb/ft 3 ; and a BET surface area of 40 m 2 /g.
  • KADOXTM 911 refers to a zinc oxide manufactured by Horsehead Corporation and is a French process, high purity, very fine particle size zinc oxide. KADOXTM 911 is designed to provide a zinc oxide with high surface area and reactivity with minimum setting and opacity. In rubber, KADOXTM 911 is designed to provide high activating power and reinforcement with an accelerating effect.
  • the specifications for KADOXTM 911 include a composition of zinc oxide 99.9%, cadmium oxide 0.005%, iron (III) oxide 0.001%, lead oxide 0.001%, and water soluble salts 0.02%; a mean surface particle diameter of 0.12 microns; a specific surface of 9.0 m 2 /g; a specific gravity of 5.6; and an apparent density of 35 lb/ft 3 .
  • ALT AXTM MBTS refers to mercaptobenzothiazole disulfide, is also referred to as benzothiazyl disulfide, manufactured by Vanderbilt Chemicals, LLC and useful in natural and synthetic rubbers as a primary accelerator and scorch-modifying secondary accelerator in NR and SBR copolymers, in neoprene G types as a retarder or plasticizer, and in W types as a cure modifier.
  • ALT AXTM MBTS is moderately soluble in toluene and chloroform, insoluble in gasoline and water and is 94% benzothiazole disulfide and 5% white mineral oil.
  • ALT AXTM MBTS includes an ash content of 0.7% maximum, a heat loss of 1.0% maximum, a melting range of 164°C to 179°C, and a density at 20°C of 1.54 Mg/m 3 .
  • MISTRONTM HAR refers to a talc, an insoluble mineral of the magnesium silicate, and made by a delamination process designed to increase aspect ratio and result in a more lamellar talc produced by Imerys.
  • MISTRONTM HAR is used as a reinforcing filler in partial replacement of carbon black in tire inner liners and has properties that restrict liquid and gas diffusion increasing the diffusion path and improving impermeability.
  • MISTRONTM HAR can limit oxygen diffusion in the tire carcass preventing steel cord oxidation and improving durability.
  • MISTRONTM HAR can improve scorch time, viscosity, and cut growth resistance.
  • LINPLASTTM 812 refers to a Di-C 8 Cio C 12 alkyl phthalate fatty alcohol produced by Sasol and can be used as a plasticizer to provide thermal resistance and cold flexibility in elastomers, sealing compounds, and lubricants.
  • JAYFLEX refers to a plasticizer and substitute for Di (2-ethylhexyl) phthalate (DOP) in most flexible PVC applications.
  • BENZOFLEX TX 2088 refers to a high solvating plasticizer manufactured by Eastman useful in PVC, polyvinyl acetate, and water-based adhesive systems for flooring and interior surfaces, latex caulks, latex sealants, polysulfide sealants, pressure sensitive adhesives, PVAc water based adhesives, PVC plastisol sealant, and VAE water based adhesives.
  • BENZOFLEX TX 2088 properties include a maximum acidity of 0.1%, a specific gravity of 1.16, a flash point of 202°C, and a viscosity of 71 mPas.
  • WINGTACKTM 10 refers to a liquid aliphatic C-5 petroleum hydrocarbon resin manufactured by Cray Valley having low color and low specific gravity.
  • WINGTACK TM 10 is used as tackifying resin of elastomers such as SIS, SBS, polyisoprene, butyl, EPDM, and SBR. It is generally soluble in solvents having low to medium polarity and design to improve low temperature properties of compounds.
  • WINGTACK TM 10 properties include a molecular weight of 500g/mole, a specific gravity of 0.90, and a viscosity of 30,000 cps.
  • Natural Rubber SMR-L refers to natural rubber, specifically standard Malaysian rubber of the L technical specifications which include: a dirt content ⁇ 0.02, ash content ⁇ 0.05, nitrogen content ⁇ 0.60, volatile matter ⁇ 0.50, plasticity retention index of 60%, a Wallace Rapid Plasticity minimum of 35.0.
  • Natural Rubber SMR-CV refers to natural rubber, specifically standard Malaysian rubber of the CV 60 technical specifications which include: a dirt content ⁇ 0.02, ash content ⁇ 0.05, nitrogen content ⁇ 0.60, volatile matter ⁇ 0.80, plasticity retention index of 60%.
  • Rubbermakers Sulfur OT refers to an oil treated grade of sulfur used to vulcanize rubber compounds having properties which include a sulfur purity of 99.0%, a heat loss of 0.15%, ash content of 0.10%, an acidity as H2SO4 of 0.01%, an oil treatment of 0.5%, and a specific gravity of 2.07.
  • Santicizer 711 refers to a compound of the composition of diundecyl benzene- 1 ,2- dicarboxylate, also known as di(c7-9-l l-alkyl) phthalate; 1 ,2-Benzenedicarboxylic acid; or Di-C7-9-l l-akyl ester.
  • Dioctyl Terephthalate refers to bis(2-ethylhexyl) benzene- 1 ,4-dicarboxylate, also known as Di(2-ethylhexyl)terephthalate, DOTP, or DEHT, a compound having the formula C6H4(C02C8H17)2 and is a non-phthalate plasticizer useful for softening PVC plastics.
  • Bis 2 ethyl hexyl sebacate refers to bis(2-ethylhexyl) decanedioate, or dioctyl sebacate and useful as a plasticizer.
  • the present disclosure provides a butyl based composition comprising at least one low Tg liquid hydrocarbon resin, or mixtures of two or more hydrocarbon resins, or mixture of one or more low Tg hydrocarbon resins with high Tg hydrocarbon resins.
  • the low Tg liquid hydrocarbon resin is also referred to as a "hydrocarbon resin.”
  • the hydrocarbon resin is comprised of aliphatic and aromatic components, or a blend of the same in varying ratios, or a derivative.
  • the present hydrocarbon resin improves filler dispersion, aids as a processing aid to improve mixing efficiency, improves (increases) elongation and imparts excellent flex fatigue resistance properties to the composition.
  • permeability characteristics are not affected by varying quantities of the present hydrocarbon resin.
  • Hydrocarbon resins are used in butyl based compositions to achieve a balance in mechanical and flex fatigue resistance properties.
  • prior art liquid resins referred to herein as "homogenizing resins”
  • Mw molecular weight
  • Examples of prior art/homogenizing resin systems include (but are not limited to) STRUKTOLTM 40 MS (Struktol Inc.) and PROMIXTM 400 (Flow Polymers).
  • One disadvantage of prior art homogenizing resin is the high resin Tg.
  • prior art homogenizing resins have high softening points between ⁇ 80°C to 150°C and Tg between 30°C to 100°C, resulting in a butyl based composition with a high Tg (and LTB) and decreased low temperature flex fatigue resistance.
  • Tg (or LTB) of the butyl polymers such as bromobutyl
  • the polymer Tg cannot be altered unless a change in the molecular structure is created.
  • the present hydrocarbon resin has a number average molecular weight (“Mn”) between 10 and 1000, preferably between 20 and 500, and more preferably between 50 and 300; and a weight average molecular weight (“Mw”) between 50 and 5000, preferably between 100 and 2000, and more preferably between 200 and 1000.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the properties of an exemplary hydrocarbon resin is compared to a prior art resin in Table 1 below.
  • Mw, Mn, and MWD was measured by the test method described herein.
  • the molecular weight was measured using Tosoh EcoSEC HLC-8320GPC instrument with enclosed Refractive Index (RI) Ultraviolet and (UV) detectors. The instrument was controlled and molecular weight was calculated using EcoSEC Workstation (Version 1.11) software. 4 columns (PLgel 5 ⁇ 500A; 5 ⁇ 500A; 5 ⁇ 10E3A; 5 ⁇ Mixed-D) were connected in series for effective separation.
  • a sample was prepared by dissolving 24mg (+/-lmg) of hydrocarbon resin in 9 mL of tetrahydrofuran (THF) solution.
  • THF tetrahydrofuran
  • the sulfur/THF solution (having a ratio of lmL sulfur solution per lOOmL THF solvent) was used as flow marker, for measurement of molecular weight.
  • the dissolved sample was filtered using 0.45mm syringe filter.
  • the GPC calibration was done using a series of selected polystyrene standards that are of narrow molecular weights and cover the molecular weight range of the columns respective range of separation.
  • the aromatic H mole content of the present hydrocarbon resin is 0 - 10%, preferably between 0 - 7%, and more preferably between 0 - 5%; the olefin H mole content is 0 - 30%, preferably between 0 - 20%, and more preferably between 5 - 15%; the aliphatic H mole content is 70 - 100%, preferably between 75 - 95%, and more preferably between 80 - 90%.
  • H NMR proton nuclear magnetic resonance
  • Aromatic H mole content, olefin H mole content, and aliphatic H mole content was determined by the test method described herein. 500 MHz Aglient or Bruker Pulsed Fourier Transforms Nuclear Magnetic resonance Spectrometer (FT-NMR) was used for measurement of aromaticity. The IHNMR data is used to determine the percentage of aromatic, olefinic and aliphatic protons. Samples are prepared by dissolving 20(+/-l) mg of sample in 2.5 ml of deuterated tetrachloroethane. The percentage of aromatic, olefinic, and aliphatic protons was obtained by normalizing the total integral area of aliphatic, olefinic, and aromatic to 100.
  • the glass transition (Tg) of the present hydrocarbon resin is between 0°C and -80°C, preferably between -10°C and -75°C, and more preferably between -15°C and -60°C. 8(+/-lmg) of the sample was weighed and introduced in an aluminum pan. A cover was placed on the pan and sealed with a press. The sample was conditioned by one heating and cooling cycle as described. Sample was heated from 25 °C to 80°C at a rate of 20°C/min followed by a 1 min hold at 80°C (first heating cycle).
  • the sample was cooled from 80°C to -100°C at a rate of 10°C/min followed by 5 minute hold at -100°C (first cooling cycle).
  • the Tg of resin is measured by again heating the sample from -100°C to 80°C at a rate of 20°C/min (second heating cycle).
  • the glass transition temperature reported is the midpoint of step change when heated during the second heating cycle.
  • the Tg (or LTB) of the present butyl based composition is a function of the Tg of the individual components (as per the Flory-Fox equation) and can be altered by changing the formulation. To maintain cold temperature flex properties, the butyl based composition Tg (or LTB) is then reduced without increasing permeability coefficient.
  • the present butyl based compositions comprise a primary polymer.
  • the present butyl based composition can also include a secondary polymer, a tackifier resin, stearic acid, an anti-scorch agent, process oil, and a filler.
  • the butyl based composition can also include a curative package.
  • An exemplary butyl based composition is set out in Table 2 below.
  • the primary polymer (also referred to as "the polymer”) described herein is at least one isobutylene based polymer, homo-polymers, copolymers, blends of the same, or blends of primary polymer with other secondary polymers.
  • a primary polymer include isobutylene-isoprene elastomers such as butyl ("IIR"), halogenated elastomers such as bromobutyl ("BUR”), chlorobutyl (“CIIR”), star branched bromobutyl (“SBB”), and star branched chlorobutyl (“SBC”).
  • Isobutylene copolymers include isobutylene polymerized with co-monomers other than isoprene and include, for example, isobutylene-co-para-methyl styrene copolymers and halogenated versions of the same such as EXXPROTM. Table 3 provides exemplary primary polymers and associated properties.
  • the halogenated butyl or star- branched butyl rubber can be halogenated such that the halogenation is primarily allylic in nature. This can be achieved as a free radical bromination or free radical chlorination, or by such methods as secondary treatment of electrophilically halogenated rubbers, such as by heating the rubber, to form the allylic halogenated butyl and star-branched butyl rubber. Exemplary methods of forming the allylic halogenated polymer are disclosed by Gardner et al., in U.S. Patent Nos. 4,632,963, 4,649,178, and 4,703,091.
  • the halogenated butyl rubber can be halogenated in multi-olefin units which are primary allylic halogenated units, and wherein the primary allylic configuration is present to at least 20 mole percent (relative to the total amount of halogenated multi-olefin).
  • Star-branched halogenated butyl rubber (“SBHR”) is a composition of a butyl rubber, either halogenated or not, and a polydiene or block copolymer, either halogenated or not. This halogenation process is described in detail in U.S. Patent Nos. 4,074,035, 5,071,913, 5,286,804, 5,182,333 and 6,228,978.
  • the secondary polymer is not limited by the method of forming the SBHR.
  • polydienes/block copolymer or branching agents
  • polydienes are typically cationically reactive and are present during the polymerization of the butyl or halogenated butyl rubber, or can be blended with the butyl or halogenated butyl rubber to form the SBHR.
  • the branching agent or polydiene can be any suitable branching agent, and the invention is not limited to the type of polydiene used to make the SBHR.
  • the SBHR is typically a composition of the butyl or halogenated butyl rubber as described above and a copolymer of a polydiene and a partially hydrogenated polydiene selected from the group including styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber, styrene- butadiene-styrene and styrene-isoprene-styrene block copolymers.
  • These polydienes are present, based on the monomer wt. %, greater than 0.3 wt. %, or from 0.3 to 3 wt. % or from 0.4 to 2.7 wt. %.
  • a commercial SBHR is Bromobutyl 6222 (ExxonMobil Chemical Company), having a Mooney viscosity (ML 1+8 at 125°C, ASTM 1646, modified) of from 27 to 37, and a bromine content of from 2.2 to 2.6 wt. % relative to the SBHR. Further, cure characteristics of Bromobutyl 6222 are as follows: MH is from 24 to 38 dNm, ML is from 6 to 16 dNm (ASTM D2084, modified)
  • An exemplary halogenated butyl rubber is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is from 27 to 37 (ML 1+8 at 125°C, ASTM 1646, modified), and the bromine content is from 1.8 to 2.2 wt. % relative to the Bromobutyl 2222. Further, cure characteristics of Bromobutyl 2222 are as follows: MH is from 28 to 40 dNm, ML is from 7 to 18 dNm (ASTM D2084, modified). Another commercial available halogenated butyl rubber used as the secondary polymer is Bromobutyl 2255 (ExxonMobil Chemical Company).
  • Mooney viscosity is from 41 to 51 (ML 1+8 at 125°C, ASTM 1646, modified), and the bromine content is from 1.8 to 2.2 wt. %.
  • cure characteristics of Bromobutyl 2255 are as follows: MH is from 34 to 48 dNm, ML is from 11 to 21 dNm (ASTM D2084, modified).
  • the hydrocarbon resin described herein is not limited to the commercial source of any of the halogenated rubber.
  • Cure properties were measured using a MDR 2000 and 0.5 degree arc or an ODR 2000 and 3 degree arc at the indicated temperature, according to ASTM D2084. Test specimens were cured at the indicated temperature, typically from 150°C to 160°C, for a time corresponding to t90 + appropriate mold lag.
  • the values "MH” and “ML” used here and throughout the description refer to "maximum torque” and “minimum torque”, respectively.
  • the “MS” value is the Mooney scorch value
  • the "ML(l+4)” value is the Mooney viscosity value.
  • the error (2 ⁇ ) in the later measurement is + 0.65 Mooney viscosity units.
  • the values of "t” are cure times in minutes, and “ts” is scorch time" in minutes.
  • Oxygen permeability was measured using a MOCON OxTran Model 2/61 operating under the principle of dynamic measurement of oxygen transport through a thin film as published by Pasternak et al. in JOURNAL OF POLYMER SCIENCE: PART A-2, P 467 (1970).
  • the units of measure are cc-mm/m 2 -day-mmHg.
  • the method is as follows: flat film or rubber samples are clamped into diffusion cells which are purged of residual oxygen using an oxygen free carrier gas. The carrier gas is routed to a sensor until a stable zero value is established. Pure oxygen or air is then introduced into the outside of the chamber of the diffusion cells. The oxygen diffusing through the film to the inside chamber is conveyed to a sensor which measures the oxygen diffusion rate.
  • Permeability was tested by the following method. Thin, vulcanized test specimens (0.4 mm + 0.05 mm) from the sample compositions were mounted in diffusion cells and conditioned in an oil bath at 65 °C. The time required for air to permeate through a given specimen is recorded to determine its air permeability. Test specimens were circular plates with 12.7-cm diameter and 0.38-mm thickness. The error (2 ⁇ ) in measuring air permeability is + 0.245 (xlO 8 ) units.
  • Primary polymers can be solution mixed, melt mixed, solid state mixed or reactor mixed blends of two or more of the above elastomers.
  • the isobutylene based composition can comprise of primary polymers from 30 to 100 phr, or from 50 to 100 phr, or from 70 to 100 phr.
  • the butyl based composition can also include secondary polymers.
  • Secondary polymers include, but are not limited to, natural rubber (“NR”), cis-polyisoprene (“IR”), solution and emulsion styrene butadiene rubber (“s-SBR” and “e-SBR”), ethylene propylene diene rubber (“EPDM”).
  • NR natural rubber
  • IR cis-polyisoprene
  • s-SBR solution and emulsion styrene butadiene rubber
  • EPDM ethylene propylene diene rubber
  • the secondary polymer can include derivatives and functionalized variations of polymer, and solution mixed, melt mixed, solid state mixed or reactor mixed blends of two or more of the above mentioned primary and secondary elastomers and their derivatives.
  • the butyl based composition comprises a secondary polymer (or a combination of their blends) from 0 to 70 phr, from 0 to 50 phr, and from 0 to 30 phr.
  • the total of the primary and secondary polymer is 100 phr.
  • the butyl based composition can also include at least one filler or multiple fillers.
  • Fillers are used for imparting sufficient green strength to the compound to enable smooth processing, and for achieving the required balance of mechanical properties in the cured compounds (high strength, modulus and toughness). Addition of a filler or combination of fillers can assist in significantly reducing the butyl based composition permeability. However, increased amounts of filler can result in poor fatigue resistance and crack properties.
  • Specific fillers include carbon black, silica, silicates, calcium carbonate, clays (low and high aspect ratio), mica, aluminum oxide, starch, or mixtures thereof. Furthermore, the fillers may be intercalated, exfoliated, layered, functionalized or pre-treated with certain chemicals in some cases.
  • the filler can be pre-mixed with the primary or secondary polymer, or their combination, and introduced as a masterbatch into the composition.
  • the butyl based composition comprises fillers (or a combination of fillers) from 0 to 100 phr, from 20 to 90 phr, and from 30 to 80 phr.
  • the inorganic fillers (type and amount) do not affect the Tg.
  • the butyl based composition also includes process oil, or blends of two or more process oils.
  • process oil or blends of two or more process oils.
  • the presence of oil aids in processing the polymer during mixing.
  • the addition of oil increases the mixing time by reducing the compound temperature.
  • the molecular weight of oils is low. Therefore, the oil also acts as a plasticizer by increasing the free volume and decreasing the overall compound Tg.
  • naphthalenic oil has been shown to decrease the Tg (and LTB) of isobutylene based innerliner compounds.
  • the addition of oil has also been shown to increase the permeability coefficient, which is undesirable for butyl based composition for inner liner applications.
  • Figures 2A and 2B show the effect of varying amounts of naphthalenic oil on Tg (and LTB) and permeability properties of two butyl based compositions.
  • the effect of varying amounts of naphthalenic oil on other butyl based compositions are shown in Table 4A and 4B below:
  • useful process oils include paraffinic oils, naphthalenic oils, treated distillate aromatic extracts ("TDAE”), methyl-ethyl-ketone oils (“MEK”), poly-alpha-olefins (“PAO”), hydrocarbon fluid additives ("HFA”), polybutene oils (“PB”), or mixtures thereof.
  • the amount of process oil (or a combination of fillers) in the present butyl based compositions comprise from 0 - 20 phr, preferably from 0 - 14 phr, and more preferably from 0 - 8 phr.
  • the present butyl based composition can further comprise a plasticizer including
  • isobutylene based compositions are often limited by low green strength (during processing), difficulty mixing, presence of blisters during sheeting, low tack (to the carcass), low carcass adhesion, low self-to-self adhesion, high Tg (and LTB) and poor low temperature fatigue resistance.
  • a secondary polymer such as natural rubber
  • addition of natural rubber can decrease the Tg (and LTB) of isobutylene based compositions described herein.
  • the addition of natural rubber can also increase the permeability coefficient, which is undesirable for inner liner butyl based compositions.
  • Hydrocarbon resins of the present butyl based compositions can be produced by different processes and are not limited to any one manufacturing methodology.
  • present hydrocarbon resins are made by combining the feed streams described below in a polymerization reactor with a Friedel-Crafts or Lewis Acid catalyst at a temperature between 0°C and 200°C (generally around 20°C to 30°C).
  • the feed streams comprise raffinates of the ESCOREZTM E5000 process.
  • Friedel-Crafts polymerization is generally accomplished by use of known catalysts in a polymerization solvent, and the solvent and catalyst may be removed by washing and distillation.
  • Nonaromatic components can include recycle feed stream of the chemical plant.
  • the component of the feed streams are generally a synthetic mixture of cis-1, 3-pentadiene, trans-1, 3-pentadiene, and mixed 1, 3-pentadiene.
  • feed components do not include branched C5 diolefins such as isoprene.
  • the feed component may be supplied in one embodiment as a mixed distillate cut or synthetic mixture comprising up to 20 wt. % cyclopentadiene or dimer of cyclopentadiene up to 30 wt.
  • % of other components such as, for example, 10 - 20 wt. % cyclopentene, 10 - 20 wt. % inert hydrocarbons, and optionally relatively minor amounts of one or more other olefins and diolefins such as methyl-cyclopentadiene or dimer or trimers of methyl-cyclopentadiene, and the like.
  • Petroleum fractions containing aliphatic C5 to C6 linear, branched, alicyclic mono-olefins, diolefins, and alicyclic CIO diolefins can be polymerized.
  • the aliphatic olefins can comprise one or more natural or synthetic terpenes, preferably one or more of alpha- pinenne, dipentene, limonene or isoprene dimers.
  • C8-C12 aromatic/olefinic streams containing styrene, vinyl toluene, indene, or methyl -indene can also be polymerized as such or in mixture with the aliphatic streams.
  • reaction product is quenched with isopropanol and water mixture.
  • aqueous layer is then separated from the reaction product using a separating funnel.
  • the reaction product can contain several non-polymerizable molecules/paraffins. These are separated from the polymerized hydrocarbon resin by steam stripping at 250°C. The resin yield is ⁇ 31%.
  • the effect of each of the components of the butyl based composition on the Tg of the butyl based composition can vary.
  • the components of the butyl based composition can include, but are not limited to, a primary polymer, a secondary polymer, an oil, the hydrocarbon resin, a tackifier, additives and the curing system.
  • the Tg of the primary polymer can largely impact the Tg of the butyl based composition.
  • Tg of the butyl based composition is effected by the oil, hydrocarbon resin and tackifier components.
  • oil has a low Tg and can increase the free volume of the polymer chains.
  • a low Tg reduces the Tg of the butyl based composition and improves fatigue, cold temperature properties, and ease of manufacture.
  • a large amount of oil in the butyl based composition can increase permeability.
  • CF correction factor
  • the difference between calculated and experimental Tg was applied.
  • Tg of the butyl based composition was then calculated using different Tg values for oils and resins. Components were then selected to produce the desirable Tg ranges.
  • Figures 5A and 5B show Tg of the butyl based composition plotted with assumed Tg values of oils and resins. From these graphs, we inferred that a butyl based composition having a Tg value of -35°C require either an oil Tg that is lower or equal to -85°C (at the same resin type and amount), or a hydrocarbon resin Tg that is equal to or lower than 5°C.
  • EXXPROTM 3433 and EXXPROTM 3745 Commercially available polymers (EXXPROTM 3433 and EXXPROTM 3745) were obtained from ExxonMobil Chemical Company.
  • EXXPROTM inner liner program trial grades (EXXPROTM 03-1, EXXPROTM NPX 1603 and EXXPROTM XP-50) were manufactured at ExxonMobil Chemical Company Baytown Chemical Plant ("BTCP"). Properties of the different EXXPROTM grades can be found in Table 4. Natural rubber SMR- L and SMR CV 60 was used, whenever needed. Carbon black N660 (Continental Carbon) was used as the primary filler. ESCOREZTM 1102 (ExxonMobil Chemical Company) was used as the tackifier.
  • STRUKTOLTM 40 MS flakes was used as the homogenizing resin.
  • Naphthalenic oil (CALSOL-810, Calumet Specialty Products) was used as the process oil.
  • Magnesium Oxide (MAGLITE-K, Hallstar) was used as the scorch retarder.
  • Zinc Oxide (KADOXTM 911, Horsehead Corporation) and Sulfur (Rubbermakers OT, Akrochem Corporation) were used as the vulcanizing agents.
  • MBTS (ALTAX TM, Vanderbilt Chemicals) was used as the accelerator.
  • Talc AMTAL 6000D, Winfield Chemical Company
  • Mistron HAR were used as high aspect ratio fillers wherever required.
  • compositions were prepared by conventional methods used in the tire and rubber industries.
  • isobutylene based elastomers are prepared in two stages (although, in some cases, it could be done in one stage).
  • the first stage also called the non-productive stage
  • the elastomers are mixed with the filler and processing aids (excluding the curative package).
  • the second stage also called the productive stage (or final stage)
  • the non-productive batch is mixed with the curative package.
  • the final temperatures and total mixing times achieved in the non-productive stage is much greater than the productive stage.
  • the final temperatures in the non-productive and productive mix ranges from 120°C to 170°C and 90°C to 110°C respectively.
  • the mixing times depend on the mixer, the rotor configuration, rotor speed, the mixer cooling mechanism, the amount and type of filler used, the composition of the elastomer (heat conductivity of the elastomer), the oil addition time, and several other factors.
  • the compositions described were prepared in a 1570 cc BANBURRYTM mixer (Black BR) or 5310 cc BANBURRYTM (Black OOC).
  • NP non-productive
  • the industry uses a non-productive (“NP") master batch fill factor of around - 75% to 80% and a rotor speed of 40 to 60 rpm. In our studies, we tried to keep the fill factor at around ⁇ 77% and a rotor speed of 70 rpm.
  • the total NP mixing time was approximately 5 to 7 minutes. This is the typical mix time for 2 wing mixers; for 4 wing mixers, the mix time could be as low as 3.5 minutes. In all cases, the material dumping was temperature controlled and not time controlled.
  • the fill factors were kept at - 77% and the rotor speed was kept at 40 rpm.
  • the final batch was dumped at 100°C to 105°C.
  • the total final batch mixing times were 2 - 3 minutes. This is the typical mix time for 2 wing mixers; for 4 wing mixers, the mix time could be as low as 1.5 minutes.
  • the final batch material dumping was also temperature controlled and not time controlled.
  • the produced compositions were for several minutes on two roll mills to prepare thick pads. Whenever required, these pads were then remixed on large two roll mills to achieve the desired thickness for certain molds.
  • Butyl based compositions were made with varying amounts of natural rubber (from 0 to 30 phr natural rubber) for both BUR 2222 (isobutylene-isoprene based elastomer) and EXXPROTM MDX 03-1 (isobutylene-co-para-methyl-styrene based elastomer) using the model formulation provided in Table 2 above. In all cases the total elastomer content
  • Figures 1A and IB show the effect of varying the amounts of natural rubber on the composition Tg (and LTB) and permeability properties of both BUR 2222 and EXXPROTM MDX 03- 1 based compositions. The effect of varying the amounts of natural rubber on the composition properties of both BUR 2222 and
  • EXXPROTM MDX 03-1 are shown below in Table 6A, 6B and 6C.
  • Butyl based compositions were made with varying amounts of process oils, namely naphthalenic oil (from 0 - 12 phr oil) for both BUR 2222 (isobutylene-isoprene based elastomer) and EXXPROTMMDX 03-1 (isobutylene-co-para-methyl-styrene based elastomer) using the butyl based composition provided in Table 2 above.
  • Figures 2A and 2B show the effect of varying the amounts of oil on the composition Tg (and LTB) and permeability properties of both BUR 2222 and EXXPROTM MDX 03-1 based compositions.
  • Butyl based compositions were made with several commercially available plasticizers using BUR 2222 (isobutylene-isoprene based elastomer). The formulation described above in Table 2 above was modified. Here, plasticizers were added (by 10 phr) in addition to the ingredients specified in Table 2.
  • Table 7 shows effect of several plasticizers on ATg depression and permeability increase when introduced at 5 wt. % (10 phr) to the composition.
  • Example 4 Butyl based compositions were made with varying amounts of homogenizing hydrocarbon resin, namely, STRUKTOLTM 40 MS (from 0 phr to 10 phr resin) for both BUR 2222 (isobutylene-isoprene based elastomer) and EXXPROTM MDX 03-1 (isobutylene-co- para-methyl-styrene based elastomer) using the formulation of the butyl based composition provided in Table 2.
  • the effect of varying the amounts of oil on the composition properties of both BUR 2222 and EXXPROTM MDX 03-1 are shown below in Table 8.
  • Butyl based compositions were made with a different low Tg liquid resins (replacing the homogenizing resin) and EXXPROTM MDX 03-1 (isobutylene-co-para- methyl- styrene based elastomer) using the butyl based composition provided in Table 2.
  • Table 9 shows the effect on ATg depression and permeability increase when the hydrocarbon resin was substituted for the homogenizing resin.
  • Butyl based compositions were made with various blends of different low Tg liquid resins Struktol 40 MS with EXXPROTMMDX 03-1 (an isobutylene-co-para-methyl- styrene based elastomer).
  • Table 11A through Table 11B shows the effect of blended resins on composition properties. The addition of these blends can be used to balance the butyl based composition properties, which is desirable for applications such as tire inner liners.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition à base de butyle contenant des résines hydrocarbonées. La résine hydrocarbonée a une Tg de -10 à 25 °C, un poids moléculaire moyen en nombre entre 20 et 500, un poids moléculaire moyen en poids entre environ 100 et environ 2000, et une température de transition vitreuse entre environ 0 et environ -80° C.
PCT/US2018/035305 2017-08-18 2018-05-31 Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation WO2019036085A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18731345.7A EP3668923A1 (fr) 2017-08-18 2018-05-31 Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation
CN202211283875.8A CN115466466A (zh) 2017-08-18 2018-05-31 用于基于丁基的组合物的烃树脂及其制造方法
US16/634,389 US10982081B2 (en) 2017-08-18 2018-05-31 Hydrocarbon resins for butyl based compositions and methods of making the same
CN201880053521.XA CN110997797B (zh) 2017-08-18 2018-05-31 用于基于丁基的组合物的烃树脂及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201762547349P 2017-08-18 2017-08-18
US62/547,349 2017-08-18
EP17196049.5 2017-10-12
EP17196049 2017-10-12

Publications (1)

Publication Number Publication Date
WO2019036085A1 true WO2019036085A1 (fr) 2019-02-21

Family

ID=60083172

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/035305 WO2019036085A1 (fr) 2017-08-18 2018-05-31 Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation

Country Status (1)

Country Link
WO (1) WO2019036085A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021021417A1 (fr) * 2019-07-26 2021-02-04 Exxonmobil Chemical Patents Inc. Agents de modification de polymère hydrocarboné ayant une aromaticité élevée et leurs utilisations

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2631984A (en) 1950-04-18 1953-03-17 Goodrich Co B F Isoolefin polyolefin interpolymer derivatives and compositions comprising the same
US3099644A (en) 1959-10-06 1963-07-30 Exxon Research Engineering Co Continuous chlorination and bromination of butyl rubber
US4074035A (en) 1975-04-22 1978-02-14 Exxon Research & Engineering Co. Halomethylated aromatic interpolymers
US4384072A (en) 1981-09-30 1983-05-17 Exxon Research & Engineering Co. Process for the manufacture of halogenated elastomers
US4395506A (en) 1980-06-13 1983-07-26 Exxon Research & Engineering Co. Addition of mineral rubber to halobutyl blends
US4513116A (en) 1983-04-01 1985-04-23 Exxon Research And Engineering Co. Process for the manufacture of halogenated polymers
US4554326A (en) 1983-04-01 1985-11-19 Exxon Research & Engineering Co. Process for the manufacture of halogenated polymers
US4632963A (en) 1984-04-05 1986-12-30 Exxon Research & Engineering Co. Halogenated butyl rubber
US4649178A (en) 1984-10-01 1987-03-10 Exxon Research & Engineering Co. Process for producing brominated butyl rubber high in primary allylic bromine
US4650831A (en) 1977-10-08 1987-03-17 Shell Internationale Research Maatschappij B.V. Tires
US4681921A (en) 1984-04-05 1987-07-21 Exxon Research & Engineering Co. Process for preparing improved halogenated butyl rubber
US4703091A (en) 1984-04-05 1987-10-27 Exxon Research & Engineering Co. Halogenated butyl rubber
US5071913A (en) 1987-12-11 1991-12-10 Exxon Chemical Patents Inc. Rubbery isoolefin polymers exhibiting improved processability
US5162445A (en) 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
US5182333A (en) 1987-12-11 1993-01-26 Exxon Chemical Patents Inc. Production of rubbery isoolefin polymers
US5286804A (en) 1991-09-17 1994-02-15 Exxon Chemical Patents Inc. Halogenation of star-branched butyl rubber with improved neutralization
US5681901A (en) 1996-07-24 1997-10-28 Exxon Chemical Patents Inc. Process for halogenating isomonoolefin copolymers
US6228978B1 (en) 1997-06-25 2001-05-08 Exxon Mobil Chemical Patents Inc Star-branched polymer with dendrimer core
US20040092648A1 (en) * 2002-11-07 2004-05-13 Jones Glenn Edward Elastomeric blend for air barriers comprising low glass transition temperature petroleum hydrocarbon resins
US7666341B2 (en) * 2004-02-07 2010-02-23 Tnt Holdings, Llc Screed mold method
EP2348077A1 (fr) * 2010-01-26 2011-07-27 Jotun A/S Composition antisalissure
WO2012050658A1 (fr) * 2010-10-13 2012-04-19 Exxonmobil Chemical Patents Inc. Modificateurs polymères hydrocarbonés
US20130331498A1 (en) * 2012-06-12 2013-12-12 Sumitomo Rubber Industries, Ltd. Rubber composition for tread, and pneumatic tire
US20180194934A1 (en) * 2015-07-02 2018-07-12 Compagnie Generale Des Etablissements Michelin Rubber composition including a hydrocarbon resin having a low glass transition temperature, a specific coupling agent and a primary amine

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2631984A (en) 1950-04-18 1953-03-17 Goodrich Co B F Isoolefin polyolefin interpolymer derivatives and compositions comprising the same
US3099644A (en) 1959-10-06 1963-07-30 Exxon Research Engineering Co Continuous chlorination and bromination of butyl rubber
US4074035A (en) 1975-04-22 1978-02-14 Exxon Research & Engineering Co. Halomethylated aromatic interpolymers
US4650831A (en) 1977-10-08 1987-03-17 Shell Internationale Research Maatschappij B.V. Tires
US4395506A (en) 1980-06-13 1983-07-26 Exxon Research & Engineering Co. Addition of mineral rubber to halobutyl blends
US4384072A (en) 1981-09-30 1983-05-17 Exxon Research & Engineering Co. Process for the manufacture of halogenated elastomers
US4513116A (en) 1983-04-01 1985-04-23 Exxon Research And Engineering Co. Process for the manufacture of halogenated polymers
US4554326A (en) 1983-04-01 1985-11-19 Exxon Research & Engineering Co. Process for the manufacture of halogenated polymers
US4632963A (en) 1984-04-05 1986-12-30 Exxon Research & Engineering Co. Halogenated butyl rubber
US4681921A (en) 1984-04-05 1987-07-21 Exxon Research & Engineering Co. Process for preparing improved halogenated butyl rubber
US4703091A (en) 1984-04-05 1987-10-27 Exxon Research & Engineering Co. Halogenated butyl rubber
US4649178A (en) 1984-10-01 1987-03-10 Exxon Research & Engineering Co. Process for producing brominated butyl rubber high in primary allylic bromine
US5071913A (en) 1987-12-11 1991-12-10 Exxon Chemical Patents Inc. Rubbery isoolefin polymers exhibiting improved processability
US5182333A (en) 1987-12-11 1993-01-26 Exxon Chemical Patents Inc. Production of rubbery isoolefin polymers
US5162445A (en) 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
US5286804A (en) 1991-09-17 1994-02-15 Exxon Chemical Patents Inc. Halogenation of star-branched butyl rubber with improved neutralization
US5681901A (en) 1996-07-24 1997-10-28 Exxon Chemical Patents Inc. Process for halogenating isomonoolefin copolymers
US6228978B1 (en) 1997-06-25 2001-05-08 Exxon Mobil Chemical Patents Inc Star-branched polymer with dendrimer core
US20040092648A1 (en) * 2002-11-07 2004-05-13 Jones Glenn Edward Elastomeric blend for air barriers comprising low glass transition temperature petroleum hydrocarbon resins
US7666341B2 (en) * 2004-02-07 2010-02-23 Tnt Holdings, Llc Screed mold method
EP2348077A1 (fr) * 2010-01-26 2011-07-27 Jotun A/S Composition antisalissure
WO2012050658A1 (fr) * 2010-10-13 2012-04-19 Exxonmobil Chemical Patents Inc. Modificateurs polymères hydrocarbonés
US20130331498A1 (en) * 2012-06-12 2013-12-12 Sumitomo Rubber Industries, Ltd. Rubber composition for tread, and pneumatic tire
US20180194934A1 (en) * 2015-07-02 2018-07-12 Compagnie Generale Des Etablissements Michelin Rubber composition including a hydrocarbon resin having a low glass transition temperature, a specific coupling agent and a primary amine

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"THE VANDERBILT RUBBER HANDBOOK", vol. 105-122, 1990, R.T. VANDERBILT CO., INC.
E. KRESGE; H. C. WANG: "8 KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY", vol. 934-955, 1993, JOHN WILEY & SONS, INC.
PASTERNAK ET AL., JOURNAL OF POLYMER SCIENCE, 1970, pages 467
RUBBER TECHNOLOGY, vol. 298-299, 1995
RUBBER TECHNOLOGY, vol. 311-321, 1995

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021021417A1 (fr) * 2019-07-26 2021-02-04 Exxonmobil Chemical Patents Inc. Agents de modification de polymère hydrocarboné ayant une aromaticité élevée et leurs utilisations
CN114531880A (zh) * 2019-07-26 2022-05-24 埃克森美孚化学专利公司 具有高芳香性的烃聚合物改性剂及其用途

Similar Documents

Publication Publication Date Title
EP2763829B1 (fr) Vessies de vulcanisation de pneus
JP5126987B2 (ja) 炭化水素ポリマー添加物を添加した、優れた不透過性を有するエラストマ組成物
EP0597362B1 (fr) Compositions à base de caoutchouc butyle
JP5027379B2 (ja) エラストマー組成物
US20070270538A1 (en) Elastomeric compositions comprising butyl rubber and propylene polymers
KR20120125548A (ko) 고무 이오노머 및 중합체 나노복합체의 제조 방법
WO2013011820A1 (fr) Composition de caoutchouc, composition de caoutchouc polymérisé, pneumatique, et procédé pour la production de polymère à base d'isobutylène
KR101975723B1 (ko) 고연화점 탄화수소 수지
CA1332019C (fr) Compositions de caoutchouc butylique
EP3999359A1 (fr) Pneus comprenant des composés de caoutchouc qui comprennent des polymères de propylène-alpha-oléfine-diène
JP2005511829A (ja) ハロゲン化イソオレフィン系ターポリマー
JP5543467B2 (ja) ゴム組成物、架橋ゴム組成物及び空気入りタイヤ
US10982081B2 (en) Hydrocarbon resins for butyl based compositions and methods of making the same
PL201635B1 (pl) Mieszanka gumowa na wykładziny wewnętrzne opon, sposób jej wytwarzania i wykładzina wewnętrzna opon ją zawierająca
WO2019036085A1 (fr) Résines hydrocarbonées pour compositions à base de butyle et leurs procédés de préparation
US20210187886A1 (en) Brominated Isobutylene Paramethyl-Styrene Elastomer Curing Bladders
JP7105317B2 (ja) チオアセタート官能化イソブチレン系ポリマー及びそれを含有する硬化性組成物
US20190144654A1 (en) Curative System for Butyl Based Compositions
CN112135848A (zh) 具有烯属侧链取代基的基于异丁烯的聚合物及含有它的可固化组合物
JP2013040234A (ja) ブロック共重合体、その製造方法、それを含むゴム組成物、架橋ゴム組成物及び空気入りタイヤ
WO2023121918A1 (fr) Compositions, vulcanisats et procédés de durcissement

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18731345

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018731345

Country of ref document: EP

Effective date: 20200318