CN112639007A - Expandable thermoplastic microsphere doped tire innerliner - Google Patents
Expandable thermoplastic microsphere doped tire innerliner Download PDFInfo
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- CN112639007A CN112639007A CN201980039383.4A CN201980039383A CN112639007A CN 112639007 A CN112639007 A CN 112639007A CN 201980039383 A CN201980039383 A CN 201980039383A CN 112639007 A CN112639007 A CN 112639007A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- 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
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Abstract
固化的弹性体，其包含：100份的弹性体/100份橡胶(phr)；和大约0.1‑大约10phr的可膨胀的热塑性微球。这样的固化的弹性体可以非必要地与添加剂一起用于选自下面的气密制品：轮胎内衬、充气轮胎、轮胎硫化胶囊、风向袋、隔膜和软管。使用微球时，所述配混的固化的弹性体表现出比重降低和渗透性降低。这些性能在轮胎设计和性能中都是非常令人期望的。A cured elastomer comprising: 100 parts elastomer per 100 parts rubber (phr); and about 0.1 to about 10 phr expandable thermoplastic microspheres. Such cured elastomers may optionally be used with additives in airtight articles selected from the group consisting of tire inner liners, pneumatic tires, tire curing bladders, windsocks, membranes and hoses. The compounded cured elastomers exhibit reduced specific gravity and reduced permeability when microspheres are used. These properties are highly desirable in tire design and performance.
Description
Inventors Xin Jin, Michael B.Rodgers, Pei T.Bao, Ck Shanawas, Babu Shanmugasudaram
Cross reference to related applications
The present invention claims priority and benefit from USSN 62/671113 filed on day 5/14 in 2018 and EP application No.18177409.2 filed on day 12/6 in 2018, which are incorporated herein by reference in their entirety.
Technical Field
The present disclosure relates to elastomers doped with expandable thermoplastic microspheres, their method of manufacture, and their use in air-tight articles such as tire innerliners.
Background
Halogenated isobutylene/isoprene copolymers, also known as halogenated butyl rubbers, are an option for inner liners of tires for passenger cars, trucks, buses, farm and off-road vehicles, and aircraft vehicles because they exhibit low air permeability, yet are flexible. Bromobutyl rubber, chlorobutyl rubber, and halogenated star-branched butyl rubber can be formulated for special tire applications such as pipes or innerliners. The selection of ingredients and additives for the final commercial ingredient depends on the balance of desired properties, i.e., processability and tack of the green (uncured) compound in the tire factory, and the in-use properties of the cured tire composite.
While halobutyl rubber exhibits low air permeability, additives such as clays have been compounded with halobutyl rubber to further reduce air permeability. However, due to the hydrophobic and polymeric nature of butyl rubber, it is difficult to achieve good dispersion or effective exfoliation of the clay. Publications describing blends of elastomers and exfoliated clays include U.S. patent application publication No. 2004/0194863; U.S. patent nos. 7425591; 7485677, respectively; 7514491, respectively; 7576155, respectively; 7985793, respectively; 8980978, respectively; and 9475910; and international application publication No. wo/2008/118174.
There is a need to develop additional rubber compositions that have sufficiently low air permeability and are flexible to be suitable for the production of tire innerliners and other air-tight articles.
Disclosure of Invention
Described herein is a cured elastomer comprising: 100 parts of elastomer per 100 parts of rubber (phr); and from about 0.1 to about 10phr of expandable thermoplastic microspheres.
Also disclosed herein is a method comprising: mixing components comprising 100 parts elastomer per 100 parts rubber (phr) and from about 0.1 to about 10phr of expandable thermoplastic microspheres to produce a doped elastomer, wherein the temperature of mixing is above the expansion onset temperature of the expandable thermoplastic microspheres and below the maximum exposure temperature of the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured doped elastomer.
Detailed Description
The present invention relates to elastomers doped with expandable thermoplastic microspheres (referred to herein as "doped elastomer compositions"), methods for their manufacture, and their inclusion in air-tight articles such as tire innerliners. More specifically, the doped elastomers described herein may comprise about 100 parts of elastomer (preferably halogenated butyl rubber) per 100 parts of rubber (phr) and from about 0.1phr to about 5phr of expandable thermoplastic microspheres. Optionally, other additives may be included for specific applications. For example, a doped elastomer for use in a tire innerliner may comprise about 100phr of a halogenated butyl rubber, about 0.1phr to about 5phr of expandable thermoplastic microspheres, about 0.1phr to about 3phr of a dust control agent, about 20phr to about 90phr of a filler, about 0.1phr to about 10phr of a processing oil, about 1 to about 15phr of a phenolic resin, and 0phr to about 15phr of a curing agent and system.
Definition of
The various illustrative elements and numerical ranges disclosed herein may be combined with other illustrative elements and numerical ranges to describe preferred embodiments of the compositions, air-tight articles (e.g., innerliners and innerliner-containing tires), and methods of making the same described herein; furthermore, any numerical upper limit on an element may be combined with any numerical lower limit on the same element to describe a preferred embodiment. In this regard, the phrase "in the range of X-Y" is intended to include within the range of "X" and "Y" values.
Unless otherwise indicated, when a certain amount of a component is specified, that amount is understood to be a combined amount if two or more different substances of that component are present at the same time.
As used herein, "polymer" may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, etc. Likewise, a copolymer may denote a polymer comprising at least two monomers, optionally with other monomers. As used herein, when a polymer is referred to as "comprising" a monomer, then the monomer is present in the polymer in the polymerized form of the monomer or in the form of a derivative of the monomer. Also, when the catalyst component is described as comprising a neutral stable form of the component, it is well known to those skilled in the art that the ionic form of the component is the form that reacts with the monomer to produce a polymer.
As used herein, "elastomer" or "elastomer composition" refers to any polymer or composition of polymers (e.g., a blend of polymers) that meets the ASTM D1566 definition. Elastomers include mixed blends of polymers, such as melt-mixed and/or reactor blends of polymers. The term may be used interchangeably with the term "rubber".
As used herein, "phr" is parts per 100 parts of rubber and is a measure commonly used in the art, wherein the components of the composition are measured relative to the main elastomeric component, based on 100 parts by weight of elastomer(s) or rubber(s). Unless otherwise indicated, phr values are percentile significant decimal places. Thus, the expressions "1 phr" and "60 phr" are equivalent to 1.00phr and 60.00phr, respectively.
As used herein, "isobutylene-based elastomer" or "isobutylene-based polymer" or "isobutylene-based rubber" refers to an elastomer or polymer comprising at least 70 mol% isobutylene.
As used herein, the term "doped elastomeric composition" is a generic term for all compositions of the present disclosure. Unless otherwise specified, the term does not describe any point in the production process (mixing, molding or curing) and includes cured, doped elastomeric compositions or mixtures (or compounds) of components suitable for producing cured doped elastomeric compositions.
Expandable thermoplastic microspheres
Expandable thermoplastic microspheres are hollow spheres having a thermoplastic shell that encapsulates a gas. When heated, the thermoplastic shell softens and the encapsulated gas expands, which increases the microsphere diameter and volume. Expandable thermoplastic microspheres of 12 micron sphere diameter, for example, with a shell thickness of 2 microns, will expand to a diameter of 40 microns when heated and a shell thickness of 0.1 microns. As used herein, unless otherwise specified, the term "expandable thermoplastic microspheres" does not denote an expanded state and encompasses an unexpanded state and an expanded state. As used herein, the term "expanded" includes partial expansion and full expansion unless otherwise specified.
The expandable thermoplastic microspheres may be included in the doped elastomeric compositions described herein in an amount of from about 0.1phr to about 10phr, from about 0.5phr to about 7phr, or from about 1phr to about 5 phr.
The expandable thermoplastic microspheres may have an average unexpanded diameter of from about 5 microns to about 50 microns, from about 10 microns to about 40 microns, from about 10 microns to about 20 microns, or from about 20 microns to about 40 microns.
The expandable thermoplastic microspheres may have an average fully expanded diameter of from about 10 microns to about 125 microns, from about 15 microns to about 100 microns, from about 25 microns to about 85 microns, or from about 30 microns to about 50 microns.
The expandable thermoplastic microspheres may have a density of about 5kg/m3-about 75kg/m3About 5kg/m3About 30kg/m3Or about 5kg/m3About 10kg/m3Or about 10kg/m3-about 25kg/m3。
The temperature at which the expandable thermoplastic microspheres begin to expand (expansion onset temperature) and the maximum exposure temperature of the expandable thermoplastic microspheres before degradation or explosion depend on the shell size and shell composition.
The expansion start temperature can be from about 80 ℃ to about 175 ℃, from about 80 ℃ to about 115 ℃, from about 115 ℃ to about 135 ℃, or from about 135 ℃ to about 175 ℃.
The maximum exposure temperature of the expandable thermoplastic microspheres prior to degradation or explosion may be from about 120 ℃ to about 210 ℃, from about 120 ℃ to about 175 ℃, or from about 175 ℃ to about 210 ℃.
Examples of commercially available expandable thermoplastic microspheres include, but are not limited to, EXPANCEL listed in table 1TMDU (unexpanded thermoplastic microspheres, available from Akzo Nobel) grade and EXPANCEL as listed in Table 2TMDE (expanded thermoplastic microspheres, available from Akzo Nobel) grades.
TABLE 1 EXPANCELTMExamples of DUs
TABLE 2 EXPANCELTMExamples of DE
| Grade | Mean unexpanded diameter (micrometers) | Density (kg/m)3) |
| 551 DE40d42 | 30-50 | 42±4 |
| 551 DE40d42 ±2 | 30-50 | 42±2 |
| 461 DE20d70 | 15-25 | 70±6 |
| 461 DE40d60 | 20-40 | 60±5 |
| 461 DET40d25 | 35-55 | 25±3 |
| 092 DET100d25 | 80-120 | 25±3 |
| 920 DE40 d30 | 35-55 | 30±3 |
| 920 DET40 d25 | 30-60 | 25±3 |
| 920 DE80 d30 | 55-85 | 30±3 |
| 043 DET80 d20 | 60-95 | 20±3 |
Elastic body
The doped elastomer compositions described herein comprise at least one elastomer. The elastomer may be selected from butyl rubber (isoprene-isobutylene rubber, "IIR"), branched ("star-branched") butyl rubber, star-branched polyisobutylene rubber, bromobutyl rubber ("BIIR"), chlorobutyl rubber ("CIIR"), random copolymers of isobutylene and para-methylstyrene (poly (isobutylene-co-para-methylstyrene)), halogenated poly (isobutylene-co-para-methylstyrene) ("BIMSM"), polybutadiene rubber ("BR"), high cis-polybutadiene, polyisoprene rubber, isoprene-butadiene rubber ("IBR"), styrene-isoprene-butadiene rubber ("SIBR"), styrene-butadiene rubber ("SBR"), solution-styrene-butadiene rubber ("SBR"), emulsion-styrene-butadiene rubber, nitrile rubber, ethylene-propylene rubber ("EP"), ethylene-propylene-diene rubber ("EPDM"), SynthesisThe polyisoprene of (a), general purpose rubber, natural rubber, any halogenated version of these elastomers, and combinations thereof. Preferred elastomers include isobutylene-based elastomers such as butyl rubber, halogenated butyl rubber, and halogenated poly (isobutylene-co-p-methylstyrene). Examples of commercial products include, but are not limited to EXXPROTMElastomers (halogenated random copolymers of isobutylene and para-methylstyrene available from ExxonMobil Chemical Company), EXXONTM2222 (brominated copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM2255 (brominated copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM6222 (brominated star-branched copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), EXXONTM1066 (chlorinated copolymer of isobutylene and isoprene, available from ExxonMobil Chemical Company), and combinations thereof.
The total amount of elastomer in the doped elastomer composition described herein is 100 phr. For example, the doped elastomeric composition may include 30 to 50phr of butyl rubber, 30 to 50phr of bromobutyl rubber, 30 to 50phr of chlorobutyl rubber, and 30 to 50phr of BIMSM.
Additive agent
Depending on the particular application, the doped elastomeric compositions described herein may optionally further comprise one or more additives including, but not limited to, anti-dust 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 air when added during compounding. This is especially problematic when an open mixer is used. The anti-dusting agent may be used to reduce the flotation of the expandable thermoplastic microspheres to maintain the microspheres in contact with the rubber until introduction. Examples of anti-dust agents include, but are not limited to, calcium carbonate, clay, and combinations thereof.
When included, the anti-dust agent may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 3phr, from about 1phr to about 3phr, or from about 1.5phr to about 2.5 phr.
Fillers can improve the mechanical properties and/or barrier properties of the doped elastomeric compositions described herein. Examples of fillers include, but are not limited to, silica, talc, titanium dioxide, and carbon black.
Silica means any type or particle size of silica or other silicic acid derivative, or silicic acid, which is processed by solution, high heat, etc., and has a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and combinations thereof.
Preferably, the surface area of the carbon black is less than 40m2Oil absorption rate of dibutyl phthalate is less than 80cm3And/100 gm. Examples of carbon blacks include, but are not limited to, N550, N660, N650, N762 and N990,
85 (carbon black, available from Cabot),
90 (carbon black, available from Cabot), and combinations thereof.
When included, fillers may be present in the doped elastomeric composition in an amount ranging from about 20phr to about 90phr, from about 30phr to about 80phr, or from about 40phr to about 70 phr.
Processing oils are used primarily to improve the processability of the compositions during compounding and molding. The processing oil may be a petroleum-derived processing oil, a synthetic plasticizer, or a combination thereof. Examples of processing oils include, but are not limited to, paraffinic oils, naphthenic oils, aromatic oils, Mild Extraction Solvates (MES), Treated Distillate Aromatic Extracts (TDAE), and combinations thereof. The preferred plasticizer oils for standard, non-DVA (dynamically vulcanized alloy), engineering resin-free liner compositions are paraffinic petroleum oils; suitable hydrocarbon plasticizer oils for such liners include oils having the following general characteristics.
Processing oils, when included, may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 10phr, from about 1phr to about 7phr, or from about 3phr to about 5 phr.
Tackifying resins also improve the processability of the composition. Examples of 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, dicyclopentadiene derivatives, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, rosin esters, rosin acids, graft monomer grafted resins, and combinations thereof.
Tackifying resins, when included, can be present in the doped elastomeric composition in an amount of from about 0.1phr to about 10phr, from about 1phr to about 7phr, or from about 3phr to about 5 phr.
The curing agent may include a curing agent, phenolic resin, vulcanizing agent, crosslinking agent, and the like. In general, the curing agent, when included, may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 15phr, from about 1phr to about 10phr, or from about 5phr to about 8 phr.
Examples of curing agents include, but are not limited to, ZnO, CaO, MgO, Al2O3，CrO3，FeO，Fe2O3And NiO. These metal oxides may be used alone or in combination with the corresponding metal fatty acid complexes (e.g., zinc stearate, calcium stearate, etc.), or with separately added organic and fatty acids such as stearic acid, and optionally other curing agents such as sulfur or sulfur compounds, alkyl peroxide compounds, diamines, diamine derivatives (e.g., DIAK available from DuPont)TM) And combinations thereof.
Elastomer curing with curatives can be accelerated and is often used for vulcanization of elastomers. The mechanism for accelerating the vulcanization of natural rubber involves complex interactions between the curative, accelerator, activator and polymer. Preferably, all of the available curing agent is consumed in forming effective crosslinks that bind the two polymer chains together and enhance the overall strength of the polymer matrix. A variety of accelerators are known in the art and include, but are not limited to, stearic acid, Diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4, 4' -dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazole disulfide (MBTS), hexamethylene-1, 6-disulfuric acid disodium salt dihydrate (e.g., DURALINK)TMHTS, available from Flexsys), 2-morpholinothiabenzothiazole (MBS or MOR), 90% MOR and 10% MBTS blend (MOR 90), N-tert-butyl-2-benzothiazolesulfenamide (sulfenamide) (TBBS), N-oxydiethylene thiocarbamoyl-N-oxydiethylene sulfonamide (OTOS), zinc 2-ethylhexanoate (ZEH), thiourea and combinations thereof.
The curing agent, when included, may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 10phr, from about 1phr to about 8phr, or from about 3phr to about 7 phr.
Phenolic resins (or phenol-formaldehyde resins) may be used as curing agents. Examples of phenol-formaldehyde resins include resins having the following structure:
wherein m is 1 to 50, more preferably 2 to 10; r is selected from hydrogen and C in one embodiment1-C20An alkyl group; and in one embodiment selected from C4-C14A branched alkyl group; and Q is selected from-CH2-and-CH2-O-CH2A divalent group of (a). Mixtures of phenolic resins may be used.
The phenolic resin may 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, paraffin oils, polyolefin oils, mineral oils, silicone oils, and combinations thereof.
Phenolic resin, when included, may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 10phr, from about 1phr to about 8phr, or from about 3phr to about 7 phr.
One or more crosslinking agents such as coupling agents may also be used, particularly when silica is also present in the composition. The coupling agent may be a difunctional organosilane crosslinking agent which is any silane-coupled filler and/or crosslinking activator and/or silane reinforcing agent. Examples of coupling agents include, but are not limited to, vinyltriethoxysilane, bis- (3-triethoxysilylpropyl) tetrasulfide, vinyl-tris- (β -methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, γ -aminopropyltriethoxysilane (e.g., A1100 from Witco)TM) Gamma-mercaptopropyltrimethoxysilane (e.g. A189 from Witco)TM) And combinations thereof.
The leveling agent can enhance the processability of the rubber during compounding, extrusion, and molding. An example of a leveling agent includes STRUCKTOLTM40MS (mixture of dark aromatic hydrocarbon resins from Struktol Company).
Such agents, when included, may be present in the doped elastomeric composition in an amount of from about 0.1phr to about 15phr, from about 3phr to about 12phr, or from about 5phr to about 10 phr.
Machining
The doped elastomeric compositions described herein can be formed into airtight articles such as tire innerliners, pneumatic tires, tire curing bladders, windsocks (e.g., air dampers), membranes, hoses (e.g., gas and fluid transport hoses). Typically, the article is prepared by mixing the components at a temperature above the expansion onset temperature of the expandable thermoplastic microspheres and below the maximum exposure temperature of the expandable thermoplastic microspheres, shaping the mixed components into the desired shape, and then curing to produce an article comprising the cured, doped elastomeric composition.
The components may be mixed (or compounded) by mixing the components in any suitable internal mixing vesselE.g. BANBURYTMMixer, BRABENDERTMA Krupp internal mixer with intermeshing rotors, or an extruder (e.g., a single screw extruder or a twin screw extruder). Mixing may be conducted at a temperature above the expansion onset temperature of the expandable thermoplastic microspheres and below the maximum exposure temperature of the expandable thermoplastic microspheres, and at a rate sufficient to cause uniform dispersion of the expandable thermoplastic microspheres and additives within the rubber.
The mixing can be performed in a single step or in multiple steps. For example, the components of the doped elastomeric composition (except for the curing agent) may be mixed in a non-productive stage. The curing agent may then be mixed into the composition during the production phase.
Suitable mixing rates may be from about 10RPM to about 100 RPM. Preferably, the mixing rate may be from a low of about 10RPM, 30RPM or 50RPM to a high of about 60RPM, 80RPM or 100 RPM.
After mixing, the doped elastomeric composition is shaped (or formed) into a desired shape. Suitable methods include, but are not limited to, extrusion, calendering, and combinations thereof. For example, when producing a liner, an innerliner layer or "stock" is prepared as follows: (1) calendering or extruding the blended elastomeric composition into a sheet having a thickness of 0.5mm to 2mm, and (2) cutting the sheet material into strips of appropriate width and length for use in innerliner applications for a particular size or type of tire. The innerliner may then be cured while in contact with the tire carcass and/or sidewalls in which it is placed.
The curing temperature may be from about 100 ℃ to about 250 ℃, or from about 125 ℃ to about 200 ℃. The curing time may be from minutes to hours, from about 1 minute to about 3 hours, or from about 5 minutes to about 30 minutes.
Compositions and methods of the examples
Example 1. a cured elastomer comprising: 100 parts of elastomer per 100 parts of rubber (phr); and from about 0.1 to about 10phr of expandable thermoplastic microspheres.
Example 2. the cured elastomer of example 1, wherein the elastomer comprises from about 50phr to about 100phr of the halogenated butyl rubber.
Embodiment 3. the cured elastomer of any of the preceding embodiments, wherein the elastomer comprises from about 50phr to about 100phr of bromobutyl rubber, chlorobutyl rubber, or a combination thereof.
Embodiment 4. the cured elastomer of any of the preceding embodiments, wherein the expandable thermoplastic microspheres have an average unexpanded diameter of about 5 microns to about 50 microns.
Embodiment 5. the cured elastomer of any of the preceding embodiments, wherein the expandable thermoplastic microspheres have a density of about 5 to about 30kg/m3。
Embodiment 6. the cured elastomer of any of the preceding embodiments, further comprising: from about 0.1 to about 3phr of an anti-dusting agent.
Embodiment 7. the cured elastomer of any of the preceding embodiments, further comprising: from about 20phr to about 90phr of filler.
Embodiment 8. the cured elastomer of any of the preceding embodiments, further comprising: from about 0.1 to about 10phr of process oil.
Embodiment 9. the cured elastomer of any of the preceding embodiments, further comprising: from about 0.1phr to about 10phr of a tackifier.
Embodiment 10. the cured elastomer of any of the preceding embodiments, further comprising: from about 1phr to about 10phr of phenolic resin.
Embodiment 11. the cured elastomer of any of the preceding embodiments, further comprising: from about 0.1phr to about 10phr of curing agent.
Embodiment 12. the cured elastomer of any of the preceding embodiments, further comprising: from about 0.1phr to about 1.0phr of peptizer.
Embodiment 13. the cured elastomer of any of the preceding embodiments, further comprising: from about 1phr to about 15phr of peptizer.
Embodiment 14. the cured elastomer of any of the preceding embodiments, comprising: 100phr of an elastomer comprising from about 50phr to 100phr of bromobutyl rubber; from about 1 to about 5phr of expandable thermoplastic microspheres; from about 1 to about 3phr of an anti-dusting agent comprising calcium carbonate, clay, wax, or a combination thereof; from about 40phr to about 70phr of a filler comprising carbon black; about 5 to about 10phr of process oil; from about 5phr to about 10phr of a tackifier; and from about 1phr to about 10phr total of phenolic resin and curing agent.
Embodiment 15. an airtight article comprising the cured elastomer of any of the preceding embodiments, wherein the airtight article is selected from the group consisting of a tire innerliner, a pneumatic tire, a tire curing bladder, a windsock, a membrane, and a hose.
Example 16. a tire comprising an innerliner made from the cured elastomer of one of examples 1-14.
Embodiment 17. a method, comprising: mixing components comprising 100 parts elastomer per 100 parts rubber (phr) and from about 0.1 to about 10phr of expandable thermoplastic microspheres to produce a doped elastomer, wherein the temperature of mixing is above the expansion onset temperature of the expandable thermoplastic microspheres and below the maximum exposure temperature of the expandable thermoplastic microspheres; and curing the doped elastomer to produce a cured doped elastomer.
Embodiment 18 the method of embodiment 16, wherein the mixing temperature is about 80 ℃ to about 235 ℃.
Embodiment 19. the method of any of embodiments 16 to 17, wherein the expandable thermoplastic microspheres have an average unexpanded diameter of about 5 microns to about 50 microns.
Embodiment 20. the method of one of embodiments 16 to 18, wherein the expandable thermoplastic microspheres have a density of about 5 to about 30kg/m3。
Embodiment 21. the method of one of embodiments 16 to 19, further comprising: prior to curing, the elastomeric compound is shaped into an innerliner shape in a tire.
Example 22. the method of one of examples 16-20, wherein the composition further comprises from about 1 to about 3phr of a dust control agent, from about 20phr to about 90phr of a filler, from about 0.1 to about 10phr of a processing oil, from about 0.1phr to about 10phr of a tackifier, and from about 0.1phr to about 10phr of a curing agent.
Embodiment 23. the method of one of embodiments 16 to 21, wherein the composition comprises: 100phr of an elastomer comprising from about 50phr to 100phr of bromobutyl rubber; from about 1 to about 5phr of expandable thermoplastic microspheres; from about 1 to about 3phr of an anti-dusting agent comprising calcium carbonate, a wax, a clay, or a combination thereof; from about 40phr to about 70phr of a filler comprising carbon black; about 5 to about 10phr of process oil; from about 5phr to about 10phr of a tackifier; and from about 1phr to about 10phr total of phenolic resin and curing agent.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
One or more exemplary embodiments are set forth herein that incorporate the embodiments of the invention disclosed herein. In the interest of brevity, not all features of a physical implementation are described or shown in this application. It will be appreciated that in the development of a physical embodiment incorporating the embodiments of the present invention, numerous implementation-specific decisions must be made to achieve the developers' goals, such as compliance with system-related, business-related, government-related and other constraints, which will vary from one implementation to another and from one time to another. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for those of ordinary skill in this art having benefit of this disclosure.
Although 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.
In order to facilitate a better understanding of embodiments of the invention, the following examples of preferred or representative embodiments are given. The following examples should in no way be construed as limiting or defining the scope of the invention.
Examples
Three elastomeric compositions were prepared according to the formulation of table 3. The components are mixed in an open mixer. Therefore, calcium carbonate dust control agents are used to mitigate flotation of the expandable thermoplastic microspheres and to maximize their incorporation into the composition.
TABLE 3 formulation of elastomer compositions
| Component (c) | Sample 1 (control) | Sample 2 | Sample 3 |
| EXXONTM2222 | 100 | 100 | 100 |
| N660 carbon Black | 60 | 60 | 60 |
| Naphthenic oil | 8 | 8 | 8 |
| STRUKTOLTM40MS | 7 | 7 | 7 |
| SP-1068 resin | 4 | 4 | 4 |
| Stearic acid | 1 | 1 | 1 |
| MgO | 0.15 | -- | -- |
| ZnO | 1 | 1 | 1 |
| MBTS | 1.25 | 1.25 | 1.25 |
| Sulfur | 0.5 | 0.5 | 0.5 |
| CaCO3 | -- | 2 | 2 |
| EXPANCELTM909DU80 | -- | 2 | -- |
| EXPANCELTM930DU120 | -- | -- | 2 |
SP-1068 resin (a thermoplastic resin made from octylphenol and formaldehyde, available from Akrochem Corporation)
The components are mixed together to form a lined green compound and then cured at either 160 ℃ or 180 ℃. The rheological properties (moving die rheometer temperature 160 ℃), air barrier properties (Mocon permeability test temperature 40 ℃) and mechanical properties of the compositions are provided in table 4.
TABLE 4 sample Properties
Measured according to BRDTC OP-01 (based on ASTM D5289)
Measured according to BRDTC OP-65
Hardness was measured according to BRDTC OP-07 (based on ASTM D2240) and physical properties of the cured articles were measured according to BRDTC OP-03 (based on ASTM D412)
The rheological properties of samples 2 and 3 are within acceptable limits, which allows the compound to be processed by standard methods.
The air permeability performance of samples 2 and 3 decreased by 4% and 16%, respectively, which means that the permeability to air decreased and the suitability of the compound for use in airtight articles increased.
The hardness, tensile strength and elongation of samples 2 and 3 are within acceptable limits for tire innerliner and other air tight applications. However, the density is advantageously reduced by as much as 10%.
The present invention is, therefore, well adapted to attain the ends and advantages mentioned, as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the invention. The invention illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein and/or any optional element which is not disclosed herein. Although 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 be varied 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, each range of values (in the form of "about a to about b," or, equivalently, "about a to b," or, equivalently, "from about a to b") disclosed herein is to be understood as setting forth each number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Furthermore, the indefinite articles "a" or "an" as used in the claims are defined herein to mean one or more than one of the element it introduces.
Claims (24)
1. A cured elastomer comprising:
100 parts of elastomer per 100 parts of rubber (phr); and
from about 0.1 to about 10phr of expandable thermoplastic microspheres.
2. The cured elastomer of claim 1, wherein the elastomer comprises from about 50phr to about 100phr of the halogenated butyl rubber.
3. The cured elastomer of any of the foregoing claims, wherein the elastomer comprises from about 50phr to about 100phr of bromobutyl rubber, chlorobutyl rubber, natural rubber, or combinations thereof.
4. The cured elastomer of any of the foregoing claims, wherein the expandable thermoplastic microspheres have an average unexpanded diameter of from about 5 microns to about 50 microns.
5. The cured elastomer of any preceding claim, wherein the expandable thermoplastic microspheres have a density of from about 5 to about 30kg/m3。
6. The cured elastomer of any of the foregoing claims, further comprising:
from about 0.1 to about 3phr of an anti-dusting agent.
7. The cured elastomer of any of the foregoing claims, further comprising:
from about 20phr to about 90phr of filler.
8. The cured elastomer of any of the foregoing claims, further comprising:
from about 0.1 to about 10phr of process oil.
9. The cured elastomer of any of the foregoing claims, further comprising:
from about 0.1phr to about 10phr of a tackifier.
10. The cured elastomer of any of the foregoing claims, further comprising:
from about 1phr to about 10phr of phenolic resin.
11. The cured elastomer of any of the foregoing claims, further comprising:
from about 0.1phr to about 10phr of curing agent.
12. The cured elastomer of any of the foregoing claims, further comprising:
from about 0.1phr to about 15phr of a leveling agent.
13. The cured elastomer of any of the foregoing claims, comprising:
100phr of an elastomer comprising from about 50phr to 100phr of bromobutyl rubber;
from about 1 to about 5phr of expandable thermoplastic microspheres;
from about 1 to about 3phr of an anti-dusting agent comprising calcium carbonate, clay, or a combination thereof;
from about 40phr to about 70phr of a filler comprising carbon black;
about 5 to about 10phr of process oil;
from about 5phr to about 10phr of a tackifier; and
from about 1phr to about 10phr total of phenolic resin and curing agent.
14. An airtight article comprising the cured elastomer of any of the preceding claims, wherein the airtight article is selected from the group consisting of a tire innerliner, a pneumatic tire, a tire curing bladder, a windsock, a membrane, and a hose.
15. The hermetic article of claim 14 wherein air permeability is reduced by about 4% to about 16% as compared to the same hermetic article without the expandable thermoplastic microspheres.
16. The hermetic article of claim 14 wherein the density is reduced by about 3% to about 10% compared to the same hermetic article without the expandable thermoplastic microspheres.
17. A tire comprising an innerliner made from the cured elastomer of any of claims 1-13.
18. A method, comprising:
mixing components comprising 100 parts elastomer per 100 parts rubber (phr) and from about 0.1 to about 10phr of expandable thermoplastic microspheres to produce a doped elastomer, wherein the temperature of mixing is above the expansion onset temperature of the expandable thermoplastic microspheres and below the maximum exposure temperature of the expandable thermoplastic microspheres; and
curing the doped elastomer to produce a cured doped elastomer.
19. The method of claim 18, wherein the mixing temperature is about 80 ℃ to about 235 ℃.
20. The process according to any of claims 18 to 19, wherein the expandable thermoplastic microspheres have an average unexpanded diameter of from about 5 microns to about 50 microns.
21. The process according to any of claims 18 to 20, wherein the expandable thermoplastic microspheres have a density of about 5 to about 30kg/m3。
22. The method of any one of claims 18-21, further comprising:
prior to curing, the elastomeric compound is shaped into the shape of an innerliner in a tire.
23. The method of any of claims 18-22, wherein the components further comprise from about 1 to about 3phr of an anti-dust agent, from about 20phr to about 90phr of a filler, from about 0.1 to about 10phr of a processing oil, from about 0.1phr to about 10phr of a tackifier, and from about 0.1phr to about 10phr of a curing agent.
24. The method of any of claims 18-23, wherein the components comprise:
100phr of an elastomer comprising from about 50phr to 100phr of bromobutyl rubber;
from about 1 to about 5phr of expandable thermoplastic microspheres;
from about 1 to about 3phr of an anti-dusting agent comprising calcium carbonate, clay, or a combination thereof;
from about 40phr to about 70phr of a filler comprising carbon black;
about 5 to about 10phr of process oil;
from about 5phr to about 10phr of a tackifier; and
from about 1phr to about 10phr total of phenolic resin and curing agent.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201862671113P | 2018-05-14 | 2018-05-14 | |
| US62/671,113 | 2018-05-14 | ||
| EP18177409 | 2018-06-12 | ||
| EP18177409.2 | 2018-06-12 | ||
| PCT/US2019/030342 WO2019221918A1 (en) | 2018-05-14 | 2019-05-02 | Expandable thermoplastic microsphere doped tire innerliner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112639007A true CN112639007A (en) | 2021-04-09 |
Family
ID=66440159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980039383.4A Pending CN112639007A (en) | 2018-05-14 | 2019-05-02 | Expandable thermoplastic microsphere doped tire innerliner |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3794069A1 (en) |
| CN (1) | CN112639007A (en) |
| WO (1) | WO2019221918A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12116431B2 (en) | 2021-08-17 | 2024-10-15 | Industrial Technology Research Institute | Light-curing resin composition, three-dimensional object containing the same, and manufacturing method of three-dimensional object |
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| WO2016099695A1 (en) * | 2014-12-19 | 2016-06-23 | Exxonmobil Chemical Patents Inc. | Expansible barrier film assemblies |
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| US20040194863A1 (en) | 2001-06-14 | 2004-10-07 | Grah Michael D. | Tire with improved inner liner |
| JP4846135B2 (en) * | 2001-08-01 | 2011-12-28 | 住友ゴム工業株式会社 | Pneumatic tire with inner liner |
| US7576155B2 (en) | 2002-12-18 | 2009-08-18 | Bridgestone Corporation | Method for clay exfoliation, compositions therefore, and modified rubber containing same |
| EP2330144B8 (en) * | 2003-11-19 | 2018-07-25 | Matsumoto Yushi-Seiyaku Co., Ltd. | Thermally expanded microsphere, process for producing the same, thermally expandiable microsphere and use thereof |
| RU2393179C2 (en) | 2004-07-06 | 2010-06-27 | Эксонмобил Кемикэл Пейтентс Инк. | Polymer nanocomposites and preparation methods thereof |
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- 2019-05-02 CN CN201980039383.4A patent/CN112639007A/en active Pending
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| US12116431B2 (en) | 2021-08-17 | 2024-10-15 | Industrial Technology Research Institute | Light-curing resin composition, three-dimensional object containing the same, and manufacturing method of three-dimensional object |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3794069A1 (en) | 2021-03-24 |
| WO2019221918A1 (en) | 2019-11-21 |
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