WO2024059443A1 - Synthèse d'élastomères à base d'isobutylène-co-paraméthylstyrène ayant de larges distributions de poids moléculaire - Google Patents

Synthèse d'élastomères à base d'isobutylène-co-paraméthylstyrène ayant de larges distributions de poids moléculaire Download PDF

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WO2024059443A1
WO2024059443A1 PCT/US2023/073301 US2023073301W WO2024059443A1 WO 2024059443 A1 WO2024059443 A1 WO 2024059443A1 US 2023073301 W US2023073301 W US 2023073301W WO 2024059443 A1 WO2024059443 A1 WO 2024059443A1
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isobutylene
paramethylstyrene
based elastomer
elastomer
modified
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PCT/US2023/073301
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English (en)
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Sunny Jacob
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Exxonmobil Chemical Patents Inc.
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Publication of WO2024059443A1 publication Critical patent/WO2024059443A1/fr

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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
    • 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

Definitions

  • This application relates to methods for controlling the molecular weight distribution of isobutylene-co-paramethylstyrene based elastomers and, in particular, utilizing a peroxide treatment to initiate chemical and thermal cracking of isobutylene-co-paramethylstyrene based elastomers to increase the fraction of low molecular weight species.
  • adjusting the balance of the MWD of isobutylene-co-paramethylstyrene elastomers can affect various mechanical properties and/or processability factors of the polymer product.
  • High molecular weight fractions contribute to mechanical properties such as: tensile break, elongation, impact strength, and the like.
  • Low molecular weight fractions contribute to processability factors such as: low melt viscosity, plasticizer quality, and the like.
  • the breadth of MWD can affect the suitability of isobutylene-co- param ethyl styrene elastomers for various applications, such as tire products (e.g., innerliners and/or bladder components) or pharmaceutical products (e.g., pharmaceutical closures).
  • tire products e.g., innerliners and/or bladder components
  • pharmaceutical products e.g., pharmaceutical closures
  • a method for preparing an isobutylene-co-paramethylstyrene composition can comprise treating an isobutylene-co-paramethylstyrene based elastomer with a peroxide initiator at a temperature greater than or equal to about 160 °C to chemically induce a thermal breaking along the copolymer backbone of the isobutylene-co-paramethylstyrene based elastomer.
  • the treating can produce a modified isobutylene-co-paramethylstyrene based elastomer having a Mw/Mn ratio greater than 2.5.
  • another method for preparing an isobutylene-co-paramethylstyrene composition can comprise increasing a low molecular weight fraction of an isobutylene-co-paramethylstyrene based elastomer by mixing the isobutylene-co-paramethylstyrene based elastomer with a peroxide initiator at a temperature greater than or equal to about 160 °C. The mixing produces a modified isobutylene-co-paramethylstyrene based elastomer having a Mw/Mn ratio greater than 2.5.
  • an isobutylene-co- param ethyl styrene based elastomer is provided.
  • the isobutylene-co-paramethylstyrene based elastomer can comprise 80 to 99.5 mole percent of isobutylene, 0.5 to 20 mole percent of paramethylstyrene, and have a substantially homogenous compositional distribution with a Mw/Mn ratio greater than 6.0.
  • the isobutylene-co-paramethylstyrene based elastomer can be comprised within a cured article that is a tire innerliner, an innertube, a wire coating, a pharmaceutical rubber stopper, a hose, a film, an adhesive, or a sealant.
  • This application relates to methods for controlling the MWD of isobutylene-co- param ethyl styrene based elastomers compositions and, in particular, broadening the MWD of isobutylene-co-paramethylstyrene based elastomer compositions to a range of, for example, about 2.5 to 10 for various applications such as tire or pharmaceutical products.
  • the compound Mooney viscosity and the compound Mooney relaxation are important for producing tires with good innerliner splicing characteristics and splice strength after tire curing.
  • a certain ratio of the high and low molecular weight fractions is needed to obtain a balance of mechanical strength and ease of processing with good splice integrity.
  • certain fraction of higher molecular weight is necessary for desired mechanical properties, while a certain fraction of low-molecular weight portion helps improve the processability as the low molecular weight fraction can act as a plasticizer.
  • the present disclosure provides methods for producing isobutylene-co- param ethyl styrene based elastomer compositions having a broad MWD.
  • the elastomer compositions described herein are particularly useful in applications where isobutylene-co- param ethyl styrene elastomers or brominated isobutylene-co-paramethylstyrene elastomers are used and there is a desire to obtain high green strength while increasing the rate of stress relaxation.
  • various embodiments described herein provide one or more methodologies for broadening the MWD of isobutylene-co-paramethylstyrene elastomer compositions (e.g., isobutylene-co-paramethylstyrene elastomers and/or brominated isobutylene-co-paramethylstyrene elastomers) by varying the concentration of low molecular weight fractions via a chemically induced thermal breaking of the copolymer backbone with a peroxide initiator.
  • the isobutylene-co-paramethylstyrene based elastomer compositions can be subjected to the molecular weight modification pre or post bromination.
  • the MWD can be further controlled by blending the modified polymers with unmodified polymers having a higher molecular weight and/or narrower MWD.
  • the modified and unmodified elastomers can be blended together at various ratios to achieve a desired MWD.
  • the MWD of isobutylene-co-paramethylstyrene based elastomers can be modified by increasing the fraction of low molecular weight species (e.g., having a molecular weight that is less than 100,000 Daltons (Da)) via peroxide treatments performed at elevated temperatures (e.g., about 160 to 190 °C) to induce chemical and/or thermal cracking of the copolymer backbone.
  • the term “catalyst system,” and grammatical variants thereof, refers to and includes any Lewis acid(s) or other metal complex(es) used to catalyze the polymerization of hydrocarbon monomers and an optional at least one initiator. Other additives may be included, such as catalyst modifiers, for example.
  • the catalyst system is combined with a diluent for polymerization, collectively termed a “polymerization medium.”
  • a “polymerization system,” as used herein, and grammatical variants thereof, refers to the use of a polymerization medium to produce polymers.
  • the term “diluent,” and grammatical variants thereof, refers to a dilution or dissolving agent, including mixtures thereof (e.g., two or more individual diluents).
  • the diluent can further be used to impact reactor mixing (using an overhead blender) as it serves as a dilution agent.
  • solvent refers to a chemical agent that can dissolve resultant polymers.
  • a polymerization reactor include a continuous flow-stirred tank reactor, which utilizes continuous tank agitation, as well as a draft tube type reactor.
  • Commercial reactors typically can be well mixed vessels of greater than 400 to 500 liters in volume with a high circulation rate provided by a pump impeller.
  • the polymerization and a pump can both generate heat and, in order to keep the slurry cold, the reaction system can include heat exchangers.
  • slurry can circulate through tubes of a heat exchanger. Cooling can be provided, for example, by boiling ethylene on a shell side. Slurry temperature can be set by the boiling ethylene temperature, the required heat flux and the overall resistance to heat transfer.
  • slurry refers to an amount of diluent comprising polymer that has precipitated from a catalyst system and diluent.
  • the slurry concentration is the weight percent of the partially or completely precipitated polymers based on the total slurry.
  • quench refers to a process of rapidly heating and mixing a reactor effluent stream with a quench medium, wherein further polymerization is terminated.
  • polymer refers to homopolymers, copolymers, interpolymers, terpolymers, etc.
  • copolymer and grammatical variants thereof, is meant to include polymers having two or more monomers.
  • interpolymer and grammatical variants thereof, means any polymer or oligomer having a number average molecular weight of 500 or more prepared by the polymerization or oligomerization of at least two different 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 when 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.
  • olefin refers to a hydrocarbon containing a carbon-carbon double bond.
  • diolefin and grammatical variants thereof, refers to any olefin monomer having two double bonds.
  • Elastomer or “elastomeric composition,” as used herein, and grammatical variants thereof, refers to any polymer or composition of polymers consistent with the ASTM DI 566- 21 A (November 2021) definition. Elastomer may be used herein interchangeably with the term “rubber(s) .”
  • Mooney viscosity is the Mooney viscosity of a polymer or polymer composition.
  • the polymer composition analyzed for determining Mooney viscosity should be substantially devoid of diluent and solvent.
  • the sample may be placed on a boiling-water steam table in a hood to evaporate a large fraction of the diluent and unreacted monomers, and then, dried in a vacuum oven overnight (12 hours, 90°C) prior to testing, in accordance with laboratory analysis techniques, or the sample for testing may be taken from a devolatilized polymer (z.e., the polymer postdevolatilization in industrial-scale processes).
  • Mooney viscosity is measured using a Mooney viscometer according to ASTM D1646-19A (November 2019, but with the following modifications/clarifications of that procedure.
  • sample polymer is pressed between two hot plates of a compression press prior to testing.
  • the plate temperature is 125°C +/- 10°C instead of the 50 +/- 5°C as recommended in ASTM D1646-17, because 50°C is unable to cause sufficient massing.
  • ASTM DI 646- 17 allows for several options for die protection, should any two options provide conflicting results, PET 36 micron is used as the die protection.
  • ASTM DI 646- 17 does not indicate a sample weight in Section 8; thus, to the extent results may vary based upon sample weight, Mooney viscosity determined using a sample weight of 21.5 +/- 2.7 grams (g) per D1646-17 Section 8 procedures will govern. Finally, the rest procedures before testing set forth in DI 646- 17 Section 8 are 23 +/- 3°C for 30 minutes in air; Mooney values as reported herein were determined after resting at 24 +/- 3 °C for 30 minutes in air. Samples are placed on either side of a rotor according to the ASTM DI 646- 17 test method; torque required to turn the viscometer motor at 2 rpm is measured by a transducer for determining the Mooney viscosity.
  • Mooney Units (ML, 1+4 @ 125°C or ML, 1+8 @ 125°C), where MU is the Mooney viscosity number, L denotes large rotor (defined as ML in ASTM DI 646- 17), 1 is the pre-heat time in minutes, 4 or 8 is the sample run time in minutes after the motor starts, and 125°C is the test temperature.
  • a Mooney viscosity of 90 determined by the aforementioned method would be reported as a Mooney viscosity of 90 MU (ML, 1+8 @ 125°C) or 90 MU (ML, 1+4 @ 125°C).
  • the Mooney viscosity may be reported as 90 MU; in such instance, it should be assumed that the just-described (ML, 1+4 @ 125°C) method is used to determine such viscosity, unless otherwise noted.
  • a lower test temperature may be used (e.g., 100°C), in which case Mooney is reported as Mooney Viscosity (ML, 1+8 @ 100°C), or @ T°C where T is the test temperature.
  • Blends refers to a mixture of two or more polymers. Blends can be produced by, for example: solution blending, melt mixing, shear mixing, a combination thereof, and/or the like.
  • Numerical ranges used herein include the numbers recited in the range. For example, the numerical range “from 1 wt% to 10 wt%” includes 1 wt% and 10 wt% within the recited range.
  • isobutylene-co-paramethylstyrene based elastomer can refer to a polyolefin copolymer composition comprising the reaction product of isobutylene and paramethylstyrene.
  • the copolymer can have a substantially homogenous compositional distribution.
  • the isobutylene-co-paramethylstyrene based elastomers described herein can have an average molecular weight (Mw) ranging from, for example, about 200,000 Da to about 2,000,000 Da (e.g., about 200,000 Da to about 500,000 Da; about 500,000 Da to about 1,000,000 Da; about 1,000,000 Da to about 1,500,000 Da; or about 1,500,000 Da to about 200,000 Da), and a MWD (Mw/Mn) ranging from, for example, less than about 2.5.
  • Mw average molecular weight
  • the isobutylene-co-paramethylstyrene based elastomer can comprise between about 80 and about 99.5 mole percent of the isobutylene and about 0.5 to about 20 mole percent of the paramethylstryene.
  • the isobutylene-co- param ethyl styrene based elastomers can be substantially linear.
  • the paramethylstyrene can be halogenated.
  • the paramethylstyrene can be characterized by Formula 1.
  • X is hydrogen, a halogen (e.g., bromine or chlorine), or a combination of a halogen and another functional group such which can be incorporated by nucleophilic substitution of benzylic halogen with othe groups such as: carboxylic acids; carboxy salts, carboxy esters, amides, and imides; hydroxyl, alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; nitrile; amino, and mixtures thereof.
  • othe groups such as: carboxylic acids; carboxy salts, carboxy esters, amides, and imides; hydroxyl, alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; nitrile; amino, and mixtures thereof.
  • the isobutylene-co-paramethylstyrene based elastomers can be synthesized via a low temperature cationic polymerization processing using a Lewis acid catalyst system (e.g., employing ethylaluminum dichloride or ethylaluminum sequichloride).
  • a Lewis acid catalyst system e.g., employing ethylaluminum dichloride or ethylaluminum sequichloride.
  • methyl chloride can be utilized as a diluent for the reaction mixture at a temperature less than, for example, 90° C; where the methyl chloride acts a solvent for the monomers catalyst, while also acting as a non-solvent for the polymer product, thereby resulting in a slurry.
  • Suitable diluents include, but are not limited to: methylene chloride, vinyl chloride, and/or ethyl chloride.
  • one or more stabilizing agents e.g., gel free polymers and/or gelled polymers
  • the diluent can serve as a solvent for both the monomer catalyst and the polymer product.
  • the diluent solution can comprise aliphatic hydrocarbons (e.g, hexane, pentane, heptane, and/or the like) and/or mixtures of aliphatic hydrocarbons with slurry-type diluents (e.g., methyl chloride and/or methylene chloride).
  • the diluent solution can be utilized along with a catalyst system such as hydrochloric acid and ethylaluminum dichloride or ethylaluminum sequichloride.
  • a catalyst system such as hydrochloric acid and ethylaluminum dichloride or ethylaluminum sequichloride.
  • the slurry polymerization process can incorporate one or more slurry stabilizers (e.g, butyl dispersions) produced during polymerization in a diluent such as methyl chloride to prevent mass agglomeration of slurry particles.
  • slurry stabilizers can enable the formation of dispersed butyl particles containing gel in the reactor without depositing fouling rubber containing gel on the heat transfer surfaces.
  • slurry stabilizers it is possible to produce a modified rubber containing as much branching and/or gel as is desired in a practical manner without interfering with the ability to wash the reactor in order to prepare it for reuse.
  • solution polymerization can enable homogeneous polymerization and the ability to run subsequent reaction directly on the resulting polymer solution. Additionally, solution polymerization can produce the isobutylene-co-paramethylstyrene based elastomers in a desirable solution state to permit post polymerization chemical modification (e.g., MWD modification via a peroxide treatment).
  • isobutylene-co-param ethyl styrene based elastomers can be further subjected to a post-polymerization halogenation reaction (e.g., radical bromination) to achieve paramethylstyrene blocks characterized by Formula 1.
  • a post-polymerization halogenation reaction e.g., radical bromination
  • the copolymerization reaction can be quenched and residual monomers can be removed.
  • the halogenation reactions described herein can be carried out on the copolymer either in solution or in a finely dispersed slurry.
  • Suitable solvents for carrying out the halogenation reaction in solution include low boiling hydrocarbons (e.g., C4 to C7) and halogenated hydrocarbons.
  • the halogenation reaction can also be conducted with the copolymer as a fine slurry in a suitable diluent, which is a poor solvent for the copolymer.
  • the isobutylene-co-paramethylstyrene copolymers can contain little to no backbone olefinic unsaturation contribution from the paramethylstyrene, and the primary reactive halogenation site is the enchained paramethylstyrene moiety.
  • radical halogenation e.g., radical bromination
  • the enchained paramethylstyrene moiety in the isobutylene-co-paramethylstyrene copolymer can be made highly specific with substitution occurring on the para-methyl group.
  • the isobutylene-co- param ethyl styrene copolymer in hydrocarbon solvents can be selectively brominated using light, heat, or selected radial initiators as promotors of radical halogenation.
  • hydrocarbon solvents e.g., pentane, hexane, or heptane
  • halogenation reactions that can be performed to functionalize the isobutylene-co- param ethyl styrene based elastomers described herein.
  • halogenated isobutylene-co-paramethylstyrene based elastomers can comprise at least 0.25 wt% (e.g., from about 0.25 wt% to about 4 wt%) of the halogen.
  • the halogenated isobutylene-co-paramethylstyrene based elastomers can comprise from about 0.1 to about 7.5 mole percent of halogenated paramethylstyrene derived units.
  • suitable halogenated isobutylene-co-paramethylstyrene based elastomers can include elastomers that are commercially available as ExxproTM elastomers (ExxonMobil Product Solutions Company, Houston TX), and abbreviated as “BIMSM,” such as: ExxproTM 3035 (e.g., comprising about 0.47 mole percent of benzylic bromine), 3433 (e.g., comprising about 0.75 mole percent of benzylic bromine), 3563 (e.g., comprising about 0.85 mole percent of benzylic bromine), and/or 3745 (e.g., comprising about 1.2 mole percent of benzylic bromine).
  • ExxproTM 3035 e.g., comprising about 0.47 mole percent of benzylic bromine
  • 3433 e.g., comprising about 0.75 mole percent of benzylic bromine
  • 3563 e.g., comprising about 0.85 mole percent of
  • the isobutylene-co-paramethylstyrene based elastomers it is desirable to improve mechanical properties while maintaining, or improving, processability properties.
  • Such properties can be a function of molecular weight and can include, for example: extrusion rate, die swell, mixing time, filler dispersion, cold flow, green strength, tire cord strike-through, building tack, adhesion, stress relaxation rates, and/or various vulcanizate properties.
  • various properties can have conflicting relationships with the molecular weight of the elastomer. For instance, as the molecular weight of the elastomer increases, the green strength value improves while the stress relaxation rate diminishes (e.g., slows).
  • Green strength can characterize the elastomer’s ability to resist excessive flow and deformation during various handling and/or processing operations. Stress relaxation rates can characterize the elastomer’s ability to relax after being subjected to stress; thereby enabling the elastomer to avoid shape changes.
  • Stress relaxation rates can characterize the elastomer’s ability to relax after being subjected to stress; thereby enabling the elastomer to avoid shape changes.
  • the isobutylene-co-paramethylstyrene based elastomers become better able to resist flow and deformation in the various handling operations, they also become more prone to changing shape or pull apart due unrelaxed stresses.
  • increasing molecular weight in order to increase green strength can make it more difficult to process the elastomer and to disperse fillers and additives.
  • various embodiments described herein can enable an improved compromise between various conflicting properties desired in elastomer formation during processing, fabrication, and/or end-use in one or more applications.
  • improved mechanical properties e.g., green strength
  • processability e.g., stress relaxation rates
  • isobutylene-co-paramethylstyrene based elastomers can be achieved by broadening the MWD of the elastomers.
  • the isobutylene-co-paramethylstyrene based elastomers can be produced with a high molecular weight to improve the mechanical properties, whereupon one or more post polymerization modifications can increase the low molecular weight fraction of the elastomers to improve the processability (e.g., stress relaxation rates).
  • compositions that exhibit increased green strength values and faster stress relaxation rates.
  • Such compositions can be particularly useful in products such as: tire components (e.g., tire innerliners and/or tire cure bladders), innertubes, wire and/or cable components, hoses, films, automotive and/or mechanical goods, sponge products, pharmaceuticals (e.g., pharmaceutical rubber stoppers), adhesives, sealants, and/or the like.
  • the isobutylene-co-paramethylstyrene based elastomers can be subjected to one or more post-polymerization peroxide treatments to modify the MWD.
  • the post-polymerization peroxide treatment can utilize chemical and thermal cracking of the copolymer backbone to increase the low molecular weight fraction of the copolymer composition.
  • the isobutylene-co-paramethylstyrene based elastomers can be treated with a peroxide initiator at a temperature ranging from, for example, about 150 °C to about 220 °C (e.g., from about 160 °C to about 190 °C) in a melt mixer.
  • Suitable peroxides can have a decomposition temperature greater than about 130 °C (e.g., greater than 140 °C) and/or be an organic peroxide having a 10 hour half-life temperature greater than about 110 °C.
  • Example peroxides suitable for use in the peroxide treatment include, but are not limited to: dicumyl peroxide; 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane; dicumyl peroxide; alpha, alpha-bis(t-butylperoxy) diisopropylbenzene; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; t- butyl cumyl peroxide; di-t-butyl peroxide; 2,5-dimethyl-2,5-di(-t-butylperoxy)hexyne, and/or mixtures thereof; organic peroxides such as dialkylperoxides,
  • the amount of peroxide initiator can range from, for example, about 0.2 to about 4.5 wt %, based on the amount of isobutylene-co- param ethyl styrene based elastomer.
  • the amount of peroxide initiator utilized in the MDW modification can increase as the concentration of halogen increases in the isobutylene-co-paramethylstyrene based elastomer.
  • the post polymerization peroxide treatment can be performed prior to the halogenation reactions described herein or subsequent to the halogenation reactions (e.g., prior or post a bromination reaction).
  • the peroxide treatment can result in a modified isobutylene-co-paramethylstyrene based elastomer having a high fraction of low molecular weight species (as compared to the isobutylene-co-paramethylstyrene based elastomer prior to the peroxide treatment); thereby broadening the copolymer’s MWD.
  • the peroxide treatment can chemically induce a thermal breaking along the copolymer backbone of the isobutylene-co-paramethylstyrene based elastomer to increase the fraction of low molecular weight species.
  • the modified isobutylene-co-paramethylstyrene based elastomer can have a Mw ranging from, for example, about 10,000 Da to about 1,000,000 Da (e.g., from about 25,000 Da to about 500,000 Da).
  • the modified isobutylene-co- param ethyl styrene based elastomer can have a Mn less than 150,000 Da, less than 100,000 Da, or less than 50,000 Da.
  • the low molecular weight species can have a molecular weight ranging from, for example, about 10,000 Da to about 200,000 Da (e.g., from about 25,000 Da to about 100,000 Da).
  • the peroxide treatment can increase the low molecular weight fraction to a range of about 20 Da to about 60 Da (e.g., from about 20 Da to about 40 Da).
  • the modified isobutylene-co-paramethylstyrene based elastomer can have a MWD ranging from, for example, about 2.5 to 10 (e.g., from 6.1 to 10).
  • the modified isobutylene-co-paramethylstyrene based elastomer can further comprise one or more branch moieties resulting from one or more coupling reactions occurring from the peroxide treatment.
  • the modified isobutylene-co-paramethylstyrene based elastomers described herein can have branched structures formed by the incorporation (e.g., during the peroxide treatment process) of crosslinking or cationically active co-monomers and/or agents, referred to herein as “branching agents.”
  • branching e.g, long chain branching
  • the amount of branching can be controlled to achieve a desired MWD (e.g, to achieve a desired MWD that can subsequently be broadened by one or more peroxide treatments described herein).
  • the MWD of the modified isobutylene-co-paramethylstyrene based elastomer can further be a function of linear fractions of the polymer versus branched fractions of the polymer.
  • branching agents are employed to promote crosslinking reactions
  • randomized long chain branching can occur to modify the entire MWD of the isobutylene-co- param ethyl styrene based elastomer.
  • soluble moieties containing multiple reactive sites can be employed as the branching agent to introduce a controlled amount of a high molecular weight branched fraction into the distribution without modifying the entire molecular weight distribution of the polymer.
  • a small amount of a very highly functional and reactive soluble moiety can be used to introduce a small amount of very high molecular weight highly branched material into the distribution.
  • a larger amount of a less reactive, lower functionality moiety can be used to introduce more of the branched fraction, but of lower molecular weight.
  • the cationically reactive branching agents can be present during polymerization process in an amount effective for producing desired changes in MWD (e.g., which can later serve as the high molecular weight component in one or more blended compositions).
  • the amount of cationically reactive branching agents can vary depending on the number and reactivity of the cationically active species, including such variables as molecular weight and reactivity of the agent (particularly that portion of the agent containing the cationically active moiety). Additionally, polymerization conditions can influence the effective concentration (e.g., batch versus continuous, temperature, monomer conversion, and/or the like). In one or more embodiments, the amount of cationically reactive branching agents can range from, for example, about 0.3 to about 3.0 weight percent, based on the monomers.
  • the modified isobutylene-co-paramethylstyrene based elastomers can be mixed with unmodified isobutylene-co-paramethylstyrene elastomers (e.g., not subjected to the peroxide treatment) to form a blended composition.
  • blending modified and unmodified elastomers can further control the MWD.
  • the modified isobutylene-co-paramethylstyrene elastomers and the unmodified isobutylene-co-paramethylstyrene based elastomers can have widely different and defined molecular weights; with the modified isobutylene-co- param ethyl styrene based elastomers contributing low molecular weight species to the blended composition, and the unmodified isobutylene-co-paramethylstyrene based elastomers contributing the majority of the high molecular weight species.
  • a tailor-made MWD can be achieved.
  • the blended composition can maintain, or improve, the polymer’s mechanical properties (e.g., green strength levels) while also improving the polymer’s processability (e.g., increasing the stress relaxation rate).
  • the effects of blending the modified isobutylene-co- param ethyl styrene based elastomers and unmodified isobutylene-co-paramethylstyrene based elastomers can be achieved via a direct synthesis process by utilizing the polymer product of two or more reactors (e.g., operating in parallel or series) or polymerization zones (e.g., of a single reactor).
  • each zone, or reactor can produce a polymer (e.g., modified isobutylene-co-paramethylstyrene based elastomers or unmodified isobutylene-co- param ethyl styrene based elastomers) with molecular weight characteristics desired for the final product, where blending the polymer products together can achieve a target MWD and/or incorporate desired characteristics (e.g., mechanical and/or processability properties).
  • the blended compositions described herein can have a MWD ranging from 2.5 to 10.0.
  • a blending ratio of unmodified isobutylene-co-paramethylstyrene based elastomer to modified isobutylene-co-paramethylstyrene based elastomer can range from, for example, about 0.1 : 1 to about 1 :0.1.
  • the blended composition can have a low molecular weight fraction (e.g., characterizing the amount of species having a molecular weight less than 100,000 Da) ranging from, for example, about 10 wt% to about 90 wt%; and a high molecular weight fraction (e.g., characterizing the amount of species having a molecular weight greater than 100,000 Da) ranging from, for example, about 10 wt% to about 90 wt%.
  • a low molecular weight fraction e.g., characterizing the amount of species having a molecular weight less than 100,000 Da
  • a high molecular weight fraction e.g., characterizing the amount of species having a molecular weight greater than 100,000 Da
  • the various embodiments and/or features described herein can be practiced in various orders.
  • the peroxide treatment can be applied to isobutylene-co- param ethyl styrene based elastomers before or after halogenation.
  • modified isobutylene-co-paramethylstyrene based elastomers, or blended compositions thereof, can be subsequently halogenated to achieve the various halogen composition characteristics described herein.
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize a non-blended, non-halogenated isobutylene- co-param ethyl styrene based elastomer with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise treating a non-halogenated isobutylene-co- param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve the desired MWD.
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize a blended, non-halogenated isobutylene-co- param ethyl styrene based elastomer composition with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise: treating a non-halogenated isobutylene- co-paramethylstyrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve a modified non-halogenated isobutylene-co-paramethylstyrene based elastomer; and blending the modified non-halogenated isobutylene-co-paramethylstyrene based elastomer with a non-modified isobutylene-co-paramethylstyrene based elastomer (e.g., having substantially the same composition as the non-halogenated isobutylene-co-paramethylstyrene based elastomer previously treated) to achieve a blended composition with the desired MWD.
  • the peroxide treatment e.g., at 160 °C to 190 °C
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize a non-blended, halogenated isobutylene-co- param ethyl styrene based elastomer with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise: treating a non-halogenated isobutylene-co- param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve a modified non-halogenated isobutylene-co-paramethylstyrene based elastomer; and treating the modified non-halogenated isobutylene-co-paramethylstyrene based elastomer to a halogenation reaction to achieve a modified halogenated isobutylene-co-paramethylstyrene based elastomer with the desired MWD.
  • the peroxide treatment e.g., at 160 °C to 190 °C
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize another non-blended, halogenated isobutylene- co-param ethyl styrene based elastomer with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise treating a halogenated isobutylene-co- param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve the desired MWD.
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize a blended, halogenated isobutylene-co- param ethyl styrene based elastomer composition with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise: treating a non-halogenated isobutylene- co-param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve a modified non-halogenated isobutylene-co-paramethylstyrene based elastomer; blending the modified non-halogenated isobutylene-co-paramethylstyrene based elastomer with a non-modified isobutylene-co-paramethylstyrene based elastomer (e.g., having substantially the same composition as the non-halogenated isobutylene-co-paramethylstyrene based elastomer previously treated) to achieve a blended composition; and treating the blended composition to a halogenation reaction described herein to achieve a blended, halogenated isobutylene-co-paramethylstyrene based e
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize another blended, halogenated isobutylene-co- param ethyl styrene based elastomer composition with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise: treating a non-halogenated isobutylene- co-param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve a modified non-halogenated isobutylene-co-paramethylstyrene based elastomer; treating the modified non-halogenated isobutylene-co-paramethylstyrene based elastomer to a halogenation reaction; and blending the modified halogenated isobutylene-co- param ethyl styrene based elastomer with a non-modified isobutylene-co-paramethylstyrene based elastomer (e.g., halogenated or non-halogenated) to achieve a blended, halogenated isobutylene-co-paramethylstyrene based elastomer
  • the synthesis methodology of one or more embodiments described herein can be employed to synthesize another blended, halogenated isobutylene-co- param ethyl styrene based elastomer composition with a MWD ranging from 2.5 to 10.0 (e.g., 6.1 to 10).
  • the synthesis can comprise treating a halogenated isobutylene-co- param ethyl styrene based elastomer with the peroxide treatment (e.g., at 160 °C to 190 °C) to achieve a modified halogenated isobutylene-co-paramethylstyrene based elastomer; and blending the modified halogenated isobutylene-co-paramethylstyrene based elastomer with a non-modified isobutylene-co-paramethylstyrene based elastomer (e.g., having substantially the same composition as the halogenated isobutylene-co-paramethylstyrene based elastomer previously treated) to achieve a blended composition with the desired composition.
  • a halogenated isobutylene-co- param ethyl styrene based elastomer with the peroxide treatment (e.
  • Non-limiting example embodiments of the present disclosure include:
  • Embodiment A A method for preparing an isobutylene-co-paramethylstyrene composition, the method comprising:_treating an isobutylene-co-paramethylstyrene based elastomer with a peroxide initiator at a temperature greater than or equal to 160 °C to chemically induce a thermal breaking along the copolymer backbone of the isobutylene-co- param ethyl styrene based elastomer, where the treating produces a modified isobutylene-co- param ethyl styrene based elastomer having a Mw/Mn ratio greater than 2.5.
  • Non-limiting example embodiment A can include one or more of the following elements.
  • Element 2 A wherein the temperature ranges from 160 to 190 °C.
  • Element 3 A wherein the isobutylene-co-paramethylstyrene based elastomer comprises 80 to 99.5 mole percent of isobutylene and 0.5 to 20 mole percent of paramethylstyrene.
  • Element 4A wherein the isobutylene-co-paramethylstyrene based elastomer comprises 5 mole percent of the paramethylstyrene.
  • Element 5 A wherein the isobutylene-co-paramethylstyrene based elastomer has an average molecular weight (Mw) ranging from, for example, about 200,000 to about 2,000,000 Daltons.
  • Mw average molecular weight
  • Element 6A wherein the isobutylene-co-paramethylstyrene based elastomer has a Mw/Mn ratio less than 2.5.
  • Element 7A wherein the isobutylene-co-paramethylstyrene based elastomer has a Mw/Mn ratio less than 2.0.
  • Element 8A further comprising: blending the modified isobutylene-co- param ethyl styrene based elastomer with an amount of the isobutylene-co-paramethylstyrene based elastomer to control a Mw/Mn ratio of the isobutylene-co-paramethylstyrene composition.
  • Element 9A wherein the blending is performed with a blending ratio of the isobutylene-co-paramethylstyrene based elastomer to the modified isobutylene-co- param ethyl styrene based elastomer that ranges from 0.5: 1.0 to 2.0: 1.0.
  • Element 10 A wherein the blending ratio is 1 : 1.
  • Element 11 A wherein the Mw/Mn ratio of the isobutylene-co-param ethylstyrene composition is at least two times greater than the Mw/Mn ratio of the isobutylene-co- param ethyl styrene based elastomer.
  • Element 12A wherein the Mw/Mn ratio of the isobutylene-co-paramethylstyrene composition ranges from 6.0 to 10.0.
  • Element 13 A wherein the isobutylene-co-paramethylstyrene based elastomer is halogenated prior to the treating with the peroxide initiator.
  • Element 14A further comprising: halogenating the modified isobutylene-co- param ethyl styrene based elastomer.
  • Element 15 A further comprising: halogenating the modified isobutylene-co- param ethyl styrene based elastomer prior to the blending.
  • Element 16 A further comprising: halogenating the modified isobutylene-co- param ethyl styrene based elastomer subsequent to the blending.
  • Embodiment B A method for preparing an isobutylene-co-paramethylstyrene based elastomer, the method comprising:_increasing a low molecular weight fraction of an isobutylene-co-paramethylstyrene based elastomer by mixing the isobutylene-co- param ethyl styrene based elastomer with a peroxide initiator at a temperature greater than or equal to 160 °C, where the mixing produces a modified isobutylene-co-param ethylstyrene based elastomer having a Mw/Mn ratio greater than 2.5.
  • Non-limiting example embodiment B can include one or more of the following elements.
  • Element IB wherein the isobutylene-co-paramethylstyrene based elastomer is a nonhalogenated elastomer, a halogenated elastomer, a branched elastomer, or a combination thereof.
  • Element 2B wherein the isobutylene-co-paramethylstyrene based elastomer comprises 80 to 99.5 mole percent of isobutylene and 0.5 to 20 mole percent of paramethylstyrene.
  • Element 3B further comprising: blending the modified isobutylene-co- param ethyl styrene based elastomer with an amount of the isobutylene-co-paramethylstyrene based elastomer to control a Mw/Mn ratio of the isobutylene-co-paramethylstyrene composition.
  • Element 4B wherein the blending is performed with a blending ratio of the isobutylene-co-paramethylstyrene based elastomer to the modified isobutylene-co- param ethyl styrene based elastomer that ranges from 0.5: 1.0 to 2.0: 1.0.
  • Embodiment C An isobutylene-co-paramethylstyrene based elastomer comprising 80 to 99.5 mole percent of isobutylene and 0.5 to 20 mole percent of paramethylstyrene, having a substantially homogenous compositional distribution, and having a Mw/Mn ratio greater than 6.0.
  • Non-limiting example embodiment C can include one or more of the following elements.
  • Element 1C wherein the paramethylstyrene is represented by the formula: wherein X is hydrogen or a halogen.
  • Element 2C wherein X is bromine.
  • Element 3C A cured article comprising the isobutylene-co-paramethylstyrene based elastomer of embodiment C, wherein the cured article is a tire innerliner, an innertube, a wire coating, a pharmaceutical rubber stopper, a hose, a film, an adhesive, or a sealant.
  • GPC is an analytical procedure used for separating molecules by differences in size. The procedure as applied to polymers results in a concentration distribution of molecular weights. Most often, concentration is determined using differential refractive index (DRI) and the concentration v. time elution curve is related to molecular weight by means of a calibration curve based on a "known" standard. Utilizing low-angle laser light-scattering (LALLS) photometry in conjunction with DRI, direct determination of molecular weight can be made.
  • DRI differential refractive index
  • LALLS low-angle laser light-scattering
  • Molecular weight averages can be calculated based on the data obtained from a GPC test. Molecular weight averages include: number average (Mn), weight average (Mw) and Z- average (Mz). These averages are also referred to as the various moments of the distribution. Higher molecular weight species have a greater influence on the Z and weight averages whereas lower molecular weight species more greatly influence the number average.
  • the breadth of the distribution overall as well as parts of it can be characterized by reference to various ratios, e.g., Mw/Mn and Mz/Mw; the higher the values of the ratio, the broader the distribution of molecular weights.
  • Molecular weights were determined by Tosoh BioScience HLC-8320 GPC equipped with an internal DRI detector, an internal UV absorbance detector UV-8320 (254 nm absorbance Detector), a Wyatt Technology miniDawn TREOS light scattering detector with three angles (45°, 90°, and 135°), and a Wyatt Technology ViscoStar-II viscometer detector, a series of three of Polymer Labs PLgel Mixed-B with peak Mw; range of 580-10,000,000. The columns were calibrated using Polymer Labs EasiVial polystyrene standards (high, medium, and low) standards.
  • THF tetrahydrofuran
  • BHT butylated hydroxyl toluene
  • Acrodisc filter membrane type PTFE
  • sample solvent tetrahydrofuran containing 250-400 ppm of butylated hydroxyl toluene
  • sample concentration 2.0 mg/mL
  • sample dissolution temperature room temp ( ⁇ 23 °C); sample dissolution time: 3 hours minimum on dissolving wheel
  • GPC pump oven and column oven temperatures 40°C;
  • Flow rate 1 mL/min
  • mobile phase solvent THF (same as sample solvent); sample injection size: 150 pL; sample elution time: 65 minutes.
  • the Wyatt Technology’s Astra 6.1 GPC software was used for data analysis.
  • the universal calibration curve methodology data was primarily used for reporting the results.
  • the non-halogenated isobutylene-co-paramethylstyrene based elastomer XP-50 commercially available from ExxonTM, was modified via the peroxide treatment described herein, where a Di -Cup® was utilized as the peroxide initiator.
  • Table 1 shown below, illustrates the composition of three example isobutylene-co-paramethylstyrene based elastomer (e.g., Elastomers 1-3).
  • the XP-50 was mixed with varying amounts of Di-Cup® in a 280 gram mixing bowl at about 100 °C. The temperature was then raised to 190 °C and the batch was further mixed for 5 minutes.
  • Table 2 presents the molecular weight and MWD data for the example isobutylene-co-paramethylstyrene based elastomers (e.g., Elastomers 1-3), as determined using a light scattering detector.
  • Table 3 presents the molecular weight and MWD data for the example isobutylene-co-paramethylstyrene based elastomers e.g., Elastomers 1-3), as determined using an universal calibration with inline viscometer data.
  • the brominated example elastomers (e.g, Elastomer 1-Br, Elastomer 2-Br, and Elastomer 3-Br) were blended with a non-halogenated isobutylene-co-paramethylstyrene based elastomer, refer to herein as “Comparative Elastomer A”, at various blending ratios (Comparative Elastomer A to brominated example elastomer).
  • Table 4 depicts the molecular weight and MWD data for the elastomers, as determined by the light scattering detector.
  • Table 5 depicts the molecular weight and MWD data for the elastomers, as determined using a universal calibration with inline viscometer data.
  • Tables 4-5 also include the molecular weight and MWD for the unmodified Comparative Elastomer A isobutylene-co- paramethylstyrene based elastomer, which is the brominated embodiment of XP-50.
  • Table 6 presented below, includes the FTIR data of the brominated MWD modified example elastomers (e.g., Elastomer 1-Br, Elastomer 2-Br, Elastomer 3-Br).
  • Table 6 depicts the mole percent of the brominated and non-brominated paramethylstyrene (“PMS”) component of the example elastomer.
  • PMS paramethylstyrene
  • the brominated isobutylene-co-paramethylstyrene based elastomers ExxproTM 3035 and ExxproTM 3745, commercially available from ExxonTM were modified via the peroxide treatment described herein (e.g., bromination of the isobutylene-co- param ethyl styrene based elastomers was performed pre MWD modification by the peroxide treatment), where a Di-Cup® was utilized as the peroxide initiator.
  • Table 7 shown below, illustrates the composition of six example isobutylene-co-param ethyl styrene based elastomers (e.g., Elastomers 4-9).
  • ExxproTM 3035 or ExxproTM 3745 was mixed with varying amounts of Di-Cup® in a 280 gram mixing bowl at about 100 °C. The temperature was then raised to 190 °C and the batch was further mixed for 5 minutes.
  • Table 7 Example Elastomer Compositions [0095] Additionally, Table 8 presents the molecular weight and MWD data for the example isobutylene-co-paramethylstyrene based elastomers (e.g., Elastomers 4-9), as determined using a light scattering detector. Further, Table 9 presents the molecular weight and MWD data for the example isobutylene-co-paramethylstyrene based elastomers (e.g., Elastomers 4-9), as determined using an universal calibration with inline viscometer data. Table 8 - Light Scatter Detector
  • Table 10 includes the FTIR data of ExxproTM 3035 and Elastomer 4.
  • Table 10 depicts the mole percent of the brominated and non-brominated paramethylstyrene (“PMS”) component of the elastomers.
  • PMS brominated and non-brominated paramethylstyrene
  • the brominated isobutylene-co-paramethylstyrene based elastomer ExxproTM 3035 commercially available from ExxonTM, was modified via the peroxide treatment described herein, where Di-Cup® or Luperox® 101 were utilized as the peroxide initiator.
  • ExxproTM 3035 was mixed with varying amounts of Di-Cup® or Luperox® 101 in a 280 gram mixing bowl at about 100 °C. The temperature was then raised to 190 °C and the batch was further mixed for 5 minutes.
  • Table 11 Example Elastomer Compositions [0098] Additionally, Table 12 presents the molecular weight and MWD data for example Elastomers 12-15 as determined using a light scattering detector. Further, Table 13 presents the molecular weight and MWD data for example Elastomers 12-15, as determined using a universal calibration with inline viscometer data.
  • Table 13 - Universal Calibration [0099] Moreover, Table 14 includes the FTIR data of Elastomers 10-15. In particular, Table
  • Elastomers 10-15 optimizing the amount of peroxide used to treat the isobutylene-co-paramethylstyrene based elastomer can affect the amount of brominated paramethylstyrene.
  • Elastomers 10-15 exhibit high amounts of brominated paramethylstyrene, which can promote further crosslinking in various industrial applications.
  • Table 15 depicts the Mooney viscosity of ExxproTM 3035 and Elastomers 12-14, each of which comprised 5 wt% of paramethylstyrene.
  • Elastomers 12-14 were blended with ExxproTM 3035, where Table 16 depicts the molecular weight and MWD data for the elastomers, as determined by the light scattering detector.
  • the peroxide treatment described herein can modify the MWD of halogenated (e.g., brominated) isobutylene-co-paramethylstyrene based elastomers while forming a substantially soluble non-gelatinous product (e.g., while avoiding gel formation).
  • halogenated e.g., brominated
  • the peroxide treatment conditions described herein can result in modified halogenated (e.g., brominated) isobutylene-co-paramethylstyrene elastomer compositions without substantial amounts of gel formation.
  • 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. Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein.
  • the particular examples and configurations disclosed above are illustrative only, as the present 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.
  • no limitations are intended to the details of construction or design herein shown, other than as described in the claims below.
  • 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.

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Abstract

L'invention concerne des procédés de préparation de compositions d'isobutylène-co-paraméthylstyrène. Par exemple, un ou plusieurs procédés comprennent le traitement d'un élastomère à base d'isobutylène-co-paraméthylstyrène avec un initiateur de peroxyde à une température supérieure ou égale à 160 °C pour induire chimiquement une rupture thermique le long du squelette de copolymère de l'élastomère à base d'isobutylène-co-paraméthylstyrène. Le traitement au peroxyde peut produire un élastomère à base d'isobutylène-co-paraméthylstyrène modifié ayant un rapport Mw/Mn supérieur à 2,5.
PCT/US2023/073301 2022-09-13 2023-09-01 Synthèse d'élastomères à base d'isobutylène-co-paraméthylstyrène ayant de larges distributions de poids moléculaire WO2024059443A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162445A (en) 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
EP0544767B1 (fr) * 1990-08-23 1997-09-03 Exxon Chemical Patents Inc. Procede pour produire des polymeres d'isoolefine a faible poids moleculaire
WO2004005388A1 (fr) * 2002-07-05 2004-01-15 Exxonmobil Chemical Patents Inc. Nanocomposite elastomere fonctionnalise

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162445A (en) 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
EP0544767B1 (fr) * 1990-08-23 1997-09-03 Exxon Chemical Patents Inc. Procede pour produire des polymeres d'isoolefine a faible poids moleculaire
WO2004005388A1 (fr) * 2002-07-05 2004-01-15 Exxonmobil Chemical Patents Inc. Nanocomposite elastomere fonctionnalise

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