JP2019510109A - Graft copolymer for dispersing graphene and graphite - Google Patents

Abstract

  Disclosed is a graft copolymer nanofiller dispersant comprising a polyaromatic hydrocarbon backbone and a polyaliphatic hydrocarbon comb arm, and a method for making the same. Also disclosed is an elastic nanocomposite composition comprising graphite or graphene halobutyl rubber matrix nanoparticles and a graft copolymer nanofiller dispersant. Such elastic nanocomposite compositions are useful tire inner liners or inner tubes.

Description

This application claims priority to US Provisional Patent Application No. 62 / 356,248 filed on June 29, 2016 and European Patent Application No. 16185358.5 filed on August 23, 2016. These disclosures are fully incorporated herein by reference thereto.
The present invention relates to a graft copolymer having a polyaromatic hydrocarbon backbone and a polyaliphatic hydrocarbon branch for use as a graphite or graphene dispersant in an elastic nanocomposite composition.

Halobutyl rubbers (these are halogenated isobutylene / isoprene copolymers) are exceptional polymers for best air retention in tires for passenger cars, trucks, buses, and aircraft vehicles. Bromobutyl rubber, chlorobutyl rubber, and halogenated star-branched butyl rubber can be formulated for special tire applications, such as tubes or innerliners. Selection of ingredients and additives for the final commercial formulation is the desired property, i.e., processability and stickiness of raw (uncured) compound in the tire plant during use of the cured tire composite. Depends on performance balance. Examples of halobutyl rubbers are bromobutyl (brominated isobutylene-isoprene rubber or BIIR), chlorobutyl (chlorinated isobutylene-isoprene rubber or CIIR), star-branched butyl (SBB), EXXPRO ^™ elastomer (brominated isobutylene co-p-methyl). -Styrene) copolymer or BIMSM).
For rubber compounding applications, conventional small submicron fillers such as carbon black and silica are added to halobutyl rubber to improve fatigue resistance, fracture toughness and tensile strength. More recently, methods have been developed to change product properties and improve the air barrier properties in halobutyl rubber, these methods adding nanofillers to these elastomers in addition to these conventional fillers. Producing a "composite material". Nanocomposites are polymer systems that contain inorganic particles having at least one dimension in the nanometer range (see, eg, WO Publication No. 2008/042025).

A common type of inorganic particles used in nanocomposites is phyllosilicates, which are inorganic substances from the general class of so-called “nanoclays” or “clays” that are generally provided in intercalated form, Clay platelets or leaves are stacked in individual clay articles and the interleaf spacing is usually maintained by the insertion of another compound or species between adjacent lamellae. Ideally, the interstitial additive is inserted into the space or gallery between the clay surfaces. Ultimately, it is desirable to have surface delamination, in which case the polymer is well dispersed in individual nanometer sized clay platelets.
The degree of dispersion of the plate-like nanofiller, for example, organosilicate, mica, hydrotalcite, graphite carbon, etc., surface peeling, and orientation strongly influence the permeability of the resulting polymer nanocomposite. The theoretical polymer barrier properties are just a few volumes of exfoliated high aspect ratio platy filler, simply due to the increased diffusion path length obtained from the long detour around the platelet. The percent variance improves significantly in magnitude. Nielsen, J. Macromol. Sci. (Chem.), A1 卷, p. 929 (1967), describes the permeation in polymers by taking into account the increase in bends from impervious, plane-oriented plate fillers. A simple model for measuring sex reduction is disclosed. Gusev et al., Adv. Mater., Vol. 13, p. 1641 (2001) is a volume fraction that multiplies aspect ratios that are well correlated with permeability values that are numerically simulated by direct three-dimensional finite element permeability calculations. A simple stretched exponential function is disclosed that relates permeability reduction to rate.
Therefore, to maximize the effect of aspect ratio on permeability reduction, delamination and dispersion of platelets (which are generally supplied in the form of internally added stacks of platelets) It is beneficial to maximize the degree of. However, in isobutylene polymers, the dispersion of plate-like nanofillers and delamination require a sufficiently advantageous enthalpy contribution to overcome the entropy penalty. In practice, it has thus been found that it is very difficult to disperse ionic nanofillers such as clays in generally inert, non-polar, hydrocarbon elastomers. The prior art has attempted to improve dispersion with limited success by modification of clay particles, modification of rubbery polymers, use of dispersion aids, and use of various blending methods.

Graphite carbon has been studied as an alternative plate-like nanofiller due to the difficulties encountered in dispersing ionic nanoclays in nonpolar elastomers. For example, an elastic composition comprising graphite nanoparticles is described in US Pat. No. 7,923,491.
U.S. Patent Publication No. 2006-0229404 discloses a process for producing an elastomeric composition with exfoliated graphite, in which the diene monomer is polymerized in the presence of exfoliated graphite of 10 phr or more. As a result, graphite is internally added as an elastomer. U.S. Pat. No. 8,110,026 describes a method of making functional graphene sheets (FGS) based on surface delamination of oxidized graphite suitable for high dispersion in a polymer matrix for use in nanocomposites.
Nanographene platelets (NGP) obtained by rapid expansion of graphite have recently become commercially available. These NGPs have a graphite surface as opposed to graphene oxide platelets on the surface of oxidized graphite, and are indeed compatible with nonpolar butyl halobutyl rubbers based on hydrocarbons. However, high surface delamination and dispersion of NGP without agglomeration and aggregation cannot be achieved by solid compounding or solution mixing of these nanoparticles in halobutyl rubber.
Another important document is WO Publication No. 2015/076878.
US Provisional Patent Application No. 62 / 235,116, filed on September 30, 2015, describes these polycyclic aromatic hydrocarbon functionalized isobutylene copolymers and these as nanofiller dispersants to improve the degree of NGP dispersion. The use of a copolymer is disclosed.

  However, graphite and graphene in elastic nanocomposite compositions containing halobutyl rubber useful for tires, air barriers, among others that require air retention to improve the air impermeability of these compositions There is a desire to improve the dispersion of nanofillers.

The present invention provides these nanocomposite compositions with improved air barrier properties and is an isobutylene based elastomer / nanofiller nanocomposite composition suitable for use as a tire inner liner or inner tube The need for improved dispersion of graphite and graphene nanofillers in elastic nanocomposite compositions is satisfied by providing beneficial graphite and graphene nanofiller dispersants therein. In general, nanofiller dispersants comprise the reaction product of a polyaromatic hydrocarbon and a polyaliphatic hydrocarbon, ideally a vinyl / vinylidene terminated polyisobutylene.
Furthermore, the present invention relates to a method for producing an elastic nanocomposite composition comprising these nanofiller dispersant compositions and the produced nanofiller dispersant. Preferably, the nanofiller dispersant composition combines at least one polyaromatic hydrocarbon and at least one polyaliphatic hydrocarbon with the Friedel-Crafts catalyst at a temperature in the range of 80 ° C to 200 ° C. Manufactured. Preferably, the elastic nanocomposite material comprising the nanofiller dispersant comprises the nanofiller dispersant (i) at least one halogenated elastomer component comprising units derived from isoolefins having from 4 to 7 carbons (Preferably, the elastomer component comprises units derived from at least one multiolefin) and (ii) is blended with at least one nanofiller.

The present invention relates to polyaliphatic hydrocarbon branches, ideally polyaromatic hydrocarbons with polyisobutylene, useful as nanofiller dispersants in isobutylene-based elastomer / nanofiller nanocomposite compositions. A graft copolymer having a main chain is described. The nanocomposite composition may comprise a halogenated isobutylene based elastomer and nanofiller, preferably graphite or graphene, suitable for use as an air barrier. The resulting nanocomposite composition of the present invention has improved air barrier properties and is suitable for use as an inner liner or inner tube.
Definitions As used herein, “polymer” may be used to denote a homopolymer, copolymer, interpolymer, terpolymer, and the like. Similarly, a copolymer may represent a polymer comprising at least two monomers, optionally with other monomers. As used herein, when a polymer is referred to as “comprising” a monomer, the monomer is present in the polymer in a polymerized form of the monomer or a derivative form of the monomer. Similarly, if a catalyst component is described as including a neutral, stable form of a component, it is well understood by those skilled in the art that the ionic form of that component is the form that reacts with the monomer to form a polymer. ing.
As used herein, “elastomer” or “elastomer composition” refers to any polymer or composition of polymers (eg, a blend of polymers) that meets the definition of ASTM D1566. Elastomers include mixed blends of polymers, such as melt blending of polymers and / or reactor blends. These terms may be used interchangeably with the term “rubber”.

As used herein, “nanoparticle” or “nanofiller” refers to an inorganic particle having at least one dimension (length, width, or thickness) of less than 100 nanometers.
As used herein, “elastic nanocomposite” or “elastic nanocomposite composition” refers to any elastomer or elastomeric composition further comprising a nanofiller and an optional thermoplastic resin.
As used herein, “phr” is the number of parts per hundred rubber, and is a common rule in the art, where the composition is composed of 100 parts by weight of one or more elastomers or one or more parts. Measured against the main elastomer component on a rubber basis.
As used herein, “compounding” refers to combining an elastic nanocomposite composition with nanofillers and other components other than the thermoplastic resin. These components may contain additional fillers, curing agents, processing aids, accelerators and the like.
As used herein, “isobutylene-based elastomer” or “isobutylene-based polymer” or “isobutylene-based rubber” refers to an elastomer or polymer that contains at least 70 mole percent isobutylene.
“Isoolefin” as used herein refers to any olefin monomer having at least one olefinic carbon having two substitutions on the olefinic carbon.
As used herein, “multiolefin” refers to any monomer having two or more double bonds, eg, multiolefin is any monomer that contains two conjugated double bonds, eg, conjugated dienes such as isoprene. It may be. “
As used herein, “exfoliation” refers to the separation of individual layers of the original inorganic particles so that the polymer can or will surround each separated particle. In embodiments, sufficient polymer or other material is present between each platelet so that the platelets are randomly spaced. For example, one indication of delamination or intercalation may be a plot that does not show x-ray lines or a larger d-spacing due to random spacing or increased separation of lamellar platelets. However, as recognized by the industry and by the educational setting, other evidence, such as permeability tests, electron microscopes, atomic force microscopes, etc. may be useful in showing the results of delamination.

The term “aspect ratio” is understood to mean the ratio of the larger dimension of the nanofiller leaf or platelet to the thickness of the individual leaf or the agglomerate or stack of leaves or platelets. The The thickness of individual leaves / platelets can be measured by crystallographic analysis techniques, while the larger dimensions of leaf / platelets are generally measured by transmission electron microscopy (TEM) analysis, both of which are Known in the industry.
As used herein, “solvent” refers to any substance that can dissolve another substance. When the term solvent is used, it may represent at least one solvent or two or more solvents, unless otherwise specified. The solvent may be polar. The solvent may be nonpolar.
As used herein, “solution” refers to a mixture of one or more substances (solutes) in one or more substances (solvents) uniformly dispersed at the molecular or ionic level. For example, the solution method refers to a mixing method in which both the elastomer and the modified layered filler remain in the same organic solvent or solvent mixture.
As used herein, “hydrocarbon” refers to a molecule or segment of molecules that contains primarily hydrogen and carbon atoms. Often, hydrocarbons also include halogenated variants of hydrocarbons and variants containing heteroatoms, as described in more detail below.
As used herein, “polyaromatic hydrocarbon” refers to a hydrocarbon polymer containing a plurality of aromatic rings.
As used herein, “polyaliphatic hydrocarbon” refers to a non-aromatic hydrocarbon polymer.
As used herein, the term “Friedel-Crafts alkylation reaction” refers to those reactions that are defined as Friedel-Crafts alkylation reactions and those reactions that mimic the behavior of Friedel-Crafts alkylation reactions. Represent both. As used herein, the term “Friedel-Crafts catalyst” refers to a compound capable of catalyzing a Friedel-Crafts alkylation reaction, such as a Lewis acid.

Graft Copolymer Nanofiller Dispersant The graft copolymer nanofiller dispersant of the present invention comprises a polyaromatic hydrocarbon backbone and a polyaliphatic hydrocarbon branch. In general, the graft copolymer is the reaction product between a polyaromatic hydrocarbon and a polyaliphatic hydrocarbon, ideally a vinyl / vinylidene terminated polyisobutylene. The resulting graft copolymer is useful for dispersing graphite or graphene nanoparticles in an elastic nanocomposite based on a halobutyl matrix. Although not wishing to be bound by theory, the graft copolymers herein are preferential to graphite or graphene surfaces due to π-π * interactions between the aromatic rings of polyaromatic hydrocarbons and the graphite surface of graphite or graphene nanoparticles. By acting as a graphite or graphene nanofiller dispersant by bonding to the polymer, and the polyaliphatic hydrocarbon branch extending away from the polyaromatic hydrocarbon backbone, where the dispersant effect of the copolymer acts as a brush It can be strengthened.
Generally, the graft copolymer comprises (or consists essentially of or consists of) a polyaliphatic hydrocarbon component and a polyaromatic hydrocarbon component, where the polyaromatic hydrocarbon component is in the main chain. A polymer comprising a heteroatom or heteroatom-containing moiety and a phenyl group or substituted phenyl group, wherein the polyaliphatic hydrocarbon component is covalently bonded to the polyaromatic hydrocarbon component.
Preferably, the graft copolymer has the following structure:

(I)

(I)

Wherein each of I, II, III and IV is independently 1,2-phenyl, 1,3-phenyl or 1,4-phenyl, any of which is one or more electron-donating substitutions Optionally substituted with a group
At least one of A, B, C, and D is independently an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, or a moiety containing oxygen, nitrogen, sulfur, phosphorus, or a combination thereof;
At least one of E, F, G, and H is one, two, or three polyaliphatic hydrocarbon components bonded to I, II, III, and IV, respectively (with a weight average molecular weight of at least 300 g / mol). And m is an integer in the range of 1 to 10 and n is an integer in the range of 10 to 500.
Most preferably, the polyaromatic hydrocarbon backbone is poly (phenylene ether) (“PPE”), where each of A, B, C, and D in structure (I) is oxygen, and I, II, III and IV are 2,6-dimethyl-1,4-phenyl and m is 1. Preferably, the polyaliphatic hydrocarbon is vinyl / vinylidene terminated polyolefin (“VTPO”), ideally vinyl / vinylidene polyisobutylene (“VTPIB”). In general, for graft copolymers, particularly PPE-VTPO copolymers, the branching index, g _vis.avg, is less than 0.95 or less than 0.90 or less than 0.85. The number average molecular weight (M _n ) of the graft copolymer is preferably in the range from 10,000 or 12,000 or 15,000 g / mol to 100,000 or 140,000 or 180,000 or 200,000 g / mol, and preferably the weight average molecular weight (M _w ). Within the range of 15,000 or 20,000 g / mol to 200,000 or 250,000 or 300,000 or 350,000 g / mol. Also, in general, and for PPE-VTPO copolymers, the graft copolymer has a z-average molecular weight (M _z ) from 30,000 or 35,000 to 200,000 or 300,000 or 350,000 g / mol to 400,000 or 450,000 or 500,000 or 550,000 or 600,000 g / mol. Within range. These ranges apply to both LS or DRI GPC analysis for copolymers. Preferably, the molar ratio of polyaliphatic hydrocarbon to polyaromatic hydrocarbon in the graft copolymer is in the range of 99: 1 or 90:10 to 50:50.

Graft copolymer synthesis generally utilizes a mild catalytic Friedel-Crafts alkylation reaction. It has been found that polyaliphatic hydrocarbons, particularly unsaturated polyolefins, and more particularly VTPO, can be easily grafted onto the polyaromatic hydrocarbon backbone. Specifically, the vinyl / vinylidene end group of VTPO is a good precursor of a carbocation, which acts as an electrophile under a Bronsted acid catalyst or a Lewis acid catalyst. In addition, the arene group of the polyaromatic hydrocarbon acts as a nucleophile in the Friedel-Craft reaction.
The preparation of graft copolymers by Friedel-Craft reaction between polyaromatic hydrocarbons and polyaliphatic hydrocarbons will now be described in more detail. The present invention is not limited to these aspects, and this description is not meant to exclude other aspects within the broader scope of the invention, such as when the graft copolymer is prepared by another transformation route.
Polyaromatic hydrocarbons Suitable polyaromatic hydrocarbons preferably have polymer repeat units, or one or more aromatic moieties in the monomer, which can undergo a Friedel-Crafts alkylation reaction. Polyaromatic hydrocarbons are aromatic polyamide, aromatic polyimide, aromatic poly (amidoimide), aromatic polycarbonate, aromatic polyester, poly (ether ether ketone), poly (ether ketone ketone), aromatic polysulfone, poly (phenylene Ethers), poly (phenylene sulfide), and polyxylylene, most preferably poly (phenylene ether), but are not limited thereto.
The polyaromatic hydrocarbon exemplified herein is PPE. It is expected that the disclosed method can extend beyond PPE to polyaromatic hydrocarbons that share the following generalized chemical structure (II):

(II)

(II)

In the formula, each of I, II, III and IV in (I) is independently 1,2-phenyl, 1,3-phenyl or 1,4-phenyl, any one of which is one or more May be substituted with an electron-donating substituent of
At least one of A, B, C, and D is independently an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, or a moiety containing oxygen, nitrogen, sulfur, phosphorus, or a combination thereof;
Each of E, F, G, and H is a hydrogen atom or C ₁ -C ₁₀ alkyl, or C ₆ -C ₁₂ aryl, and their heteroatom substitution variants (eg, amine, mercaptan, sulfonate, hydroxyl, carboxy, etc.) ) And m is an integer in the range of 1 to 10 and n is an integer in the range of 10 to 500.
Preferably, electron-donating substituents are C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ mercaptans, chlorine, bromine, iodine, hydroxyl, and are selected from the group consisting of. Further, more preferably, A, B, C, and D substituents are C ₁ -C ₁₀ carboxy-containing moiety, C ₁ -C ₁₀ imide-containing moiety, C ₁ -C ₁₀ sulfide-containing moiety, sulfur, sulfide, carboxy, It is selected from the group consisting of carboxylate, imide, nitrogen, and combinations thereof. More preferably, the A, B, C, and D substituents are —CH ₂ —NH—CO— (CH ₂ ) ₄ —CH ₂ —, —OCOO—, CO—, pyromellitic acid diimide, —SO ₂ —, It is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorus, and combinations thereof. The polyaromatic hydrocarbons useful herein (as reactants in the grafting reaction or as components of the copolymer) range from 5,000 or 10,000 or 15,000 g / mol to 20,000 or 30,000 or 50,000 or 80,000 g / mol. Preferably having a weight average molecular weight (M _w ) of In the above structure (II), A, B, C, and D are oxygen, I, II, III, and IV are 2,6-dimethyl-1,4-phenyl, and m is 1. Most preferably it is.

Specific examples of suitable polyaromatic hydrocarbons include, but are not limited to:
・ Nylon MXD6 (Reny ^TM , Mitsubishi Gas Chemical), (I = II = III = IV = 1,3-phenyl, m = 1, A = B = C = D = -CH ₂ -NH-CO- (CH ₂ ) ₄ -CH _2- )
・ PC (Lexan ^TM , SABIC Innovative Plastics, Makrolona ^TM , Bayer, Caliber ^TM , Dow, Panlitem ^TM , Teijin, Iupilona ^TM , Mitsubishi, Xantar ^TM , DSM) (I = II = III = IV = 1,4-phenyl, m = 1, A = C = -C (CH ₃ ) _2- , B = D = -OCOO-)
・ PEEK (Victrex ^TM , Victrex Plc, APC ^TM , Cytec) (I = II = III = 1,4-phenyl, m = 0, A = B = -O-, C = -CO-)
Polyimide, e.g., poly (pyromellitic acid imide 1,4-diphenyl ^{ether) (Kapton TM, Vespel TM,} Pyralux TM, Pyralin TM, Interra TM, Du Pont) (I = II = III = IV = 1,4- phenyl , m = 1, A = C = -O-, B = D = pyromellitic acid diimide)
・ Bisphenol-A polysulfone (Udel ^TM , Solvay) (I = II = III = IV = 1,4-phenyl, m = 1, A = -C (CH ₃ ) _2- , B = D = -O-, C = -SO _2- )
PPE, for example, poly (2,6-dimethyl-1,4-phenylene oxide) (PPO ^™ , Noryl ^™ , Noryl GTX ^™ , Prevex ^™ , Sabic Innovative Plastics, Xyron ^™ , Asahi Kasei, Iupiace ^™ , Lemalloy ^™ , Mitsubishi Engineering Plastics, Artley ^TM , Sumitomo Chemical, Blue Star ^TM , Blue Star) (I = II = III = IV = 2,6-dimethyl-1,4-phenyl, m = 1, A = B = C = D = -O-)
・ PPS (Ryton ^TM , Chevron Phillips Chemical, Fortron ^TM , Celanese, Torelina ^TM , Toray) (I = II = III = IV = 1,4-phenyl, m = 1, A = B = C = D = -S- in the case of)
・ Poly (p-xylene) (Parylene ^TM , former Union Carbide), (I = II = III = IV = 1,4-phenyl, m = 1, A = B = C = D = -CH ₂ CH _2- in the case of)

Polyaliphatic hydrocarbons Polyaliphatic hydrocarbons may be crystalline or amorphous, preferably amorphous. Suitable crystalline or amorphous polyaliphatic hydrocarbons include polyethylene, polypropylene (isotactic, syndiotactic or atactic), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, These include propylene-butene copolymers, propylene-hexene copolymers, propylene-octene copolymers, α-olefin homopolymers and copolymers, cyclic olefin homopolymers and copolymers, polydienes, polyisobutylene (“PIB”), and combinations thereof. It is not limited to.
Suitable polyaliphatic hydrocarbons are preferably polyolefins having one or more unsaturations, more preferably at the chain ends. More particularly, the preferred polyaliphatic hydrocarbon is VTPO. VTPO is made by any suitable means. Preferably, the vinyl / vinylidene terminated polyalphaolefin is a bridged metallocene catalyst compound (especially a bridged bis-indenyl or bridged, as described, for example, in US Patent Publication No. 2012-0245299). It is made using conventional slurry or solution polymerization methods using a combination of 4-substituted bis-indenyl metallocene) and a perfluorinated boron activator of high polymer volume (total volume of at least 1000 3). Also, the vinyl / vinylidene terminated polyisobutylene is preferably made using conventional solution cationic polymerization methods known in the art. Preferably, such cationic polymerization processes are initiated using strong or Lewis acids such as AlCl ₃ and HCl in combination with coinitiators.

A suitable VTPO may be any polyolefin having vinyl / vinylidene end groups, as described above, any of which may have a number average molecular weight (M _n ) of at least 300 g / mol. Preferably, 80% or 85% or more than 90% of the polyolefin contains terminal vinyl or vinylidene groups in the range of 50 or 60% to 70 or 80 or 90% by weight. As the, VTPO preferably has a M _n in the range from 200 or 400 or 500 g / mol up to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g / mol. VTPO has a weight average molecular weight (M _w ) value ranging from 500 or 800 or 1000 or 2000 g / mol to 6,000 or 10,000 or 12,000 or 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g / mol. It is preferable. Preferably, the VTPO useful herein is amorphous polyisobutylene, desirably less than 10 or 5 or 0 ° C, more preferably less than -30 ° C, or 0 or -5 or -10 ° C to -50 or It has a glass transition temperature (Tg) in the range of -60 or -70 ° C, or as described herein.
A particularly preferred VTPO is one in which the vinyl / vinylidene terminated polyolefin is a vinylidene terminated polyisobutylene as represented by the following formula (III):

(III)
式中、ｎは２又は４又は10又は20から50又は100 又は200 又は500 又は800 までの整数である。

(III)
Where n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800.

Friedel-Crafts alkylation Graft copolymers of the preferred composition are those in solution or solid state (eg, in an extruder) reaction of polyaliphatic hydrocarbons having unsaturation with selective aromatic moieties of polyaromatic hydrocarbons. It can be synthesized by Friedel-Crafts alkylation. In terms of composition, it is preferred that the polyaliphatic hydrocarbon mole% in the resulting graft copolymer is greater than 50 mole%, more preferably greater than 55 mole%, and most preferably greater than 60 mole%.
The reaction between the polyaromatic hydrocarbon and the polyaliphatic hydrocarbon is promoted with a Friedel-Crafts catalyst at a temperature in the range from 80 ° C or 100 ° C to 140 ° C or 160 ° C or 180 ° C or 200 ° C. Preferably, the polyaromatic hydrocarbon and polyaliphatic hydrocarbon are reacted in solution. Suitable solvents include high boiling saturated aliphatic hydrocarbons (C ₈ -C ₂₀ ), halogenated aliphatic hydrocarbons (C ₁ -C ₈ ), aryl hydrocarbons (C ₆ -C ₂₀ ), and halogenated aryl carbons. hydrogen (C ₆ ~C ₂₀₎ can be mentioned. Particularly preferred solvents include dodecane, toluene, xylene, and ortho-dichlorobenzene (oDCB).
Elastic Nanocomposite An unblended elastic nanocomposite composition may contain up to 49% by weight of graft copolymer nanofiller dispersant (ie, based on the total amount of nanofiller dispersant, elastomer component, and nanofiller) As). The unblended elastic nanocomposite composition may comprise from 0.5% to 49% by weight of the graft copolymer nanofiller dispersant. Preferably, the unblended elastic nanocomposite composition comprises from 2% to 49% by weight of the graft copolymer nanofiller dispersant. More preferably, the unblended elastic nanocomposite composition comprises from 5% to 45% by weight of the graft copolymer nanofiller dispersant. Ideally, the unblended elastic nanocomposite composition comprises from 10% to 40% by weight of the graft copolymer nanofiller dispersant.
In addition to the graft copolymer nanofiller dispersant, the elastic nanocomposite composition includes at least one additional elastomer component and at least one nanofiller component. If necessary, the elastic nanocomposite composition may further contain one or more thermoplastic resins. Optionally, an elastic nanocomposite composition may be formulated and may include some or all of the following components: processing aids, additional fillers, and curing / accelerators.

Elastomer component The elastomer component or part thereof is halogenated. Preferred halogenated rubbers include bromobutyl rubber, chlorobutyl rubber, brominated copolymers of isobutylene and para-methylstyrene, and mixtures thereof. Halogenated butyl rubber is produced by halogenation of butyl rubber products. The halogenation can be performed by any means, and the present invention is not limited herein by the halogenation method. Often, butyl rubber is halogenated in hexane diluent from 4 ° C. to 60 ° C. using bromine (Br ₂ ) or chlorine (Cl ₂ ) as the halogenating agent. Halogenated butyl rubber has a Mooney viscosity (ML 1 + 8 at 125 ° C.) of 20-80, or 25-60. The halogen mass% is from 0.1 mass% to 10 mass%, or from 0.5 mass% to 5 mass%, based on the mass of the halogenated butyl rubber. Preferably, the halogen mass percent of the halogenated butyl rubber is from 1 mass percent to 2.5 mass percent.
A suitable commercially available halogenated butyl rubber is bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is from 27 to 37 (ML 1 + 8 at 125 ° C., ASTM 1646, revised) and the bromine content is from 1.8% to 2.2% by weight with respect to bromobutyl 2222. Further, the cure characteristics of bromobutyl 2222 are as follows: MH is 28-40 dN · m, ML is 7-18 dN · m (ASTM D2084). Another commercial example of halogenated butyl rubber is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney viscosity is from 41 to 51 (ML 1 + 8 at 125 ° C., ASTM D1646) and the bromine content is from 1.8% to 2.2% by weight. Further, the cure characteristics of bromobutyl 2255 are as follows: MH is 34-48 dN · m and ML is 11-21 dN · m (ASTM D2084).

The elastomer may comprise branched or “star-branched” halogenated butyl rubber. The halogenated star-branched butyl rubber ("HSBB") is often a composition of butyl rubber (halogenated or non-halogenated), and polydiene or block copolymer (halogenated or non-halogenated). including. The present invention is not limited by the method for producing HSBB. The polydiene / block copolymer, or branching agent (hereinafter “polydiene”) is typically cationically reactive and is present during the polymerization of butyl rubber or halogenated butyl rubber or blended with butyl rubber or halogenated butyl rubber to produce HSBB. Can be generated. The branching agent or polydiene may be any suitable branching agent and the present invention is not limited to the type of polydiene used to make the HSBB.
HSBB is a combination of butyl rubber or halogenated butyl rubber as described above and polydienes and styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. It may be a composition of a copolymer of a partially hydrogenated polydiene selected from the group comprising. These polydienes are present in an amount greater than 0.3%, or from 0.3% to 3%, or from 0.4% to 2.7% by weight, based on the monomer weight%.
A commercially available example of HSBB is Bromobutyl 6222 (ExxonMobil Chemical), Mooney viscosity from 27 to 37 (ML 1 + 8, ASTM D1646 at 125 ° C), and from 2.2 to 2.6% by weight relative to HSBB Bromine content. Further, the cure characteristics of bromobutyl 6222 are as follows: MH is 24-38 dN · m, ML is 6-16 dN · m (ASTM D2084).

The elastomer component may be an isoolefin copolymer containing halomethylstyrene derived units. The halomethylstyrene unit may be an ortho-, meta-, or para-alkyl substituted styrene unit. The halomethylstyrene derived unit may be p-halomethylstyrene having a para-isomer of at least 80% by weight, more preferably at least 90% by weight. The “halo” group may be any halogen, preferably chlorine or bromine. The halogenated elastomer may also include a functionalized interpolymer, in which at least some of the alkyl substituents present in the styrene monomer unit include benzyl halogen or some other functional group described further below. . These interpolymers are referred to herein as “isoolefin copolymers containing halomethylstyrene derived units” or simply “isoolefin copolymers”.
The isoolefin of the copolymer may be a C ₄ -C ₁₂ compound, these non-limiting examples being isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2- Compounds such as butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4-methyl-1-pentene. The copolymer may also further comprise one or more multiolefin derived units. The multiolefin is a C ₄ -C ₁₄ multiolefin, such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene. May be. Desirable styrene monomer derived units that may constitute the copolymer include styrene, methylstyrene, chlorostyrene, methoxystyrene, indene and indene derivatives, and combinations thereof.
Often, the elastomer component of ethylene derived units or C ₃ -C ₆ alpha-olefin derived units and para - alkylstyrene comonomer, preferably at least 80 wt%, more preferably at least 90% by weight of para - para including isomers - methyl It may be a random elastic copolymer of styrene7 and includes a functionalized interpolymer in which at least some of the alkyl substituents present in the styrene monomer unit contain benzyl halogen or some other functional group. Preferred materials may be characterized as interpolymers comprising the following monomer units randomly spaced along the polymer chain.

Where R and R ¹ are independently hydrogen, lower alkyl, preferably C ₁ -C ₇ alkyl and primary or secondary alkyl halide, and X is a functional group such as halogen, triethylammonium, trimethylammonium, Or other functional groups. Desirable halogens include chlorine, bromine or combinations thereof. Preferably R and R ¹ are each hydrogen. The -CRR ₁ H group and -CRR ₁ X group can be substituted at the ortho-position or para-position, preferably para-position, in the styrene ring. Up to 60 mol%, or from 0.1 mol% to 5 mol% of the p-substituted styrene present in the interpolymer structure may be the above functionalized structure (2). The amount of functionalized structure (2) is from 0.4 mol% to 1 mol%.
In any embodiment, the functional group X is other groups, such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxides; phenoxides; thiolates; thioethers; xanthates; It may also be a functional group incorporated by nucleophilic substitution of benzyl halogen with a mixture. These functionalized isomonoolefin copolymers, methods for their preparation, methods of functionalization, and curing are more particularly disclosed in US Pat. No. 5,162,445.

The most useful of such halogenated materials are elastic random interpolymers of isobutylene and alkyl styrene, preferably 0.5 to 20 mol% alkyl styrene, preferably p-methyl styrene [in this case, on the benzyl ring. Up to 60 mol% of the methyl substituents present contain bromine or chlorine atoms, preferably bromine atoms (p-bromomethylstyrene)], as well as their acid or ester functionalized variants (in this case halogen atoms) Is substituted with maleic anhydride or acrylic acid or methacrylic acid functional groups). These interpolymers are referred to as “halogenated poly (isobutylene co-p-methylstyrene)” or “brominated poly (isobutylene co-p-methylstyrene)” and are named EXXPRO ^™ elastomer (ExxonMobil Chemical, Houston, Texas). Is commercially available. The use of the term “halogenated” or “brominated” is not limited to the method of halogenation of the copolymer, but is merely a reference to a copolymer that may contain isobutylene derived units, p-methylstyrene derived units, and p-halomethylstyrene derived units. It is understood that this is only a descriptive expression.
These functionalized copolymers preferably have a substantially uniform composition distribution such that at least 95% by weight of the polymer has a p-alkylstyrene content within 10% of the average p-alkylstyrene content of the polymer. Further preferred polymers are also narrow molecular weight distributions (Mw / Mn) less than 5, more preferably less than 2.5, preferred viscosity average molecular weights ranging from 200,000 to 2,000,000, and ranging from 25,000 to 750,000 as measured by gel permeation chromatography. Characterized by a preferred number average molecular weight.
The copolymer is a slurry polymerization of a monomer mixture using a Lewis acid catalyst, followed by halogenation, preferably bromination, in solution in the presence of a halogen and a radical initiator such as heat and / or light and / or a chemical initiator. And if necessary, it can be prepared by subsequent electrophilic substitution of bromine with different functional derivative units.
Preferred halogenated poly (isobutylene co-alkyl styrene), preferably halogenated poly (isobutylene co-p-methyl styrene), is a brominated polymer containing generally from 0.1% to 5% by weight of bromomethyl groups. Further, the amount of bromomethyl group is from 0.2% by mass to 2.5% by mass. Expressed another way, preferred copolymers contain from 0.05 mol% to 2.5 mol% bromine, more preferably from 0.1 mol% to 1.25 mol% bromine, based on the weight of the polymer, Does not contain halogen in the polymer main chain. In any embodiment, the interpolymer may be a copolymer of C ₄ -C ₇ isomonoolefin derived units and alkyl styrene, preferably p-methyl styrene, derivatives and preferably p-halomethyl styrene derived units, The p-halomethylstyrene units are present in the interpolymer from 0.4 mol% to 1 mol% based on the interpolymer. Preferably, p-halomethylstyrene is p-bromomethylstyrene. Its Mooney viscosity (1 + 8, 125 ° C, ASTM D1646, revised) is from 30MU to 60MU.

The elastomer component may include various amounts of one, two, or more different elastomers. For example, the composition described is 5-100 phr halogenated butyl rubber, 5-95 phr star-branched butyl rubber, 5-95 phr halogenated star-branched butyl rubber, or 5-95 phr halogen. Poly (isobutylene co-alkylstyrene), preferably halogenated poly (isobutylene co-p-methylstyrene). For example, the composition is 40-100 phr halogenated poly (isobutylene co-alkylstyrene), preferably halogenated poly (isobutylene co-p-methylstyrene), and / or 40-100 phr halogenated star-branched butyl rubber ( HSBB).
The elastomer component is natural rubber, polyisoprene rubber, styrene butadiene rubber (SBR), polybutadiene rubber, isoprene butadiene rubber (IBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM). , Polysulfide, nitrile rubber, propylene oxide polymer, star-branched butyl rubber and halogenated star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched brominated Butyl (polyisobutylene / isoprene copolymer) rubber; and poly (isobutylene coalkylstyrene), preferably isobutylene / methylstyrene copolymers such as isobutylene / meta-bromomethylstyrene, isobutylene / bromomethylstyrene Isobutylene / chloromethylstyrene, it may include halogenated isobutylene cyclopentadiene, and isobutylene / chloromethylstyrene and mixtures thereof.

  The elastomer components described herein include natural rubber, polyisoprene rubber, styrene butadiene rubber (SBR), polybutadiene rubber, isoprene butadiene rubber (IBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene rubber, ethylene -Propylene-diene rubber (EPDM), polysulfide, nitrile rubber, propylene oxide polymer, star-branched butyl rubber and halogenated star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, Star-branched brominated butyl (polyisobutylene / isoprene copolymer) rubber; and isobutylene / methylstyrene copolymers such as isobutylene / meta-bromomethylstyrene, isobutylene / bromomethylstyrene, isobutylene / chloromethyls It may further comprise a secondary elastomer component selected from the group consisting of ethylene, halogenated isobutylene cyclopentadiene, and isobutylene / chloromethyl styrene and mixtures thereof. Also, the elastomeric compositions described herein have an elastomer as described above as a “secondary elastomer component” of less than 10 phr, preferably 0 phr secondary elastomer component, preferably 0 phr.

The elastomer component may include one or more semicrystalline copolymers (SCC). Semicrystalline copolymers are described in US Pat. No. 6,326,433. In general, SCC is a copolymer of ethylene or propylene derived units and α-olefin derived units (the α-olefins having 4 to 16 carbon atoms), and ethylene derived units and α-olefin derived units (the α-olefins). Having 4 to 10 carbon atoms), in which case the SCC has some degree of crystallinity. The SCC may also be a copolymer of 1-butene derived units and another α-olefin derived unit, the other α-olefin having 5 to 16 carbon atoms, in which case the SCC is to some extent It has the crystallinity. The SCC may also be a copolymer of ethylene and styrene.
An unblended elastic nanocomposite composition may include up to 99% by weight of one or more elastomeric components or elastomers (eg, based on the weight of the nanocomposite composition). The unblended elastic nanocomposite composition may comprise from 30% to 99% by weight of one or more elastomer components or elastomers. Preferably, the unblended elastic nanocomposite composition comprises from 35% to 90% by weight of one or more elastomer components or elastomers. More preferably, the unblended elastic nanocomposite composition comprises from 40% to 85% by weight of one or more elastomer components or elastomers. More preferably, the unblended elastic nanocomposite composition comprises from 40% to 80% by weight of one or more elastomer components or elastomers. Ideally, the unblended elastic nanocomposite composition may comprise from 40% to 60% by weight of one or more elastomer components or elastomers.

Thermoplastic Resin The elastic nanocomposite composition can include one or more thermoplastic resins. Suitable thermoplastic resins include polyolefins, nylon, and other polymers. Suitable thermoplastic resins may be or include nitrogen, oxygen, halogen, sulfur or other groups that can interact with one or more aromatic functional groups, such as halogens or acidic groups. Suitable thermoplastic resins include polyamide, polyimide, polycarbonate, polyester, polysulfone, polylactone, polyacetal, acrylonitrile-butadiene-styrene resin (ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polystyrene, styrene-acrylonitrile resin ( SAN), styrene maleic anhydride resin (SMA), aromatic polyketones (PEEK, PED, and PEKK) and mixtures thereof.
The elastic nanocomposite composition may include any of the thermoplastic resins described above (also referred to as thermoplastics or thermoplastic polymers) that are molded into a dynamic vulcanized alloy. The term “dynamic vulcanization” is used herein to mean a vulcanization process in which engineering resins and vulcanizable elastomers are vulcanized under high shear conditions. As a result, the vulcanizable elastomer is simultaneously cross-linked and dispersed as “microgel” particulates within the engineering resin matrix. Further descriptions of suitable thermoplastic resins and dynamic vulcanization alloys are available in US Pat. No. 7,923,491, which is hereby incorporated by reference.
The unblended elastic nanocomposite composition may comprise up to 49% by weight thermoplastic resin (eg, based on the weight of the nanocomposite composition). The unblended elastic nanocomposite composition may comprise from 0.5% to 45% by weight thermoplastic resin. Preferably, the unblended elastic nanocomposite composition comprises from 2% to 35% by weight thermoplastic resin. More preferably, the unblended elastic nanocomposite composition comprises from 5% to 30% by weight thermoplastic resin. Ideally, the unblended elastic nanocomposite composition comprises 10% to 25% by weight thermoplastic resin.

Nanofillers Elastic nanocomposite compositions typically comprise nanoparticles of graphite (preferably graphene). Nanoparticles have at least one dimension (length, width or thickness) of less than 100 nanometers. Also, two dimensions (length, width or thickness) are less than 100 nanometers, and all three dimensions (length, width and thickness) are less than 100 nanometers. Preferably, the sheet has a thickness of less than 100 nanometers and a length and / or width that is at least 10 times greater than the thickness (preferably 20 to 500 times, preferably 30 to 500 times the thickness) is there. Also, the shape of the graphite is needle-like or plate-like with an aspect ratio greater than 1.2 (preferably greater than 2, preferably greater than 3, preferably greater than 5, preferably greater than 10, preferably greater than 20). Where the aspect ratio is the ratio of the longest dimension of the particle to the shortest dimension (length, width, and thickness) on average. Also, the graphite is finely pulverized. Useful graphite 10~2000 m ² / g, preferably 50~1000 m ² / g, preferably may have a specific surface area of 100 ~900 m ² / g.

Preferably, the unblended nanocomposite comprises 0.01% to 15.0% by weight graphite (preferably graphene) nanoparticles (ie, based on the total weight of the nanofiller dispersant, elastomer, and nanofiller) . More preferably, the unblended nanocomposite material comprises 0.05 wt% to about 10.0 wt% graphite (preferably graphene) nanoparticles. More preferably, the uncomposited nanocomposite material comprises about 0.1% to about 10.0% by weight; about 0.5% to about 10.0% by weight; about 1.0% to about 10.0% by weight graphite (preferably graphene) nanoparticles. Including. Ideally, uncomposited nanocomposites have a graphite (preferably graphene) ranging from as low as about 0.05, 0.5, or 1.2% to as high as about 5.0, 7.5, or 10.0% by weight. ) Contains nanoparticles.
Preferably, it has a beta form in which graphite (preferably graphene) is present up to 50% by weight, typically from 5% to 30% by weight. Also, graphite (preferably graphene) is present in alpha form and typically has less than 1 wt% beta form, preferably 0 wt% beta form.
The graphite is preferably in the form of nanographene platelets (NGP) obtained by rapid expansion of the graphite. Expanded graphite is typically made by immersing natural flake graphite in a bath of acid (eg, sulfuric acid, nitric acid, acetic acid, and combinations thereof, or chromic acid, followed by concentrated sulfuric acid), which is crystallized. Force the lattice plane away, thus expanding the graphite.

Preferably, the expandable graphite may have one or more of the following properties (before expansion): a) 32 to 200 mesh particle size (also 0.1 to 500 microns (also 0.5 to 350 microns, or 1 Median particle diameter) of ˜100 microns), and / or b) expansion ratio up to 350 cc / g, and / or c) pH of 2-11 (preferably 4-7.5, preferably 6-7.5). Expandable graphite can be purchased from GRAFTech International or Asbury Carbons, Anthracite Industries, among others. Particularly useful expandable graphite includes GRAFGUARD ^™ expandable graphite flakes. The expandable graphite is further ground for the production of NGP, described in US Pat. No. 7,550,529, having a thickness in the range of 1 nanometer to 20 nanometers and a width in the range of 1 micron to 50 microns. obtain. A particularly useful NGP, or short stack of graphene sheets, available from XG Sciences, Inc., xGnP® NGP brands H, M, and C, and from Angstron Materials, Inc. N008-N, N008-P, and N006-P NGP materials.
Preferably, the expandable graphite has an onset temperature (the temperature at which it begins to expand) of at least 160 ° C or higher, 200 ° C or higher, 400 ° C or higher, 600 ° C or higher, 750 ° C or higher, or 1000 ° C or higher. Preferably, the expandable graphite has an expansion ratio at 600 ° C. of at least 50: 1 cc / g, preferably at least 100: 1 cc / g, preferably at least 200: 1 cc / g, preferably at least 250: 1 cc / g. Have The expandable graphite also has an expansion ratio at 150 ° C. of at least 50: 1 cc / g, preferably at least 100: 1 cc / g, preferably at least 200: 1 cc / g, preferably at least 250: 1 cc / g. Have. The graphite may be expanded before it is combined with other blend components, or it may be expanded during blending with other blend components. Often, the graphite does not expand (or is not expandable) after molding into an article (eg, air barrier, or tire inner liner).

Preferably, the graphite is or includes graphene. Graphene is a one-atom-thick planar sheet of sp ² -bonded carbon atoms that are densely packed into the honeycomb crystal lattice. The bond length between carbons in graphene is about 1.42 mm. Graphene is the basic structural element of graphite materials including graphite. This is because graphite is considered to be a multilayer of graphene. Graphene can be prepared by micromechanical cleavage of graphite (eg, removal of graphene flakes from graphite) or surface exfoliation of intercalated graphite compounds. Similarly, graphene fragments can be prepared by chemical modification of graphite. First, microcrystalline graphite is treated with a strongly acidic mixture of sulfuric acid and nitric acid. The material is then oxidized and exfoliated resulting in small graphene plates (with carboxyl groups at their ends). These are converted to acid chloride groups by treatment with thionyl chloride, which are then converted to the corresponding graphenamide by treatment with octadecylamine. The resulting material (5.3 mm thick circular graphene layer) is soluble in tetrahydrofuran, tetrachloromethane, and dichloroethane (Niyogi et al., Solution Properties of Graphite and Graphene, J. Am. Chem. Soc., 128 ( 24), pp. 7720-7721 (2006)). Graphite is also present in the elastomeric composition as dispersed nanosheets having a thickness of less than 100 nanometers, preferably less than 50 nanometers, preferably less than 30 nanometers.

Additional fillers In addition to the nanofillers, a blended elastic nanocomposite composition can be blended, and one or more non-surface release fillers such as calcium carbonate, clay, mica, silica and silicates, talc, Includes titanium dioxide, starch, and other organic fillers such as wood flour, and carbon black. These filler components are typically present at a level of 10 to 200 phr, more preferably 40 to 140 phr of the formulated composition. Preferably, two or more carbon blacks are used in combination. For example, Regal 85 is not just one but carbon black having a plurality of particle sizes. Combinations also include those where the carbon black has different surface areas. Similarly, two different blacks treated differently may also be used. For example, chemically treated carbon black is combined with carbon black that has not been chemically treated.
Elastic nanocomposite formulated may include carbon black having a dibutyl phthalate oil absorption of less than 35 m ² / surface area of less than g and 100 cm ^3/100 g. Carbon black includes, but is not limited to, N660, N762, N774, N907, N990, Regal 85, and Regal 90. Table 1 shows useful carbon black properties.

35 m ² / surface area of less than g and 100 cm ^3/100 carbon black having a dibutyl phthalate oil absorption of less than g is typically 10 to 200 phr, preferably 20 to 180 phr, more preferably 30 to 160 phr, More preferably present in the nanocomposite at a level of 40-140 phr.
Curing agents, processing aids, and accelerators The blended elastic nanocomposite composition is one or more other components and curing additives commonly used in rubber mixtures, such as pigments, accelerators, crosslinking agents, and curing agents. Agents, antioxidants, anti-ozone agents, and fillers. Preferably, it may be present in 1 to 30 phr of a composition formulated with processing aids (resins), such as naphthenic, aromatic or paraffinic extender oils. Also, naphthenic, aliphatic, paraffinic and other aromatic resins and oils are substantially absent from the composition. “Substantially absent” means that naphthenic, aliphatic, paraffinic and other aromatic resins, if any, are present in the composition to the extent of 2 phr or less.

Generally, polymer compositions, such as those used to make tires, are crosslinked. It is known that the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number of crosslinks formed during the vulcanization reaction (crosslink density) and type (eg, by Helt et al., See Post-vulcanization stabilization for NR, Rubber World 18-23 (1991)). Crosslinking agents and curing agents include sulfur, zinc oxide, and organic fatty acids. A peroxide cure system may also be used. In general, the polymer composition can be crosslinked by adding curable molecules such as sulfur, metal oxides (eg, zinc oxide), organometallic compounds, radical initiators, etc., followed by heating. In particular, the following substance is a usual curing agent which functions in the present invention: ZnO, CaO, MgO, Al 2 O 3, CrO 3, FeO, Fe 2 O,, and NiO. Metal stearate complexes to which these metal oxides correspond (e.g. Zn (stearic acid) ₂ , Ca (stearic acid) ₂ , Mg (stearic acid) ₂ , and Al (stearic acid) ₃ )), or stearic acid, And can be used in conjunction with sulfur compounds or alkyl peroxide compounds (see also Production Design and Curing Properties of NBR Mixtures for Sealing, Rubber World 25-30 (1993)). This process can be accelerated and is often used for vulcanization of elastomeric compositions.

Examples of the accelerator include amine, guanidine, thiourea, thiazole, thiuram, sulfenamide, sulfenimide, thiocarbamate, and xanthate. Acceleration of the curing process can be achieved by adding a certain amount of accelerator to the composition. The mechanism for accelerated vulcanization of natural rubber involves a complex interaction between curing agents, accelerators, activators and polymers. Ideally, all of the available curing agent is consumed to form effective crosslinks, which join the two polymer chains together and increase the total strength of the polymer matrix. Many accelerators are known in the art and include, but are not limited to: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4,4'-dithiodi. Morpholine (DTDM), alkyl disulfides, such as tetrabutyl thiuram disulfide (TBTD) and 2,2′-benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate, 2- (morpholinothio) benzothiazole (MBS or MOR), composition of 90% MOR and 10% MBTS (MOR 90), N-tertiary butyl-2-benzothiazole sulfenamide (TBBS), N-oxydiethylene Thiocarbamyl-N-oxydiethylenesulfonamide (OTOS), zinc 2-ethylhexanoate (ZEH), and N, N′-diethylthiourea.
Preferably, it is present at 0.2 to 15 phr, or 0.5 to 10 phr of the composition with at least one curing agent. Curing agents include the above-described components that promote or affect the curing of the elastomer, such as metals, accelerators, sulfur, peroxides, and other agents common in the art such as those described above.

Processing The mixing of the components to produce an elastic nanocomposite composition and / or the compounding of the elastic nanocomposite composition can be accomplished by mixing the components into any suitable internal mixing device, such as a Banbury ^™ mixer, BRABENDER ^™ mixer, For example, it can be done by combining in a single screw extruder or a twin screw extruder. Mixing is sufficient to allow graphite and / or graphene to be uniformly dispersed within the polymer at temperatures up to the melting point of the elastomer and / or rubber used in the composition to form a nanocomposite. You can do it at speed.
Suitable mixing speeds can range from about 10 RPM to about 8,500 RPM. Preferably, the mixing speed can range from as low as about 10 RPM, 30 RPM, or 50 RPM to as high as about 500 RPM, 2,500 RPM, or 5,000 RPM. More preferably, the mixing speed can range from as low as about 10 RPM, 30 RPM, or 50 RPM to as high as about 200 RPM, 500 RPM, or 1,000 RPM.
Mixing temperatures can range from about 40 ° C to about 340 ° C, or from about 80 ° C to about 300 ° C, or from about 50 ° C to about 170 ° C. Preferably, the mixing temperature can range from as low as about 30 ° C, 40 ° C, or 50 ° C to as high as about 70 ° C, 170 ° C, or 340 ° C. Also, the mixing temperature can range from as low as about 80 ° C, 90 ° C, or 100 ° C to as high as about 120 ° C, 250 ° C, or 340 ° C. Furthermore, the mixing temperature can range from as low as about 85 ° C, 100 ° C, or 115 ° C to as high as about 270 ° C, 300 ° C, or 340 ° C.
Often, 70% to 100% of one or more elastomeric components with one or more graft copolymer nanofiller dispersants are mixed at the rate described above for 20 to 90 seconds or until the temperature reaches 40-60 ° C. obtain. Then 75% to 100% of the nanofiller, and the remaining amount of elastomer and / or nanofiller dispersant (if present) can be added to the mixer and mixed until the temperature reaches 90 ° C to 150 ° C. It can continue. Next, processing oil can be added, as well as the remaining nanofillers and / or additional fillers, and mixing can continue until the temperature reaches 140 ° C to 190 ° C. The finished mixture is then finished by sheeting in an open mill and cooled to 60-100 ° C. when the curing agent is added.
Also, 75% to 100% of one or more graft copolymer nanofiller dispersants and 75% to 100% of nanofillers can be mixed, preferably by solution blending. Preferably, the mixing is performed at a temperature in the range from 50 ° C to 170 ° C, more preferably from 90 ° C to 150 ° C. The resulting mixture may be mixed with 75% to 100% of one or more elastomeric components for 20 to 90 seconds or at the previously noted rate until the temperature reaches from 40C to 60C. The remaining amount of elastomer and / or nanofiller dispersant (if present) is then added to the mixer and mixing can continue until the temperature reaches from 90 ° C to 150 ° C. Next, processing oil may be added as well as the remaining nano-fillers and / or additional fillers, and mixing may continue until the temperature reaches 140 ° C. to 190 ° C. The finished mixture is then finished by sheeting on an open mill and cooled to 60 ° C. to 100 ° C. as the curing agent is added.

Industrial Applicability The compositions described herein can be incorporated into articles such as films, sheets, molded parts, and the like. Specifically, the compositions described herein are tires, tire components (eg, sidewalls, treads, tread caps, inner tubes, inner liners, apex, chafers, wire coats, and ply coats), tubes, pipes, It can be molded into a barrier film / membrane or any other application where air impermeability is advantageous.
Preferably, an article molded from the elastic composition described herein is 180 mm-cc / measured on a MOCON OX-TRAN 2/61 permeability tester at 40 ° C. as described below. M ² -day or less, preferably 160 mm-cc / M ² -day or less, preferably 140 mm-cc / M ² -day or less, preferably 120 mm-cc / M ² -day or less, preferably 100 mm- It has a permeability of cc / M ² -day or less. Preferably, the elastic nanocomposites produced in accordance with the present invention have a permeability that is at least 10% lower, more preferably at least 20% lower, more preferably at least 30% lower, and ideally at least 50% lower than the elastomer component. Have.

The above description can be further described with reference to the following non-limiting examples.
Exemplary syntheses of PPE-g-PIB graft copolymers and their properties Typical synthetic procedures are described herein. Under nitrogen protection, a 1 L reaction vessel equipped with an overhead mechanical stirrer and condenser was charged with 60 g of PPE (Sigma-Aldrich, Mn measured by GPC based on polystyrene, Mn = 15K), VTPIB (obtained from BASF Obtain Glissopal ^™ 1000, Mn = 1K) 20 g, 0.08 g stabilizer package containing a mixture of 50 wt% Irganox ^™ 1076 (Sigma-Aldrich) and 50 wt% Irgafos ^™ 168 (Sigma-Aldrich), and anhydrous 1 , 700 mL of 2-dichlorobenzene (o-DCB) (Sigma-Aldrich) was charged. The mixture was heated to 120 ° C. to completely dissolve the reactants, after which methanesulfonic acid (MSA) catalyst (Sigma-Aldrich) was gradually added to the reaction mixture. The temperature of the reaction mixture was then raised and the reaction was allowed to proceed at reflux for 4 hours under nitrogen protection. The reaction mixture was precipitated in 3.5 L of methanol. The resulting product was filtered, washed with fresh methanol and dried in a vacuum oven at 60 ° C. until a constant mass was reached.
PPE-PIB graft copolymer was characterized by proton nuclear magnetic resonance ( ¹ H NMR). Using the 600 MHz spectrometer obtained from Bruker Corporation, won the NMR spectrum using 1,1,2,2-tetrachloroethane -d ₂ a (TCE-d ₂₎ as the solvent. The acquired NMR spectrum was compared with that of the starting material to determine that 89% of the PIB was grafted to the PPE backbone.

Solution Blend of PPE-PIB Graft Copolymer and Nanographene Platelets A solution blend of synthesized PPE-PIB graft copolymer and nanographene platelets was prepared according to the following procedure. 10 g of brand C xGnP ^™ nanographene platelets commercially available from XG Sciences, Inc. with an average surface area of 500 m ² / g and a density of 2-2.25 g / cc were initially fitted with 1 L of condenser. Dissolved in 500 mL o-DCB at 120 ° C. under nitrogen protection in a 3 neck round bottom flask. Thereafter, 40 g of PPE-PIB graft copolymer was added and the ingredients were mixed under reflux for 4 hours. The mixture was then precipitated in 1 L of isopropanol while still warm. The resulting product was filtered, washed with fresh isopropanol and dried at 60 ° C. in a vacuum oven.
Sample Preparation and Oxygen Permeability Characterization Five samples (Samples 1-5) were prepared for oxygen permeability testing. Sample 1 (comparative example) contains neat bromobutyl 2222 brand BIIR compound 36 g, and sample 2 (comparative example) blends 75% bromobutyl 2222 brand BIIR compound copolymer and 25% strength PPE blend 36 Each of Samples 3-5 (invention) contains BI and nanocomposites based on BIIR containing prepared solution blends of PPE-PIB graft copolymer and NGP at various concentrations (shown in Table 2) Contains 36 g.
Each of Samples 1-5 was formulated by charging the material (36 g) into a BRABENDER ^™ mixer at 135 ° C. and 60 RPM. After 1 minute, 20 g of N660 carbon black (CB) filler was added. The mixing was then continued for an additional 6 minutes for a total mixing time of 7 minutes. The material was then removed, chopped and fed back into the BRABENDER ^™ mixer at 45 ° C. and 40 RPM. One minute later, 0.33 g of MBTS (mercaptobenzothiazole disulfide), 0.33 g of zinc oxide, and 0.33 g of stearic acid curing agent were added. The mixing was then continued for an additional 3 minutes for a total mixing time of 4 minutes.
The compounded material was pressed between Teflon sheets and molded / cured at 170 ° C. for 15 minutes. The resulting cured pad was then used for property measurement and dispersion characterization. Oxygen permeability values were measured using a MOCON OX-TRAN 2/61 permeability tester at 40 ° C., 0% RH, and 760 mm Hg. Table 2 summarizes the results of the oxygen permeability test, along with the compositional composition of each sample (shown for unblended samples). The change in permeability value reported in Table 2 was calculated for the permeability of Sample 1.

  PPE is more permeable to BIIR. Thus, as shown in Table 2, addition of PPE to BIIR (Sample 2) resulted in an undesirable 38.6% increase in permeability to the neat BIIR compound of Sample 1. Similarly, the addition of NGP would be expected to reduce the permeability of BIIR-based compounds, but sample 3 with 1 wt% NPG loading and 4 wt% PPE-PIB copolymer content was Showed an increase in permeability of 5.42%. This result suggests that at low NGP loadings, the NGP permeability-reducing effect is not large enough to offset the increase in permeability due to the addition of the PPE-PIB copolymer. In contrast, Despite having an even higher PPE-PIB copolymer content of 40% by weight, Sample 5 (with an NGP loading of 10% by weight) has a significant permeation of 59.6% for neat BIIR compound. Decreased sex.

Additional Test Methods Molecular weight (number average molecular weight (Mn) and weight average molecular weight molecular weight (Mw)) for on-line differential refractive index (DRI) detector, light scattering (LS) detector, and viscometer (VIS) Measurement is performed using a Polymer Laboratories Model 220 high temperature GPC-SEC (so-called GPC-3D, gel permeation chromatography-3 detector) equipped with a detector. It uses three Polymer Laboratories PLgel 10 m Mix-B columns for separation using a flow rate of 0.54 ml / min and a nominal injection volume of 300 μL. The detector and column are contained in an oven maintained at 135 ° C. The stream emerging from the size exclusion chromatography (SEC) column is sent to a miniDAWN (Wyatt Technology, Inc.) optical flow cell and then to a DRI detector. The DRI detector is an integral part of Polymer Laboratories SEC. The viscometer is located in the SEC oven, located after the DRI detector. As well as details of these detectors, their calibration with respect to polystyrene is described, for example, by T.Sun, P.Brant, RRChance, and WWGraessley in 34 (19) Macromolecules, 6812-6820, (2001). Has been.
All documents cited in this specification (including priority documents and / or test procedures) shall be subject to all jurisdiction purposes where such practices are allowed to the extent that they are not inconsistent with this specification. Therefore, it is included herein as a reference. While the invention has been illustrated and described, as will be apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not intended to be limited thereby. For example, the compositions described herein may not include ingredients or compositions not explicitly mentioned or disclosed herein. Any method may lack steps that are not mentioned or disclosed herein. Similarly, the term “comprising” is considered synonymous with the term “including”. And whenever a method, composition, element, or group of elements is preceded by the transitional phrase “comprising”, we “substantially” precede the reference to the composition, one or more elements. Intended to be the same group of compositions or elements with the transitional phrases “consisting of”, “consisting of”, “chosen from the group consisting of” It is understood that the reverse is also true.

を有し、
式中、それぞれのＩ、II、III 、及びIVは、独立に、1,2-フェニル、1,3-フェニル又は1,4-フェニルであり、これらのいずれかが１個以上の電子供与性置換基で置換されていてもよく、
Ａ、Ｂ、Ｃ、及びＤの少なくとも一つは、独立に、酸素原子、窒素原子、硫黄原子、もしくはリン原子、又は酸素、窒素、硫黄、リンを含む部分、或いはこれらの組み合わせであり、
Ｅ、Ｆ、Ｇ、及びＨの少なくとも一つはそれぞれＩ、II、III 、及びIVに結合された一つ、二つ又は三つのポリ脂肪族炭化水素成分であり、そのポリ脂肪族炭化水素成分のそれぞれが少なくとも300 g/モルの重量平均分子量を有し、かつ
ｍは１から10までの範囲内の整数であり、かつｎは10から500 までの範囲内の整数である、付記５又は６記載の組成物。
［付記８］
その電子供与性置換基がC₁〜C₁₀ アルキル、C₁〜C₁₀ アルコキシ、C₁〜C₁₀ メルカプタン、塩素、臭素、ヨウ素、ヒドロキシル、及びこれらの組み合わせからなる群から選ばれる、付記７記載の組成物。
［付記９］
Ａ、Ｂ、Ｃ、及びＤ置換基がC₁〜C₁₀ カルボキシ含有部分、C₁〜C₁₀ イミド含有部分、C₁〜C₁₀ スルフィド含有部分、硫黄、スルフィド、カルボキシ、カルボキシレート、イミド、窒素、及びこれらの組み合わせからなる群から選ばれる付記７又は８記載の組成物。
［付記１０］
Ａ、Ｂ、Ｃ、及びＤ置換基が-CH₂-NH-CO-(CH₂)₄-CH₂-、-OCOO-、CO- 、ピロメリット酸ジイミド、-SO₂- 、硫黄、酸素、窒素、リン、及びこれらの組み合わせからなる群から選ばれる、付記７から９のいずれかに記載の組成物。
［付記１１］
Ａ、Ｂ、Ｃ、及びＤ置換基が酸素であり、かつＩ、II、III 、及びIVが2,6-ジメチル-1,4-フェニルであり、かつｍが１である、付記７から１０のいずれかに記載の組成物。
［付記１２］
ナノ充填剤がグラファイト、膨張グラファイト、ナノグラフェン小板状体 (NGP) 、及びグラフェン、並びにこれらの混合物及び組み合わせからなる群から選ばれる、付記１から１１のいずれかに記載の組成物。
［付記１３］
エラストマー成分が塩素化ポリ (イソブチレン共イソプレン) (CIIR)及び臭素化ポリ (イソブチレン共イソプレン) (BIIR)、並びにこれらの混合物及び組み合わせからなる群から選ばれる、付記１から１２のいずれかに記載の組成物。
［付記１４］
40℃における弾性ナノ複合材料の酸素透過性がエラストマー成分の透過性よりも少なくとも50％低い、付記１３記載の組成物。
［付記１５］
付加的な充填剤、加工オイル、及び硬化添加剤からなる群から選ばれた少なくとも一種の成分を更に含み、その硬化添加剤が金属酸化物、有機酸、及びアルキルジスルフィド、並びにこれらの混合物及び組み合わせからなる群から選ばれる、付記１から１４のいずれかに記載の組成物。
［付記１６］
付記１から１５のいずれかに記載の組成物を含むタイヤ用のインナーライナー。
［付記１７］
弾性ナノ複合材料組成物の製造方法であって、その方法が
(a) 少なくとも一種のポリ脂肪族炭化水素及び少なくとも一種のポリ芳香族炭化水素を80℃から200 ℃までの範囲内の温度でフリーデル−クラフツ触媒と合わせてナノ充填剤分散剤を生成し、
(b) ナノ充填剤分散剤を(i) ４個から７個までの炭素を有するイソオレフィンから誘導された単位を含む少なくとも一種のハロゲン化エラストマー成分及び(ii)少なくとも一種のナノ充填剤と混合することを含み、
そのナノ複合材料組成物が0.01質量％から15.0質量％までのナノ充填剤及び0.5 質量％から49質量％までのナノ充填剤分散剤を含み、その質量％がナノ充填剤分散剤、エラストマー成分、及びナノ充填剤の合計質量を基準とすることを特徴とする前記方法。
［付記１８］
ポリ脂肪族炭化水素がポリイソブチレンを含み、そのポリイソブチレンがビニル／ビニリデン末端であり、かつ少なくとも300 g/モルの重量平均分子量を有する、付記１７記載の方法。
［付記１９］
ビニル／ビニリデン末端ポリイソブチレンが300 g/モルから300,000 g/モルまでの範囲内の重量平均分子量(M_w)を有する、付記１８記載の方法。
［付記２０］
ポリ芳香族炭化水素が5,000 g/モルから80,000 g/モルまでの範囲内の重量平均分子量(M_w)を有する、付記１７から１９のいずれかに記載の方法。
［付記２１］
ポリ芳香族炭化水素がそのポリマー主鎖中に少なくとも１個のフェニレンを有する、付記１７から２０のいずれかに記載の方法。
［付記２２］
ナノ充填剤がグラファイト、膨張グラファイト、ナノグラフェン小板状体 (NGP) 、及びグラフェン、並びにこれらの混合物及び組み合わせからなる群から選ばれる、付記１７から２１のいずれかに記載の方法。
［付記２３］
ハロゲン化エラストマー成分が塩素化ポリ (イソブチレン共イソプレン) (CIIR)及び臭素化ポリ (イソブチレン共イソプレン) (BIIR)、並びにこれらの混合物及び組み合わせからなる群から選ばれる、付記１７から２２のいずれかに記載の方法。
［付記２４］
40℃における弾性ナノ複合材料の酸素透過性がエラストマー成分の透過性よりも少なくとも50％低い、付記２３記載の方法。
［付記２５］
弾性ナノ複合材料中のナノ充填剤分散剤としてのグラフトコポリマーを含む組成物の使用であって、そのグラフトがポリ脂肪族炭化水素成分及びポリ芳香族炭化水素成分を含み、そのポリ芳香族炭化水素成分がその主鎖中のヘテロ原子又はヘテロ原子含有部分及びフェニル基又は置換フェニル基を含むポリマーであり、そのポリ脂肪族成分がポリ芳香族炭化水素成分に共有結合されていることを特徴とする前記使用。 Additional Test Methods Molecular weight (number average molecular weight (Mn) and weight average molecular weight molecular weight (Mw)) for on-line differential refractive index (DRI) detector, light scattering (LS) detector, and viscometer (VIS) Measurement is performed using a Polymer Laboratories Model 220 high temperature GPC-SEC (so-called GPC-3D, gel permeation chromatography-3 detector) equipped with a detector. It uses three Polymer Laboratories PLgel 10 m Mix-B columns for separation using a flow rate of 0.54 ml / min and a nominal injection volume of 300 μL. The detector and column are contained in an oven maintained at 135 ° C. The stream emerging from the size exclusion chromatography (SEC) column is sent to a miniDAWN (Wyatt Technology, Inc.) optical flow cell and then to a DRI detector. The DRI detector is an integral part of Polymer Laboratories SEC. The viscometer is located in the SEC oven, located after the DRI detector. As well as details of these detectors, their calibration with respect to polystyrene is described, for example, by T.Sun, P.Brant, RRChance, and WWGraessley in 34 (19) Macromolecules, 6812-6820, (2001). Has been.
All documents cited in this specification (including priority documents and / or test procedures) shall be subject to all jurisdiction purposes where such practices are allowed to the extent that they are not inconsistent with this specification. Therefore, it is included herein as a reference. While the invention has been illustrated and described, as will be apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not intended to be limited thereby. For example, the compositions described herein may not include ingredients or compositions not explicitly mentioned or disclosed herein. Any method may lack steps that are not mentioned or disclosed herein. Similarly, the term “comprising” is considered synonymous with the term “including”. And whenever a method, composition, element, or group of elements is preceded by the transitional phrase “comprising”, we “substantially” precede the reference to the composition, one or more elements. Intended to be the same group of compositions or elements with the transitional phrases “consisting of”, “consisting of”, “chosen from the group consisting of” It is understood that the reverse is also true.
The present invention includes the following matters.
[Appendix 1]
(a) (i) at least one polyaliphatic hydrocarbon, and
(ii) a nanofiller dispersant comprising a reaction product of at least one polyaromatic hydrocarbon;
(b) at least one halogenated elastomer component comprising units derived from isoolefins having 4 to 7 carbons, and
(c) an elastic nanocomposite composition comprising at least one nanofiller,
The nanofiller dispersant is present from 0.5% to 49% by weight based on the total weight of the nanofiller dispersant, elastomer component, and nanofiller, and the nanofiller is nanofiller dispersant, elastomer component, And the elastic nanocomposite composition, wherein the elastic nanocomposite composition is present in an amount of 0.01% to 15.0% by mass based on the total mass of the nanofiller.
[Appendix 2]
The composition of claim 1, wherein the polyaliphatic hydrocarbon comprises polyisobutylene, the polyisobutylene being vinyl / vinylidene terminated and having a weight average molecular weight of at least 300 g / mol.
[Appendix 3]
Item 3. The composition of item 1 or 2, wherein the polyaromatic hydrocarbon has at least one phenylene in its polymer backbone.
[Appendix 4]
4. The composition according to any one of appendices 1 to 3, wherein the reaction between the polyaliphatic hydrocarbon and the polyaromatic hydrocarbon is promoted with a Friedel-Crafts catalyst at a temperature in the range of 80 ° C. to 200 ° C.
[Appendix 5]
The nanofiller dispersant comprises a graft copolymer comprising a polyaliphatic hydrocarbon component and a polyaromatic hydrocarbon component, the polyaromatic hydrocarbon component comprising a heteroatom or heteroatom-containing moiety in the main chain and a phenyl group or The composition according to any one of appendices 1 to 4, wherein the composition is a polymer containing a substituted phenyl group, and the polyaliphatic hydrocarbon component is covalently bonded to the polyaromatic hydrocarbon component.
[Appendix 6]
The composition of claim 5, wherein the molar ratio of the polyaliphatic hydrocarbon component to the polyaromatic hydrocarbon component in the graft copolymer is in the range of 99: 1 to 1:99.
[Appendix 7]
Graft copolymer has the structure:

Have
Wherein each I, II, III and IV is independently 1,2-phenyl, 1,3-phenyl or 1,4-phenyl, any of which is one or more electron donating May be substituted with a substituent,
At least one of A, B, C, and D is independently an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, or a moiety containing oxygen, nitrogen, sulfur, phosphorus, or a combination thereof;
At least one of E, F, G, and H is one, two, or three polyaliphatic hydrocarbon components bonded to I, II, III, and IV, respectively, and the polyaliphatic hydrocarbon component Each having a weight average molecular weight of at least 300 g / mole; and m is an integer in the range of 1 to 10 and n is an integer in the range of 10 to 500. The composition as described.
[Appendix 8]
As the electron-donating substituent C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ mercaptans, chlorine, bromine, iodine, hydroxyl, and are selected from the group consisting of, Appendix 7, wherein Composition.
[Appendix 9]
A, B, C, and D substituents are C ₁ -C ₁₀ carboxy-containing moiety, C ₁ -C ₁₀ imide-containing moiety, C ₁ -C ₁₀ sulfide-containing moiety, sulfur, sulfide, carboxy, carboxylate, imides, nitrogen And the composition according to appendix 7 or 8, selected from the group consisting of combinations thereof.
[Appendix 10]
A, B, C, and D substituents are —CH ₂ —NH—CO— (CH ₂ ) ₄ —CH ₂ —, —OCOO—, CO—, pyromellitic diimide, —SO ₂ —, sulfur, oxygen, The composition according to any one of appendices 7 to 9, selected from the group consisting of nitrogen, phosphorus, and combinations thereof.
[Appendix 11]
Supplementary notes 7-10, wherein the A, B, C, and D substituents are oxygen, I, II, III, and IV are 2,6-dimethyl-1,4-phenyl and m is 1. The composition in any one of.
[Appendix 12]
The composition according to any one of appendices 1 to 11, wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, nanographene platelets (NGP), graphene, and mixtures and combinations thereof.
[Appendix 13]
Addendum 1 to 12, wherein the elastomer component is selected from the group consisting of chlorinated poly (isobutylene co-isoprene) (CIIR) and brominated poly (isobutylene co-isoprene) (BIIR), and mixtures and combinations thereof. Composition.
[Appendix 14]
14. The composition of claim 13, wherein the oxygen permeability of the elastic nanocomposite at 40 ° C. is at least 50% lower than the permeability of the elastomer component.
[Appendix 15]
And further comprising at least one component selected from the group consisting of an additional filler, a processing oil, and a curing additive, the curing additive being a metal oxide, an organic acid, and an alkyl disulfide, and mixtures and combinations thereof. The composition according to any one of supplementary notes 1 to 14, which is selected from the group consisting of:
[Appendix 16]
An inner liner for a tire, comprising the composition according to any one of appendices 1 to 15.
[Appendix 17]
A method for producing an elastic nanocomposite composition comprising:
(a) combining at least one polyaliphatic hydrocarbon and at least one polyaromatic hydrocarbon with a Friedel-Crafts catalyst at a temperature in the range from 80 ° C to 200 ° C to produce a nanofiller dispersant;
(b) mixing the nanofiller dispersant with (i) at least one halogenated elastomer component comprising units derived from isoolefins having 4 to 7 carbons and (ii) at least one nanofiller Including
The nanocomposite composition comprises 0.01 wt% to 15.0 wt% nanofiller and 0.5 wt% to 49 wt% nanofiller dispersant, the wt% comprising nanofiller dispersant, elastomer component, And based on the total mass of the nanofiller.
[Appendix 18]
18. The process of claim 17, wherein the polyaliphatic hydrocarbon comprises polyisobutylene, the polyisobutylene is vinyl / vinylidene terminated and has a weight average molecular weight of at least 300 g / mol.
[Appendix 19]
19. The process of claim 18, wherein the vinyl / vinylidene terminated polyisobutylene has a weight average molecular weight (M _w ) in the range of 300 g / mol to 300,000 g / mol.
[Appendix 20]
20. The process according to any one of appendices 17 to 19, wherein the polyaromatic hydrocarbon has a weight average molecular weight (M _w ) in the range from 5,000 g / mol to 80,000 g / mol.
[Appendix 21]
21. A process according to any one of appendices 17 to 20, wherein the polyaromatic hydrocarbon has at least one phenylene in its polymer backbone.
[Appendix 22]
The method according to any one of appendices 17 to 21, wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, nanographene platelets (NGP), and graphene, and mixtures and combinations thereof.
[Appendix 23]
Additional notes 17 to 22 wherein the halogenated elastomer component is selected from the group consisting of chlorinated poly (isobutylene co-isoprene) (CIIR) and brominated poly (isobutylene co-isoprene) (BIIR), and mixtures and combinations thereof. The method described.
[Appendix 24]
24. The method of claim 23, wherein the oxygen permeability of the elastic nanocomposite at 40 ° C. is at least 50% lower than the permeability of the elastomer component.
[Appendix 25]
Use of a composition comprising a graft copolymer as a nanofiller dispersant in an elastic nanocomposite, the graft comprising a polyaliphatic hydrocarbon component and a polyaromatic hydrocarbon component, the polyaromatic hydrocarbon The component is a polymer containing a heteroatom or a heteroatom-containing moiety in the main chain and a phenyl group or a substituted phenyl group, and the polyaliphatic component is covalently bonded to the polyaromatic hydrocarbon component Said use.

Claims (25)

(a) (i) at least one polyaliphatic hydrocarbon, and
(ii) a nanofiller dispersant comprising a reaction product of at least one polyaromatic hydrocarbon;
(b) at least one halogenated elastomer component comprising units derived from isoolefins having 4 to 7 carbons, and
(c) an elastic nanocomposite composition comprising at least one nanofiller,
The nanofiller dispersant is present from 0.5% to 49% by weight based on the total weight of the nanofiller dispersant, elastomer component, and nanofiller, and the nanofiller is nanofiller dispersant, elastomer component, And the elastic nanocomposite composition, wherein the elastic nanocomposite composition is present in an amount of 0.01 to 15.0% by mass based on the total mass of the nanofiller.   The composition of claim 1, wherein the polyaliphatic hydrocarbon comprises polyisobutylene, the polyisobutylene being vinyl / vinylidene terminated and having a weight average molecular weight of at least 300 g / mol.   A composition according to claim 1 or 2, wherein the polyaromatic hydrocarbon has at least one phenylene in its polymer backbone.   4. A composition according to any one of claims 1 to 3, wherein the reaction of the polyaliphatic hydrocarbon and the polyaromatic hydrocarbon is promoted with a Friedel-Crafts catalyst at a temperature in the range from 80C to 200C.   The nanofiller dispersant comprises a graft copolymer comprising a polyaliphatic hydrocarbon component and a polyaromatic hydrocarbon component, the polyaromatic hydrocarbon component comprising a heteroatom or heteroatom-containing moiety in the main chain and a phenyl group or The composition according to any one of claims 1 to 4, wherein the composition is a polymer containing a substituted phenyl group, and the polyaliphatic hydrocarbon component is covalently bonded to the polyaromatic hydrocarbon component.   6. The composition of claim 5, wherein the molar ratio of polyaliphatic hydrocarbon component to polyaromatic hydrocarbon component in the graft copolymer is in the range of 99: 1 to 1:99. Graft copolymer has the structure:

Have
Wherein each I, II, III and IV is independently 1,2-phenyl, 1,3-phenyl or 1,4-phenyl, any of which is one or more electron donating May be substituted with a substituent,
At least one of A, B, C, and D is independently an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, or a moiety containing oxygen, nitrogen, sulfur, phosphorus, or a combination thereof;
At least one of E, F, G, and H is one, two, or three polyaliphatic hydrocarbon components bonded to I, II, III, and IV, respectively, and the polyaliphatic hydrocarbon component Each having a weight average molecular weight of at least 300 g / mol, and m is an integer in the range of 1 to 10 and n is an integer in the range of 10 to 500. 6. The composition according to 6. As the electron-donating substituent C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ mercaptans, chlorine, bromine, iodine, hydroxyl, and are selected from the group consisting of, claim 7 The composition as described. A, B, C, and D substituents are C ₁ -C ₁₀ carboxy-containing moiety, C ₁ -C ₁₀ imide-containing moiety, C ₁ -C ₁₀ sulfide-containing moiety, sulfur, sulfide, carboxy, carboxylate, imides, nitrogen And a composition according to claim 7 or 8 selected from the group consisting of combinations thereof. A, B, C, and D substituents are —CH ₂ —NH—CO— (CH ₂ ) ₄ —CH ₂ —, —OCOO—, CO—, pyromellitic diimide, —SO ₂ —, sulfur, oxygen, The composition according to claim 7, which is selected from the group consisting of nitrogen, phosphorus, and combinations thereof.   The A, B, C, and D substituents are oxygen, and I, II, III, and IV are 2,6-dimethyl-1,4-phenyl and m is 1. 11. The composition according to any one of 10.   12. A composition according to any preceding claim, wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, nanographene platelets (NGP), and graphene, and mixtures and combinations thereof.   The elastomer component is selected from the group consisting of chlorinated poly (isobutylene co-isoprene) (CIIR) and brominated poly (isobutylene co-isoprene) (BIIR), and mixtures and combinations thereof. Composition.   The composition of claim 13, wherein the oxygen permeability of the elastic nanocomposite at 40 ° C. is at least 50% lower than the permeability of the elastomer component.   And further comprising at least one component selected from the group consisting of an additional filler, a processing oil, and a curing additive, the curing additive being a metal oxide, an organic acid, and an alkyl disulfide, and mixtures and combinations thereof. The composition according to any one of claims 1 to 14, which is selected from the group consisting of:   An innerliner for a tire comprising the composition according to any one of claims 1 to 15. A method for producing an elastic nanocomposite composition comprising:
(a) combining at least one polyaliphatic hydrocarbon and at least one polyaromatic hydrocarbon with a Friedel-Crafts catalyst at a temperature in the range from 80 ° C to 200 ° C to produce a nanofiller dispersant;
(b) mixing the nanofiller dispersant with (i) at least one halogenated elastomer component comprising units derived from isoolefins having 4 to 7 carbons and (ii) at least one nanofiller Including
The nanocomposite composition comprises 0.01 wt% to 15.0 wt% nanofiller and 0.5 wt% to 49 wt% nanofiller dispersant, the wt% comprising nanofiller dispersant, elastomer component, And based on the total mass of the nanofiller.   18. The method of claim 17, wherein the polyaliphatic hydrocarbon comprises polyisobutylene, the polyisobutylene is vinyl / vinylidene terminated and has a weight average molecular weight of at least 300 g / mol. 19. The method of claim 18, wherein the vinyl / vinylidene terminated polyisobutylene has a weight average molecular weight ( _Mw ) in the range of 300 g / mole to 300,000 g / mole. 20. A process according to any of claims 17 to 19, wherein the polyaromatic hydrocarbon has a weight average molecular weight ( _Mw ) in the range from 5,000 g / mol to 80,000 g / mol.   21. A process according to any of claims 17 to 20, wherein the polyaromatic hydrocarbon has at least one phenylene in its polymer backbone.   The method according to any of claims 17 to 21, wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, nanographene platelets (NGP), and graphene, and mixtures and combinations thereof.   The halogenated elastomer component is selected from the group consisting of chlorinated poly (isobutylene co-isoprene) (CIIR) and brominated poly (isobutylene co-isoprene) (BIIR), and mixtures and combinations thereof. The method described in 1.   24. The method of claim 23, wherein the oxygen permeability of the elastic nanocomposite at 40 ° C. is at least 50% lower than the permeability of the elastomer component.   Use of a composition comprising a graft copolymer as a nanofiller dispersant in an elastic nanocomposite, the graft comprising a polyaliphatic hydrocarbon component and a polyaromatic hydrocarbon component, the polyaromatic hydrocarbon The component is a polymer containing a heteroatom or a heteroatom-containing moiety in the main chain and a phenyl group or a substituted phenyl group, and the polyaliphatic component is covalently bonded to the polyaromatic hydrocarbon component Said use.