EP3794069A1 - Calandrage intérieur de pneu dopé avec des microsphères thermoplastiques expansibles - Google Patents

Calandrage intérieur de pneu dopé avec des microsphères thermoplastiques expansibles

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Publication number
EP3794069A1
EP3794069A1 EP19722774.7A EP19722774A EP3794069A1 EP 3794069 A1 EP3794069 A1 EP 3794069A1 EP 19722774 A EP19722774 A EP 19722774A EP 3794069 A1 EP3794069 A1 EP 3794069A1
Authority
EP
European Patent Office
Prior art keywords
phr
elastomer
expandable thermoplastic
cured
cured elastomer
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.)
Pending
Application number
EP19722774.7A
Other languages
German (de)
English (en)
Inventor
Xin Jin
Michael B. Rodgers
Pei T. BAO
Ck Shanawas
Babu Shanmugasundaram
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
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
Publication of EP3794069A1 publication Critical patent/EP3794069A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present disclosure relates to elastomers doped with expandable thermoplastic microspheres, their method of manufacture, and their inclusion in air barrier articles such as tire innerliners.
  • Halogenated isobutylene/isoprene copolymers also referred to as halogenated butyl rubbers
  • halogenated butyl rubbers are the polymers of choice for innerliners of tires for passenger, truck, bus, farm and off-road, and aircraft vehicles because they exhibit low air permeability yet are flexible.
  • Bromobutyl rubber, chlorobutyl rubber, and halogenated star-branched butyl rubbers can be formulated for specific tire applications, such as tubes or innerliners.
  • the selection of ingredients and additives for the final commercial formulation depends upon the balance of the properties desired, namely, processability and tack of the green (uncured) compound in the tire plant versus the in-service performance of the cured tire composite.
  • a cured elastomer comprising: an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr.
  • Also disclosed herein is a method comprising: mixing components comprising an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr to produce a doped elastomer, wherein mixing is at a temperature above an expansion initiation temperature and below a maximum exposure temperature for the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured, doped elastomer.
  • mixing components comprising an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr to produce a doped elastomer, wherein mixing is at a temperature above an expansion initiation temperature and below a maximum exposure temperature for the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured, doped elastomer.
  • doped elastomer compositions elastomers doped with expandable thermoplastic microspheres
  • doped elastomer compositions can comprise an elastomer (preferably a halogenated butyl rubber) at about 100 parts per hundred rubber (phr) and expandable thermoplastic microspheres at about 0.1 phr to about 5 phr.
  • elastomer preferably a halogenated butyl rubber
  • expandable thermoplastic microspheres at about 0.1 phr to about 5 phr.
  • other additives can be included for specific applications.
  • doped elastomers for a tire innerliner can comprise halogenated butyl rubber at about 100 phr, expandable thermoplastic microspheres at about 0.1 phr to about 5 phr, an antidusting agent at about 0.1 phr to about 3 phr, a filler at about 20 phr to about 90 phr, a processing oil at about 0.1 phr to about 10 phr, a phenolic resin at about 1 to about 15 phr, and a curing agent, and system, at 0 phr to about 15 phr.
  • a component may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, etc.
  • a copolymer may refer to a polymer comprising at least two monomers, optionally with other monomers.
  • a polymer when referred to as“comprising” a monomer, the monomer is present in the polymer in the polymerized form of the monomer or in the derivative form of the monomer.
  • catalyst components are described as comprising neutral stable forms of the components, it is well understood by one skilled in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • “elastomer” or“elastomeric composition” refers to any polymer or composition of polymers (such as blends of polymers) consistent with the ASTM D1566 definition.
  • Elastomer includes mixed blends of polymers such as melt mixing and/or reactor blends of polymers. The terms may be used interchangeably with the term“rubber.”
  • “phr” is parts per hundred rubber and is a measure common in the art wherein components of a composition are measured relative to a major elastomer component, based upon 100 parts by weight of the elastomer(s) or mbber(s). Unless otherwise noted, values of phr are significant to the hundredths decimal place. Thus, the expressions“1 phr” and“60 phr” are equivalent to 1.00 phr and 60.00 phr, respectively.
  • “isobutylene-based elastomer” or“isobutylene-based polymer” or “isobutylene -based rubber” refers to elastomers or polymers comprising at least 70 mole percent isobutylene.
  • the term“doped elastomer composition” is a general term for all compositions of the present disclosure. The term does not, unless otherwise specified, delineate at what point during production (mixing, molding, or curing) is at and encompasses a cured, doped elastomer composition or a mixture (or compound) of the components suitable for producing the cured, doped elastomer composition.
  • Expandable thermoplastic microspheres are hollow spheres with the thermoplastic shell encapsulating a gas. When heated, the thermoplastic shell softens and the encapsulated gas expands, which increases the microsphere diameter and volume. For example, a 12 micron diameter expandable thermoplastic microsphere with a shell thickness of 2 microns can, when heated, expand to 40 microns in diameter with a shell thickness of 0.1 microns.
  • the term“expandable thermoplastic microspheres,” unless otherwise specified does not indicate the state of expansion and encompasses an unexpanded state and an expanded state.
  • the term “expanded,” unless otherwise specified as fully expanded encompasses partially and fully expanded.
  • Expandable thermoplastic microspheres can be included in the doped elastomer compositions described herein at about 0.1 phr to about 10 phr, about 0.5 phr to about 7 phr, or about 1 phr to about 5 phr.
  • Expandable thermoplastic microspheres can have an average unexpanded diameter of about 5 microns to about 50 microns, about 10 microns to about 40 microns, about 10 microns to about 20 microns, or about 20 microns to about 40 microns.
  • Expandable thermoplastic microspheres can have an average fully expanded diameter of about 10 microns to about 125 microns, about 15 microns to about 100 microns, about 25 microns to about 85 microns, or about 30 microns to about 50 microns.
  • Expandable thermoplastic microspheres can have a density of about 5 kg/m 3 to about 75 kg/m 3 , about 5 kg/m 3 to about 30 kg/m 3 , or about 5 kg/m 3 to about 10 kg/m 3 or about 10 kg/m 3 to about 25 kg/m 3 .
  • the temperature at which the expandable thermoplastic microspheres begin expansion (expansion initiation temperature) and the maximum exposure temperature for the expandable thermoplastic microspheres before degradation or explosion depends on the shell dimensions and the shell composition.
  • the expansion initiation temperature can be from about 80°C to about l75°C, about 80°C to about H5°C, about H5°C to about l35°C, or about l35°C to about l75°C.
  • the maximum exposure temperature for the expandable thermoplastic microspheres before degradation or explosion can be from about l20°C to about 2lO°C, about l20°C to about l75°C, or about l75°C to about 2lO°C.
  • Examples of commercially available expandable thermoplastic microspheres include, but are not limited to, the grades of EXPANCELTM DU (unexpanded thermoplastic microspheres, available from AkzoNobel) listed in Table 1 and the grades of EXPANCELTM DE (expanded thermoplastic microspheres, available from AkzoNobel) listed in Table 2. Table 1. Examples of EXPANCELTM DU (unexpanded thermoplastic microspheres, available from AkzoNobel) listed in Table 1 and the grades of EXPANCELTM DE (expanded thermoplastic microspheres, available from AkzoNobel) listed in Table 2. Table 1. Examples of EXPANCELTM DU
  • the doped elastomer compositions described herein comprise at least one elastomer.
  • Elastomers can be selected from the group consisting butyl rubber (isoprene- isobutylene rubber, “HR”), branched (“star-branched”) butyl rubber, star-branched polyisobutylene rubber, bromobutyl rubber (“BUR”), chlorobutyl rubber(“CIIR”), random copolymers of isobutylene and para- methylstyrene (poly(isobutylene-co-p-methylstyrene)), halogenated poly(isobutylene-co-p-methylstyrene) (“BIMSM”), polybutadiene rubber (“BR”), high cis-polybutadiene, polyisoprene rubber, isoprene-butadiene rubber (“IBR”), styrene- isoprene -butadiene rubber (“SIBR”), s
  • Preferred elastomers include isobutylene based elastomers such as, butyl rubber, halogenated butyl rubber, and halogenated poly(isobutylene-co-p-methylstyrene).
  • Commercial examples include, but are not limited to, EXXPROTM elastomers (halogenated random copolymers of isobutylene and para-methylstyrene, available from ExxonMobil Chemical Company), EXXONTM 2222 (brominated copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM 2255 (brominated copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM 6222 (brominated star-branched copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM 1066 (chlorinated copo
  • the elastomer in total is in the doped elastomer compositions described herein at 100 phr.
  • a doped elastomer composition can include 30-50 phr butyl rubber, 30- 50 phr bromobutyl rubber, 30-50 phr chlorobutyl, and 30-50 phr BIMSM.
  • the doped elastomer compositions described herein can optionally further comprise one or more additives, which include, but are not limited to, antidusting agents, fillers, processing oils, curing agents, activators, retarders, pigments, antioxidants, antiozonants, and combinations thereof.
  • additives include, but are not limited to, antidusting agents, fillers, processing oils, curing agents, activators, retarders, pigments, antioxidants, antiozonants, and combinations thereof.
  • Expandable thermoplastic microspheres have a very low density and, therefore, tend to float in the air when added during compounding. This is especially a problem when an open mixer is used.
  • Antidusting agents can be used to mitigate floating of the expandable thermoplastic microspheres so as to maintain the microspheres in contact with the rubber until incorporated. Examples of antidusting agents include, but are not limited to, calcium carbonate, clays, and combinations thereof.
  • Antidusting agents when included, can be in the doped elastomer composition at about 0.1 phr to about 3 phr, about 1 phr to about 3 phr, or about 1.5 phr to about 2.5 phr.
  • Fillers can improve the mechanical properties and/or barrier properties of the doped elastomer compositions described herein.
  • Examples of fillers include, but are not limited to, silica, talc, titanium dioxide, and carbon black.
  • Silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and combinations thereof.
  • carbon black has a surface area of less than 40 m 2 /g and a dibutylphthalate oil absorption of less than 80 cm 3 /l00 gm.
  • carbon blacks include, but are not limited to N550, N660, N650, N762, and N990 provided in ASTM (D3037, D1510, and D3765), Regal® 85 (carbon black, available from Cabot), Regal® 90 (carbon black, available from Cabot), and combinations thereof.
  • Fillers when included, can be in the doped elastomer composition at about 20 phr to about 90 phr, about 30 phr to about 80 phr, or about 40 phr to about 70 phr.
  • Processing oils are primarily used to improve the processability of the composition during compounding and molding. Processing oils can be petroleum-derived processing oils, synthetic plasticizers, or a combination thereof. Examples of processing oils include, but are not limited to, paraffinic oils, naphthenic oils, aromatic oils, mild extraction solvate (MES), treated distillate aromatic extract (TDAE), and combinations thereof.
  • the preferred plasticizer oil for use in standard, non-DVA (dynamic vulcanized alloy), non-engineering resin-containing innerliner compositions is a paraffinic petroleum oil; suitable hydrocarbon plasticizer oils for use in such innerliners include oils having the following general characteristics.
  • Processing oils when included, can be in the doped elastomer composition at about 0.1 phr to about 10 phr, about 1 phr to about 7 phr, or about 3 phr to about 5 phr.
  • Tackifying resins also improve the processability of the composition.
  • tackifying resins include, but are not limited to, aliphatic hydrocarbon resins, at least partially hydrogenated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic/aromatic hydrocarbon resins, aromatic hydrocarbon resins, dicyclopentadiene derivatives, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, rosin esters, rosin acids, resins grafted with graft monomers, and combinations thereof.
  • Tackifying resins when included, can be in the doped elastomer composition at about 0.1 phr to about 10 phr, about 1 phr to about 7 phr, or about 3 phr to about 5 phr.
  • Curing agents can include curatives, phenolic resins, vulcanizing agents, crosslinking agents, and the like.
  • curing agents when included, can be in the doped elastomer composition at about 0.1 phr to about 15 phr, about 1 phr to about 10 phr, or about 5 phr to about 8 phr.
  • curative examples include, but are not limited to, ZnO, CaO, MgO, AI2O3, CrC>3, FeO, Fe 2 0 3 , and NiO.
  • These metal oxides can be used alone or in conjunction with the corresponding metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.), or with the organic and fatty acids added alone, such as stearic acid, and optionally other curatives such as sulfur or a sulfur compound, an alkylperoxide compound, diamines, diamine derivatives (e.g., DIAKTM, available from DuPont), and combinations thereof.
  • Curing elastomers with curatives may be accelerated and is often used for the vulcanization of elastomers.
  • the mechanism for accelerated vulcanization of natural rubber involves complex interactions between the curative, accelerator, activators, and polymers.
  • all of the available curative is consumed in the formation of effective crosslinks that join together two polymer chains and enhance the overall strength of the polymer matrix.
  • Numerous accelerators include, but are not limited to, stearic acid, diphenyl guanidine (DPG), tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-l ,6-bisthiosulfate disodium salt dihydrate (e.g.
  • DURALINKTM HTS available from Flexsys
  • MBS 2-morpholinothio benzothiazole
  • MOR 90 blends of 90% MOR and 10% MBTS
  • TBBS N-tertiarybutyl-2-benzothiazole sulfenamide
  • OTOS N-oxy diethylene thiocarbamyl-N-oxydiethylene sulfonamide
  • ZH zinc 2-ethyl hexanoate
  • thioureas and combinations thereof.
  • Curatives when included, can be in the doped elastomer composition at about 0.1 phr to about 10 phr, about 1 phr to about 8 phr, or about 3 phr to about 7 phr.
  • Phenolic resins can be used as a curative.
  • phenol formaldehyde resins include resins having the following structure:
  • m ranges from 1 to 50, more preferably from 2 to 10;
  • R is selected from the group consisting of hydrogen and Ci to C 20 alkyls in one embodiment; and is selected from the group consisting of C 4 to C 14 branched alkyls in a particular embodiment; and
  • Q is a divalent radical selected from the group consisting of -CEE-, and -CH 2 -O-CH 2 -. Mixtures of phenolic resins can be used.
  • Phenolic resins can be in any form such as a solid, liquid, solution, or suspension.
  • suitable solvents or diluents include liquid alkanes (e.g., pentane, hexane, heptane, octane, cyclohexane), toluene and other aromatic solvents, paraffinic oils, polyolefinic oils, mineral oils, silicon oils, and combinations thereof.
  • Phenolic resins when included, can be in the doped elastomer composition at about 0.1 phr to about 10 phr, about 1 phr to about 8 phr, or about 3 phr to about 7 phr.
  • One or more crosslinking agents can also be used, especially when silica is also present in the composition.
  • the coupling agent may be a bifunctional organosilane crosslinking agent, which is any silane coupled filler and/or crosslinking activator and/or silane reinforcing agent.
  • Examples of coupling agents include, but not limited to, vinyl triethoxysilane, bis-(3-triethoxysilypropyl)tetrasulfide, vinyl-tris- (beta-methoxyethoxy)silane, methacryloylpropyltrimethoxysilane, gamma-amino-propyl triethoxysilane (e.g ⁇ , A1100TM, available from Witco), gamma- mercaptopropyltrimethoxysilane (e.g., A189TM, available from by Witco), and combinations thereof.
  • vinyl triethoxysilane bis-(3-triethoxysilypropyl)tetrasulfide
  • vinyl-tris- (beta-methoxyethoxy)silane methacryloylpropyltrimethoxysilane
  • gamma-amino-propyl triethoxysilane e.g ⁇
  • Homogenizing agents can enhance the processability of rubber during mixing, extruding, and molding.
  • An example of a homogenization agent includes STRUKTOLTM 40 MS (mixture of dark aromatic hydrocarbon resins, available from Struktol Company).
  • Such agents when included, can be in the doped elastomer composition at about 0.1 phr to about 15 phr, about 3 phr to about 12 phr, or about 5 phr to about 10 phr.
  • the doped elastomer compositions described herein can be formed into air barrier articles such as tire innerliners, pneumatic tires, tire curing bladders, air sleeves (e.g., air shock absorbers), diaphragms, hoses (e.g., gas and fluid transporting hoses).
  • air barrier articles such as tire innerliners, pneumatic tires, tire curing bladders, air sleeves (e.g., air shock absorbers), diaphragms, hoses (e.g., gas and fluid transporting hoses).
  • the articles are prepared by mixing the components at a temperature above the expansion initiation temperature and below the maximum exposure temperature for the expandable thermoplastic microspheres, shaping the mixed components into a desired shape, and then curing to produce the article comprising the cured, doped elastomer composition.
  • Mixing (or compounding) the components can be carried out by combining the components in any suitable internal mixing device such as a BANBURYTM mixer, BRABENDERTM mixer, a Krupp internal mixer with intermeshing rotors, or extruder (e.g., a single screw extruder or twin screw extruder).
  • a suitable internal mixing device such as a BANBURYTM mixer, BRABENDERTM mixer, a Krupp internal mixer with intermeshing rotors, or extruder (e.g., a single screw extruder or twin screw extruder).
  • extruder e.g., a single screw extruder or twin screw extruder.
  • Mixing can occur in a single step or multiple steps.
  • the components of the doped elastomer compositions except the curing agents can be mixed in a non-productive stage. Then, the curing agents can be mixed into the compositions during a productive stage.
  • Suitable mixing rates can range from about 10 RPM to about 100 RPM.
  • the mixing rate can range from a low of about 10 RPM, 30 RPM, or 50 RPM to a high of about 60 RPM, 80 RPM, or 100 RPM.
  • the doped elastomer composition is shaped (or formed) into the desired shape. Suitable methods include, but are not limited to, extruding, calendaring, and combinations thereof.
  • an innerliner layer or“stock” is prepared by (1) calendaring or extruding the doped elastomer composition into a sheet having a thickness of 0.5 mm to 2 mm and (2) cutting the sheet material into strips of appropriate width and length for innerliner application in a particular size or type tire. The liner can then be cured while in contact with the tire carcass and/or sidewall in which it is placed.
  • Curing temperatures can be about l00°C to about 250°C, or about l25°C to about 200°C. Curing times can be minutes to hours, about one minute to about 3 hours, or about 5 minutes to about 30 minutes.
  • Example 1 A cured elastomer comprising: an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr.
  • Example 2 The cured elastomer of example 1, wherein the elastomer comprises about 50 phr to about 100 phr halogenated butyl rubber.
  • Example 3 The cured elastomer of any of the preceding examples, wherein the elastomer comprises bromobutyl rubber, chlorobutyl rubber, or a combination thereof at about 50 phr to about 100 phr.
  • Example 4 The cured elastomer of any of the preceding examples, wherein the expandable thermoplastic microsphere has an average unexpanded diameter of about 5 microns to about 50 microns.
  • Example 5 The cured elastomer of any of the preceding examples, wherein the expandable thermoplastic microsphere has a density of about 5 to about 30 kg/m 3 .
  • Example 6 The cured elastomer of any of the preceding examples further comprising: an antidusting agent about 0.1 to about 3 phr.
  • Example 7 The cured elastomer of any of the preceding examples further comprising:
  • a filler at about 20 phr to about 90 phr.
  • Example 8 The cured elastomer of any of the preceding examples further comprising: a processing oil at about 0.1 to about 10 phr.
  • Example 9 The cured elastomer of any of the preceding examples further comprising: a tackifier at about 0.1 phr to about 10 phr.
  • Example 10 The cured elastomer of any of the preceding examples further comprising: a phenolic resin about 1 phr to about 10 phr.
  • Example 11 The cured elastomer of any of the preceding examples further comprising: a curative at about 0.1 phr to about 10 phr.
  • Example 12 The cured elastomer of any of the preceding examples further comprising: a peptizer at about 0.1 phr to about 1.0 phr.
  • Example 13 The cured elastomer of any of the preceding examples further comprising: a peptizer at about 1 phr to about 15 phr.
  • Example 14 The cured elastomer of any of the preceding examples comprising: the elastomer at 100 phr, the elastomer comprising bromobutyl rubber at about 50 phr to 100 phr; the expandable thermoplastic microsphere at about 1 to about 5 phr; the antidusting agent about 1 to about 3 phr, the antidusting agent comprising calcium carbonate, clay, wax, or a combination thereof; the filler at about 40 phr to about 70 phr, the filler comprising carbon black; the processing oil at about 5 to about 10 phr; the tackifier at about 5 phr to about 10 phr; and the phenolic resin and the curative in total at about 1 phr to about 10 phr.
  • Example 15 An air barrier article comprising the cured elastomer of any of the preceding examples, wherein the air barrier article is selected from the group consisting of a tire innerliner, a pneumatic tire, a tire curing bladder, an air sleeves, a diaphragm, and a hose.
  • Example 16 A tire comprising an innerliner made from the cured elastomer of one of examples 1-14.
  • Example 17 A method comprising: mixing components comprising an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr to produce a doped elastomer, wherein mixing is at a temperature above an expansion initiation temperature and below a maximum exposure temperature for the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured, doped elastomer.
  • mixing components comprising an elastomer at 100 parts per hundred rubber (phr); and an expandable thermoplastic microsphere at about 0.1 to about 10 phr to produce a doped elastomer, wherein mixing is at a temperature above an expansion initiation temperature and below a maximum exposure temperature for the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured, doped elastomer.
  • Example 18 The method of example 16, wherein the mixing temperature is about 80°C to about 235°C.
  • Example 19 The method of one of examples 16-17, wherein the expandable thermoplastic microsphere has an average unexpanded diameter of about 5 microns to about 50 microns.
  • Example 20 The method of one of examples 16-18, wherein the expandable thermoplastic microsphere has a density of about 5 to about 30 kg/m 3 .
  • Example 21 The method of one of examples 16-19 further comprising: shaping the elastomer compound into an innerliner shape in a tire before curing.
  • Example 22 The method of one of examples 16-20, wherein the components further comprise an antidusting agent about 1 to about 3 phr, a filler at about 20 phr to about 90 phr, a processing oil at about 0.1 to about 10 phr, a tackifier at about 0.1 phr to about 10 phr, and a curing agent at about 0.1 phr to about 10 phr.
  • an antidusting agent about 1 to about 3 phr
  • a filler at about 20 phr to about 90 phr
  • a processing oil at about 0.1 to about 10 phr
  • a tackifier at about 0.1 phr to about 10 phr
  • a curing agent at about 0.1 phr to about 10 phr.
  • Example 23 The method of one of examples 16-21, wherein the components comprise: the elastomer at 100 phr, the elastomer comprising bromobutyl rubber at about 50 phr to 100 phr; the expandable thermoplastic microsphere at about 1 to about 5 phr; the antidusting agent about 1 to about 3 phr, the antidusting agent comprising calcium carbonate, wax, clay, or a combination thereof; the filler at about 40 phr to about 70 phr, the filler comprising carbon black; the processing oil at about 5 to about 10 phr; the tackifier at about 5 phr to about 10 phr; and a phenolic resin and a curative in total at about 1 phr to about 10 phr.
  • the components comprise: the elastomer at 100 phr, the elastomer comprising bromobutyl rubber at about 50 phr to 100 phr; the expandable thermo
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps.
  • elastomer compositions were prepared according the formulations in Table 3. The components were mixed in an open mixer. Therefore, a calcium carbonate antidusting agent was used to mitigate floating of the expandable thermoplastic microspheres and maximize their incorporation into the composition.
  • SP-1068 resin (a thermoplastic resin made from octylphenol and formaldehyde, available from Akrochem Corporation)
  • the rheology property of Samples 2 and 3 are within acceptable limits that allow for processing the compounds by standard methods.
  • the air permeability properties are decreased by 4% and 16% for Samples 2 and 3, respectively, which means the permeability to air is reduced and the compounds’ suitability for use in an air barrier article is enhanced.
  • compositions and methods are described in terms of“comprising,”“containing,” or“including” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form,“from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

La présente invention concerne un élastomère durci comprenant : un élastomère à 100 parties pour cent de caoutchouc (pce) ; et une microsphère thermoplastique expansible à une proportion d'environ 0,1 à environ 10 pce. Un tel élastomère durci peut être utilisé, éventuellement avec des additifs, dans un article de barrière à l'air qui est choisi dans le groupe constitué par un calandrage intérieur de pneu, un pneu, un manchon à cuisson de pneu, un manchon pneumatique, un diaphragme et un tuyau flexible. Avec les microsphères, l'élastomère durci élaboré présente une réduction du poids spécifique et une réduction de la perméabilité. Ces deux propriétés sont très souhaitables dans la conception et la performance des pneus.
EP19722774.7A 2018-05-14 2019-05-02 Calandrage intérieur de pneu dopé avec des microsphères thermoplastiques expansibles Pending EP3794069A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201862671113P 2018-05-14 2018-05-14
EP18177409 2018-06-12
PCT/US2019/030342 WO2019221918A1 (fr) 2018-05-14 2019-05-02 Calandrage intérieur de pneu dopé avec des microsphères thermoplastiques expansibles

Publications (1)

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EP3794069A1 true EP3794069A1 (fr) 2021-03-24

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CN112639007A (zh) 2021-04-09

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