JP6437509B2 - Method for reducing melt viscosity of dynamically crosslinked alloys - Google Patents

Description

  The present invention relates to dynamic cross-linked alloys (DVA), in particular DVA with improved processability and stability. The invention further relates to a method for producing DVA.

  Compositions containing DVA are sometimes referred to in the art as thermoplastic crosslinks and often contain reinforcing fillers to improve various properties of the composition, including mechanical properties and UV resistance. .

  One of the main drawbacks of reinforcing fillers is their negative impact on the processability and other properties of the composition. Higher amounts of filler that may be needed to provide adequate UV resistance are associated with higher viscosities, which can be a process problem and concern.

  Several approaches have been attempted to increase the UV resistance of DVA films. If a UV stabilizer is added directly to the DVA during the manufacture of the DVA, the stabilizer will tend to also act as a cross-linking accelerator, resulting in rubber scorch. To solve the scorch problem, U.S. Pat. No. 7,459,212 discloses the addition of a stabilizer to the adjacent rubber layer to achieve the desired properties based on the movement of the stabilizer into the DVA. Yes. However, when used as an inner liner, since the weight of the inner liner increases, it is not always desirable to have such an adjacent rubber layer next to the DVA.

  Accordingly, there is a need for elastomeric compositions having improved UV resistance and / or processability properties and methods for making such compositions.

  In one aspect of the invention, the thermoplastic elastomer composition comprises a post-crosslinking dynamic cross-linking alloy (DVA) and a low molecular weight aromatic amine stabilizer, wherein the DVA comprises at least one thermoplastic resin in the continuous phase. As an isobutylene elastomer component dispersed as:

  In another aspect of the invention, the process for producing the thermoplastic elastomer composition comprises post-crosslinking DVA with a low molecular weight aromatic amine stabilizer, wherein the DVA is in a continuous phase comprising at least one thermoplastic resin. An isobutylene elastomer component dispersed as a domain.

  In yet another aspect of the present invention, a process for producing a thermoplastic elastomer composition comprises dynamically crosslinking an isobutylene elastomer component dispersed as a domain in a continuous phase comprising at least one thermoplastic resin to post-crosslink DVA (post -Vulcanization DVA); and after crosslinking, the DVA is mixed with a low molecular weight aromatic amine stabilizer to produce a thermoplastic elastomer composition.

  In yet another aspect of the present invention, the thermoplastic elastomer composition dynamically crosslinks a halogenated isobutylene elastomer component dispersed as a domain in a continuous phase comprising a polyamide to produce a post-crosslinking DVA; and Produced by a process comprising mixing DVA with a low molecular weight aromatic amine stabilizer to produce a thermoplastic elastomer composition.

  In another aspect of the present invention, a method of reducing the melt viscosity of DVA and improving UV resistance includes producing a post-crosslinked DVA that is stabilized by mixing with a low molecular weight aromatic amine stabilizer. The DVA comprises an isobutylene elastomer component dispersed as a domain in a continuous phase comprising at least one thermoplastic resin.

  In one embodiment, the present disclosure provides a thermoplastic elastomer composition comprising a dynamically crosslinked alloy (DVA) and a low molecular weight aromatic amine stabilizer, wherein the DVA is in a continuous phase comprising at least one thermoplastic resin. The present invention relates to a thermoplastic elastomer composition comprising an isobutylene elastomer component dispersed as a domain. Further disclosed is a manufacturing process for the composition. In one embodiment, the viscosity of the composition is sufficient to achieve a desired level of UV resistance and other physical properties while having a viscosity low enough to improve the processability of the composition. The amount is reduced so that various fillers and other additives can be included.

  In one embodiment, the DVA includes a thermosetting component dispersed as domains in a thermoplastic continuous phase. This DVA is referred to herein as a “post-vulcanized” composition, which is then mixed with a stabilizer to produce a thermoplastic elastomer composition.

  As used herein, “polymer” may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, and the like. Similarly, a copolymer can refer to a polymer comprising at least two monomers and optionally further comprising other monomers. When the polymer includes monomers, the monomers are present in the polymer in a polymerized form of the monomer or a derivative form of the monomer. However, for ease of reference, the phrase containing (each) monomer or the like is used briefly. Similarly, if the catalyst component is described as including a neutral stable form of the component, those skilled in the art will appreciate that the ionic form of the component is the form that reacts with the monomer to form a polymer.

  Rubber is consistent with ASTM D1566 definition "material that can recover from large deformations and can be changed to a state that is essentially insoluble (but can expand) in boiling solvents" or has already changed. Refers to any polymer or composition of polymers. “Elastomer” is a term that can be used interchangeably with the term rubber. “Elastomer composition” refers to any composition comprising at least one elastomer as defined above.

  The crosslinked rubber composition is formed from an elastomer that, according to the definition of ASTM D1566, “deforms greatly with a small force and can quickly and strongly return to its original size and shape when the deformed force is removed. It refers to “crosslinked elastic material”. Cross-linked elastomer composition refers to any elastomer composition that has undergone a cross-linking process and / or contains or is produced using an effective amount of a cross-linking agent or a cross-linker package. It is a term used interchangeably with the term.

  “Thermoplastic elastomer” means, as defined in ASTM D1566, “in the temperature range characteristic of a polymer, it can be repeatedly softened by heating and cured by cooling, and formed into an article in a softened state. Can refer to rubber-like material. Thermoplastic elastomers are microphase separated structures of at least two polymers. One phase is a hard polymer that does not flow at room temperature but becomes fluid when heated, giving the thermoplastic elastomer its strength. The other phase is a soft rubbery polymer that gives the thermoplastic elastomer its elasticity. The hard phase is typically the main or continuous phase.

  A thermoplastic cross-linked product as defined by ASTM D1566 refers to a "thermoplastic elastomer comprising a chemically cross-linked rubbery phase produced by dynamic cross-linking". Dynamic cross-linking is a process in which a thermoplastic polymer and a suitable reactive rubber-like polymer are homogeneously melt mixed to produce a thermoplastic elastomer comprising a chemically cross-linked rubbery phase, the cross-linkable elastomer Is a process that is crosslinked under high shear conditions. As a result, the crosslinkable elastomer is simultaneously crosslinked and dispersed as fine particles, which are sometimes described as “microgels” in resin matrix engineering.

  Dynamic cross-linking involves mixing the components at a temperature at or above the cross-linking temperature of the elastomer using equipment such as a roll mill, a Banbury® mixer, a continuous mixer, a mixer, or a mixed extruder, such as a twin screw extruder. Is made by The inherent nature of dynamically crosslinked compositions is that they can be processed and processed by conventional thermoplastic processing techniques such as extrusion, injection molding, compression molding, etc., even though the elastomer component can be fully crosslinked. It can be reworked. Scrap or flashing can be collected and reprocessed.

  In one embodiment, the thermosetting component is a small particle size elastomeric component with a number average equivalent domain diameter of 0.1 to 1 micron. In one embodiment, the continuous thermoplastic phase is a polyamide, also referred to as nylon. Such a composition is particularly suitable for use as a moisture-proof layer or the like in a pneumatic tire.

  In one embodiment, the elastomeric component comprises an isobutylene elastomer, preferably a halogenated isobutylene elastomer, more preferably a copolymer of isobutylene and para-alkyl styrene as described in EP 0344402 (B1). As used herein, “isobutylene elastomer” or “isobutylene elastomer component” refers to an elastomer or polymer comprising at least 70 mole percent of repeating units derived from isobutylene. The copolymer preferably exhibits a substantially uniform composition distribution. Preferred alkyl groups for the para-alkylstyrene moiety include alkyl groups having 1 to 5 carbon atoms, secondary haloalkyls having 1 to 5 carbon atoms, primary haloalkyls, and mixtures thereof. . A preferred copolymer comprises isobutylene and para-methylstyrene.

  Suitable halogenated isobutylene elastomer components include a number average molecular weight Mn of at least about 25,000, preferably at least about 50,000, preferably at least about 75,000, preferably at least about 100,000, preferably at least about 150. , 000 copolymers (such as brominated isobutylene-paramethylstyrene copolymer). The copolymer further comprises a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), ie Mw / Mn, of less than about 10, preferably less than about 8, preferably less than about 6, preferably less than about 4, more preferably. It may be less than about 2.5, most preferably less than about 2.0. In another embodiment, as a suitable halogenated isobutylene elastomer component, a copolymer (as measured according to ASTM D 1646-99) having a Mooney viscosity (1 + 4) of 25 or higher at 125 ° C., preferably 30 or higher, more preferably 40 or higher. (Brominated isobutylene-paramethylstyrene copolymer and the like).

  In one embodiment, the brominated copolymer of isobutylene and para-methyl styrene has 5-12 weight percent para-methyl styrene, 0.3-1.8 mol% brominated para-methyl styrene, (ASTM Those having a Mooney viscosity of from 30 to 65 (1 + 4) at 125 ° C. (measured in accordance with D 1646-99).

  In one embodiment, the halogenated isobutylene elastomer component is about 0.5 to 25 weight percent, preferably about 1 to 20 weight percent p-alkylstyrene, preferably p-methyl, based on the total weight of isobutylene and comonomer. It can be made from styrene and then halogenated. Typically, slurry polymerization of the monomer mixture is performed in the presence of a Lewis acid catalyst, and subsequent halogenation is performed in the presence of a radical initiator such as radical heat and / or light or a chemical initiator in the form of a solution. Done under. The content of halogen (eg, Br and / or Cl, preferably Br) is preferably less than about 10 weight percent, more preferably from about 0.1 to about 7 weight percent, based on the total weight of the copolymer. . In one embodiment, the preferred elastomer component comprises an isobutylene elastomer, preferably a halogenated isobutylene elastomer, most preferably a brominated p-methylstyrene-co-isobutylene polymer (BIMS).

  In the present invention, the thermoplastic material useful in the present invention (also referred to as a thermoplastic resin) is a thermoplastic polymer, copolymer, or mixture thereof having a Young's modulus greater than 200 MPa at 23 ° C. The melting temperature of the resin should be about 170 to about 260 ° C, preferably less than 260 ° C, and most preferably less than about 240 ° C. In accordance with conventional definitions, a thermoplastic is a synthetic resin that softens when heated and recovers its original properties when cooled.

  Such thermoplastic resins may be used alone or in combination and are usually nitrogen, oxygen, halogen, sulfur, or other groups capable of interacting with aromatic functional groups such as halogen or Contains 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. Includes resins selected from the group consisting of resins (SAN), styrene maleic anhydride resins (SMA), aromatic polyketones (PEEK, PED, and PEKK), ethylene copolymer resins (EVA or EVOH), and mixtures thereof. .

  Suitable polyamides (nylons) include crystalline or resinous high molecular weight solid polymers such as copolymers and terpolymers having repeating amide units in the polymer chain. Polyamides can be made by polymerization of one or more ε-lactams such as caprolactam, pyrrolidione, lauryl lactam, and aminoundecanoic lactam, or amino acids, or by condensation of a dibasic acid and a diamine. Both fiber-forming and molded grade nylons are suitable. Examples of such polyamides include polycaprolactam (nylon-6), polylauryllactam (nylon-12), polyhexamethylene adipamide (nylon-6,6) polyhexamethylene azelamide (nylon-6,9 ), Polyhexamethylene sebacamide (nylon-6, 10), polyhexamethylene isophthalamide (nylon-6, IP), and 11-amino-undecanoic acid condensate (nylon-11). Commercially available polyamides can be advantageously used in the practice of the invention, with linear crystalline polyamides having a softening point or melting point of 160-260 ° C being preferred. Copolymer nylon 48, nylon MXD6, nylon 6/66 (N6 / 66), nylon 610 (N610), nylon 612 (N612) may also be used. These copolymers and any blends thereof can also be used.

  Further examples of satisfactory polyamides include those with a softening point above 275 ° C and Kirk-Othmer, Encyclopedia of Chemical Technology, v. 10, page 919 and Encyclopedia of Polymer Science and Technology, Vol. 10, pages 392-414. Includes those described in. Commercially available thermoplastic polyamides can be advantageously used in the practice of the present invention, with linear crystalline polyamides having a softening point or melting point of 160-230 ° C. being preferred.

  In one embodiment, the polyamide is at least one member selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 69, nylon 12, nylon 610, nylon 612, nylon 6/66, and copolymers thereof. is there.

Suitable polyesters that may be used include polymer reaction products of one or a mixture of anhydride aliphatic or aromatic polycarboxylic acid esters and one or a mixture of diols. Examples of satisfactory polyesters include poly (trans-1,4-cyclohexylene C _2-6 alkanedicarboxylates such as poly (trans-1,4-cyclohexylene succinate) and poly (trans-1,4 -Cyclohexylene adipate); poly (cis or trans-1,4-cyclohexanedimethylene) alkanedicarboxylates such as poly (cis-1,4-cyclohexanedimethylene) oxalate and poly- (cis-1,4- Cyclohexanedimethylene) succinate, poly (C _2-4 alkylene terephthalate), such as polyethylene terephthalate and polytetramethylene-terephthalate, poly (C _2-4 alkylene isophthalate, such as polyethylene isophthalate and polytetramethylene-isophthalate, and Same Materials include. Preferred polyesters are derived from a C ₂ -C ₄ diols and aromatic dicarboxylic acids and polyethylene terephthalate and polybutylene terephthalate, such as naphthalene acid (naphthalenic acid) or phthalic acid. Preferred polyesters, The melting point is 160-260 ° C.

  Poly (phenylene ether) (PPE) resins that can be used in accordance with the present invention are well-known commercially available materials produced by oxidative coupling polymerization of alkyl-substituted phenols. These are generally linear amorphous polymers with a glass transition temperature of 190-235 ° C.

Ethylene copolymer resins useful in the present invention include copolymers of ethylene with unsaturated esters of lower carboxylic acids and carboxylic acids themselves. In particular, copolymers of ethylene and vinyl acetate or alkyl acrylates such as methyl acrylate and ethyl acrylate can be used. These ethylene copolymers typically contain about 60 to about 99 wt% ethylene, preferably about 70 to 95 wt% ethylene, more preferably about 75 to about 90 wt% ethylene. As used herein, the expression “ethylene copolymer resin” usually refers to unsaturated esters of ethylene and lower (C ₁ -C ₄ ) monocarboxylic acids and the acids themselves, such as acrylic acid, vinyl esters, Or a copolymer with an alkyl acrylate. This expression is further intended to include both “EVA” and “EVOH” which refer to the ethylene-vinyl acetate copolymer and its hydrolyzed counterpart, ethylene-vinyl alcohol.

  In DVA, the halogenated isobutylene elastomer constitutes no more than about 95-100 parts by weight per 100 parts by weight of the alloy, preferably about 95-5 parts by weight of the alloy. In one embodiment, the elastomer is present in an amount of 5 to 80 parts by weight of the alloy. In one embodiment, the elastomer is present in an amount of 10 to 65 parts by weight of the alloy. In one embodiment, the amount of thermoplastic resin is about 5 parts by weight or more per 100 parts by weight of the alloy, preferably about 5 to 95 parts by weight of the alloy. In one embodiment, the halogenated isobutylene elastomer comprises 5 to 80 parts by weight, the polyamide comprises 20 to 95 parts by weight, and the total weight parts of the halogenated isobutylene elastomer and polyamide total 100.

  DVA is a cross-linking or cross-linking agent, cross-linking or cross-linking accelerator, various types of oils, anti-aging agents, reinforcing agents, plasticizers, softeners, or various other additives normally mixed in general rubber May further be included. The composition is cross-linked by mixing and cross-linking the compounds in a conventional manner. The general amounts of these additives are known to those skilled in the art and are selected so as not to conflict with the improvements observed with the thermoplastic elastomer compositions according to the present disclosure.

  Thermoplastic elastomer compositions may include one or more composition additives such as carbon black; fatty acids; waxes; antioxidants; cross-linking agents; calcium carbonate; clays; ZnO; CuI; anti-scorch additive; anti-cling additive; tackifiers such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and glycerol stearate and Thermal stabilizers; antiblocking agents; mold release agents; antistatic agents; pigments; colorants; dyes; Each of the composition additives is in an amount of about 50 phr or less, about 40 phr or less, about 30 phr or less, about 20 phr or less, about 10 phr or less, about 5 phr or less, about 3 phr or less, about 2 phr or less, or about 1.5 phr or less, respectively. May be present in the composition.

  Suitable UV absorbers and UV stabilizers include hindered amine light stabilizers (HALS). In one embodiment, HALS includes amino, amino ether derivatives of 2,2,6,6-tetramethylpiperidine, and the like. In one embodiment, the HALS is an oligomeric hindered amine light stabilizer, such as TINUVIN (Ciba Specialty Chemicals, USA). Suitable antioxidants include hindered phenols. Examples include those sold under the trade name Irganox (BASF, USA). Suitable antioxidants / antiozonants include substituted aminotriazines such as 2,4,6-tris- (N--) sold under the trade name DURAZONE 37 (CHEMTURA, USA). 1,4-dimethylpentyl-p-phenylenediamino) -1,3,5-triazine and the like.

  In one embodiment, the thermoplastic elastomer composition may further comprise one or more plasticizers. Examples include sulfonamide plasticizers such as those sold under the trademark UNIPLEX, such as UNIPLEX 214n-butylbenzenesulfonamide or BBSA (Unitex Chemical, USA).

  In the present invention, the thermoplastic elastomer composition comprises DVA and a low molecular weight aromatic amine stabilizer, and the DVA and stabilizer are mixed as described herein. As described herein, “low molecular weight” refers to a compound having a number average molecular weight of less than 1000 g / mol. The low molecular weight aromatic amine stabilizer preferably has a molecular weight of about 500 g / mol or less.

  “Aromatic amine stabilizer” refers to a low molecular weight compound having an aromatic proton and at least one, preferably two or more amine groups. In one embodiment, the low molecular weight aromatic amine stabilizer can be represented by the general formula (I):

式中、Ｒ₁は、Ｃ₁〜Ｃ₂₀ヒドロカルビル基であり、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、及びＲ¹²は、個々に、Ｈ又はＣ₁〜Ｃ₂₀ヒドロカルビル基から選択される。一実施形態では、Ｒ²〜Ｒ¹²のいずれかが、個々に、Ｈ又はＣ₁〜Ｃ₁₀ヒドロカルビル基から選択される。

Where R ₁ is a C ₁ -C ₂₀ hydrocarbyl group and is R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^12. Are individually selected from H or C ₁ -C ₂₀ hydrocarbyl groups. In one embodiment, one of R ² to R ¹² is selected from individually, H, or C ₁ -C ₁₀ hydrocarbyl group.

As used herein, the term “hydrocarbyl group” refers to substituted or unsubstituted C ₁ -C ₂₀ linear, branched, and cyclic alkyl radicals, C ₆ -C ₂₀ aromatic radicals, C ₇ -C ₂₀ alkyls. substituted aromatic radicals, and C ₇ -C ₂₀ aryl-substituted alkyl radicals, refers to a halide radical, which may comprise various substituents. Furthermore, two or more such radicals can be joined together to form a fused ring system, including a partially or fully hydrogenated fused ring system. In one embodiment, the hydrocarbyl group is a substituted or unsubstituted C ₁ -C ₁₀ linear, branched, and cyclic alkyl radicals, C ₆ -C ₁₀ aromatic radical, C ₇ -C ₁₀ alkyl-substituted aromatic radicals , And C ₇ -C ₁₀ aryl substituted alkyl radicals, halogenated radicals, which may contain various substituents. Exemplary hydrocarbyl substituents include mono-, di-, and tri-substituted functional groups (also referred to herein as radicals) including Group 14 elements, each hydrocarbyl group having 1-20 carbons. Contains atoms. Examples of various hydrocarbyl substituents include substituents containing Group 15 and / or Group 16 heteroatoms. Examples include amine, phosphine, ether, thioether, and / or derivatives thereof such as amide, phosphide, per-ether, and / or thioether groups.

  Other functional groups suitable for use as substituents include: each functional group is hydrogen and an element of group 13, 14, 15, 16, and / or 17, preferably 1-20 or 1-10 carbons Organic and inorganic radicals are included, including atoms, oxygen, sulfur, phosphorus, silicon, selenium, or combinations thereof. Furthermore, the functional group may include one or more functional groups substituted with one or more additional functional groups. Examples of functional radicals include: hydrogen, hydroxyl, alkyl, alkyloxy, alkenyloxy, aryl, aryloxy, aralkyl, aralkyloxy, alkaryl, arylalkenyl, cycloalkyl, cycloalkyloxy, fatty Aliphatic, hydroxyl, alkanol, alkanolamine, oxy, acetyl, acetamide, acetoacetyl, acetonyl, acetonylidene, acrylyl, alanyl, allophanoyl, anisyl, benzamide, butryl, carbonyl, carboxy, carbazoyl, caproyl, capryl, Caprylyl, carbamide, carbamoyl, carbamyl, carbazoyl, chromyl, cinnamoyl, crotoxyl (c otoxyl), cyanato, decanol, disiloxanoxy, epoxy, formamide, formyl, furyl, furfuryl, furfurylidene, glutaryl, glycinamide, glycolyl, glycyl, glyosilyl, heptadecanoyl, heptanolyl, hydroperoxy, hydroxyamino (hydrox) , Hydrazide / hydrazide, hydroxy, iodoso, isocyanato, isonitroso, keto, lactyl, methacrylyl, malonyl, nitroamino, nitro, nitrosoamino, nitrosoimino, nitrosylnitroso, nitrilo, oxamide, peroxy, phosphinyl, phosphide / phosphido), phosphite (pho phospho / phosphono, phosphoryl, selenil, selenonyl, siloxy, succinamyl, sulfamino, sulfamyl, sulfeno, thiocarboxy, toluyl, ureido, valeryl radical, acetimide, amidino, amide, amino, aniline, anilino, arsino, Azide, azino, azo, azoxy, benzidine, benzidine, biphenyl, butylene, iso-butylene, sec-butylene, tert-butylene, cyano, cyanamide, diazo, diazoamino, ethylene, disilanyl, glycidyl, guanidino, guanyl, heptane Amide, hydrazino, hydrazo, hypophosphite, imide, isobutylidene, isopropylidene, silyl, Silylene, methylene, mercapto, methylene, ethylene, naphthal, naphthobenzyl, naphthyl, naphthylidene, propylene, propylidene, pyridyl, pyryl, phenethyl, phenylene, pyridino, sulfinyl, sulfo, sulfonyl, tetramethylene, tenenyl, thienyl, thiobenzyl Thiocarbamyl, thiocarbonyl, thiocyanate, thionyl, thiuram, toluidino, tolyl, a-tolyl, tolylene, a-tolylene, tosyl, triazano, ethenyl (vinyl), selenyl, trihydrocarbylamino, trihaloamino, trihydrocarbylphos Phyto, trihalophosphine, trimethylene, trityl, vinylidene, xenyl, xylidino, xylyl, xylylene, diene, and these Combination.

  In one embodiment, the low molecular weight aromatic amine stabilizer comprises diaryl-p-phenylenediamine. Examples of diaryl-p-phenylenediamine include compounds represented by the following formulae.

  In one embodiment, the aromatic amine stabilizer comprises N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine of formula (II).

  Stabilizer is about 1 part by weight (part per hundred of rubber by weight: phr) or more, about 1.5 phr or more, about 2 phr or more, about 2.5 phr or more, about 3 phr or more, about 3.5 phr or more. Or present in the thermoplastic elastomer composition at about 4 phr or more. Further, the stabilizer is present in the thermoplastic elastomer composition at about 20 phr or less, about 10 phr or less, about 9 phr or less, about 8 phr or less, about 7 phr or less, about 6 phr or less, or about 5 phr or less. The stabilizer is mixed with the DVA in an amount ranging from any of the aforementioned minimum parts by weight to any of the aforementioned maximum parts by weight.

Process In the present invention, the process for producing a thermoplastic elastomer composition comprises post-crosslinking a dynamically crosslinked alloy with a low molecular weight aromatic amine stabilizer, wherein the DVA is in a continuous phase comprising at least one thermoplastic resin. And an isobutylene elastomer component dispersed as a domain.

  In one embodiment, the process for producing a thermoplastic elastomer composition comprises dynamically cross-linking isobutylene elastomer components dispersed as domains in a continuous phase comprising at least one thermoplastic resin to produce DVA, which is then converted to DVA. Mixing with a low molecular weight aromatic amine stabilizer to produce a thermoplastic elastomer composition.

  In one embodiment, the thermoplastic elastomer composition first heats the DVA after cross-linking to a temperature above the glass transition temperature or softening temperature of the alloy, and then the alloy that has been melted at least partially under high shear conditions. It is produced by mixing with a group amine stabilizer and optionally other composition additives, plasticizers, etc. to form a mixture or blend. In one embodiment, the mixture is a uniform mixture comprising various components interdispersed with each other. When referring to a homogeneous mixture, it is not intended that the mixture be a single phase, but is intended to represent a well blended mixture of various materials present in the composition. In one embodiment, the mixing can be performed by a roll mill, a Banbury mixer, a continuous mixer, a mixer, a mixing extruder, such as a twin screw extruder, combinations thereof, and / or the like.

  In one embodiment, a method for reducing the viscosity of a DVA and improving UV resistance includes mixing DVA with a low molecular weight aromatic amine stabilizer to produce a stabilized composition, wherein: DVA comprises an isobutylene elastomer component dispersed as domains in a continuous phase comprising polyamide. As used herein, the viscosity of DVA is as described in ASTM D3855-08 at 1200 s-1, 220 ° C. using a die length of 30.0 mm and a diameter of 1.0 mm. Refers to the viscosity as determined by Laboratory Capillary Rheometry (LCR). As used herein, “ultraviolet resistant” refers to a modified composition that causes a thermoplastic elastomer composition to age by ultraviolet exposure as defined herein. Refers to the ability to resist changes in tensile strength relative to the tensile strength of the modified composition without ageing.

In one embodiment, the tensile strength of the thermoplastic elastomer composition after aging is greater than the tensile strength of the composition determined before said aging. As used herein and in the claims, “aging” refers to aging a composition at 1875 kJ / m ² , 340 nm according to SAE J1960 or equivalent, and tensile strength is ASTM D882-02. Or determined according to its equivalent.

In one embodiment, the rupture elongation of the thermoplastic elastomer composition after aging is greater than the rupture elongation of the composition determined prior to aging, wherein the composition is 1875 kJ / m ² , 340 nm according to SAE J1960 or equivalent. Aged. As used herein and in the claims, elongation at break is determined according to ASTM D882-02 or equivalent.

Accordingly, the present invention provides the following embodiments.
A. A thermoplastic elastomer composition comprising a post-crosslinking dynamic cross-linking alloy and a low molecular weight aromatic amine stabilizer, wherein the dynamic cross-linking alloy comprises an isobutylene elastomer component dispersed as a domain in a continuous phase comprising at least one thermoplastic resin. object.
B. A process for producing a thermoplastic elastomer composition comprising mixing a dynamically crosslinked alloy after crosslinking with a low molecular weight aromatic amine stabilizer, wherein the dynamically crosslinked alloy is in a continuous phase comprising at least one thermoplastic resin. A process comprising an isobutylene elastomer component dispersed as a domain.
C. Dynamically cross-linking isobutylene elastomer components dispersed as domains in a continuous phase comprising at least one thermoplastic resin to form a post-cross-linking dynamic cross-linking alloy; and the dynamic cross-linking alloy into a low molecular weight aromatic amine stabilizer. A process for producing a thermoplastic elastomer composition, comprising: mixing with said solution to produce a thermoplastic elastomer composition.
D. Thermoplastic elastomer composition produced by a process comprising: dynamically crosslinking a halogenated isobutylene elastomer component containing 10 phr or less of a curing agent or cross-linking agent dispersed as a domain in a continuous phase containing polyamide and post-crosslinking Forming a dynamically crosslinked alloy; and mixing the crosslinked dynamic crosslinked alloy with a low molecular weight aromatic amine stabilizer to form a thermoplastic elastomer composition.
E. A method of reducing the viscosity of a dynamically cross-linked alloy and improving UV resistance comprising mixing the dynamic cross-linked alloy with a low molecular weight aromatic amine stabilizer to produce a stabilized composition, A method wherein the dynamically crosslinked alloy comprises an isobutylene elastomer component dispersed as domains in a continuous phase comprising a polyamide.
F. The invention of any one of embodiments A to E, wherein the tensile strength of the composition after aging is greater than the tensile strength of the composition determined before aging.
G. The invention of any one of Embodiments A to F, wherein the rupture elongation of the composition after aging is greater than the rupture elongation of the composition determined before the aging.
H. The invention of any one of embodiments A to G, wherein the isobutylene elastomer component is halogenated.
I. Embodiments AH wherein the isobutylene elastomer comprises 95-25 parts by weight of the composition, the polyamide comprises 5-75 parts by weight of the composition, and the total weight of the halogenated isobutylene elastomer and polyamide is 100. The invention according to any one of the above.
J. et al. The invention of any one of embodiments AI, wherein the stabilizer is present in the composition at 1.5 phr or greater.
K. The invention of any one of embodiments AJ, wherein the stabilizer is present in the composition at 20 or 10 phr or 8 phr or less.
L. The invention of any one of embodiments AK, wherein the isobutylene elastomer component comprises brominated poly (isobutylene-co-p-methylstyrene).
M.M. The polyamide is at least one member selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 69, nylon 12, nylon 610, nylon 612, nylon 48, nylon MXD6, nylon 6/66, and copolymers thereof. The invention according to any one of Embodiments A to L.
N. Low molecular weight aromatic amine stabilizers have the general formula:

（式中、Ｒ¹は、Ｃ₁〜Ｃ₂₀ヒドロカルビル基であり、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、及びＲ¹²は、個々に、Ｈ又はＣ₁〜Ｃ₂₀ヒドロカルビル基から選択される）で表される、実施形態Ａ〜Ｍのいずれか１項に記載の発明。
Ｏ．Ｒ²〜Ｒ¹²のいずれかが、個々に、Ｈ又はＣ₁〜Ｃ₁₀ヒドロカルビル基から選択される、実施形態Ｎに記載の発明。
Ｐ．低分子量芳香族アミン安定剤の分子量が約５００ｇ／ｍｏｌ以下である、実施形態Ａ〜Ｏのいずれか１項に記載の発明。
Ｑ．低分子量芳香族アミン安定剤がジアリール−ｐ−フェニレンジアミンを含む、実施形態Ａ〜Ｐのいずれか１項に記載の発明。
Ｒ．低分子量芳香族アミン安定剤がＮ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミンである、実施形態Ａ〜Ｑのいずれか１項に記載の発明。
Ｓ．組成物が、カーボンブラック、脂肪酸、ワックス、酸化防止剤、硬化剤、炭酸カルシウム、クレー、シリカ、紫外線吸収剤、オゾン劣化防止剤、粘着付与剤、ＺｎＯ、ＣｕＩ、スコーチ防止剤、又はこれらの組合せを更に含む、実施形態Ａ〜Ｒのいずれか１項に記載の発明。

(Wherein R ¹ is a C ₁ -C ₂₀ hydrocarbyl group, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^12, individually, represented by is selected from H or C ₁ -C ₂₀ hydrocarbyl group) the invention according to any one of embodiments a to M.
O. The invention of embodiment N, wherein any of R ² -R ¹² is individually selected from H or C ₁ -C ₁₀ hydrocarbyl groups.
P. The invention of any one of embodiments AO, wherein the low molecular weight aromatic amine stabilizer has a molecular weight of about 500 g / mol or less.
Q. The invention of any one of embodiments AP, wherein the low molecular weight aromatic amine stabilizer comprises diaryl-p-phenylenediamine.
R. The invention of any one of embodiments A to Q, wherein the low molecular weight aromatic amine stabilizer is N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine.
S. The composition is carbon black, fatty acid, wax, antioxidant, curing agent, calcium carbonate, clay, silica, ultraviolet absorber, ozone degradation inhibitor, tackifier, ZnO, CuI, scorch inhibitor, or a combination thereof The invention according to any one of Embodiments A to R, further comprising:

  By heating while mixing dynamic cross-linking alloy (DVA) to partially melt the material, and then adding stabilizers and other ingredients to the melt while mixing to produce a post-crosslinking composition, A series of compositions for illustration and comparison were prepared. The composition was prepared using the materials listed in Table 1.

  The compositions were tested according to the test parameters of the method described in Table 2.

  A series of six compositions was prepared by first forming a DVA to form a post-crosslinking DVA, and then melt mixing the DVA with or without selected low molecular weight amine stabilizers. The results are shown in Table 3 below. The resulting composition was then manufactured and tested. The test results are shown in Table 4.

  As can be seen in Tables 3 and 4, the melt viscosity indicated by the torque at dump is decreasing in proportion to the amount of added amine stabilizer (6PPD), which is very surprising. It should be noted that the UV stabilization reflected in the permanent elongation data is about the same and is not significantly different regardless of the amount of stabilizer. This shows that it can be UV stabilized with an amine stabilizer and at the same time the amount of stabilizer added to the DVA after crosslinking can be used to adjust the desired melt viscosity of the composition.

In another set of examples, the DVA used in Composition 1 was compared with various samples of carbon black and TiO ₂ without an amine stabilizer and with 2.5 phr low molecular weight amine stabilizer (6PPD) for comparison. Inventive compositions were made by melt blending after crosslinking. The LCR, tensile strength, and elongation at break of each composition were measured. The composition was subjected to aging and the tensile strength was measured again to determine the change in tensile strength after aging. The data is shown in Table 5.

The data in Table 5 shows that the presence of the amine stabilizer is carbon black and / or TiO ₂ as seen in the lower LCR data for compositions 16-24 compared to compositions 7-15 without amine stabilizer. And reduce the viscosity of the produced composition. The amine stabilizer further improved (increased) the tensile strength and elongation at break, and further reduced or increased the overall decrease in tensile strength after aging.

  The composition was prepared by melt mixing the post-crosslinked DVA used in Composition 1 with various components typical for end use in pneumatic tire applications. The compositions were made with carbon black, zinc oxide, with or without various stabilizers and antioxidants. Tensile strength and elongation were measured, samples were aged, and tensile strength and elongation were measured again to determine changes in tensile strength and elongation at break after aging. The results are shown in Tables 6, 7, and 8.

Thus, as the data show, the post-crosslinking mixing of low molecular weight stabilizers in DVA, especially in the case of inventive low molecular weight amine stabilizers in compositions 31, 32, 43-46 , 49 and 50, Resulting in a composition having improved processability including a reduction in UV resistance and improved UV resistance.

  All numerical ranges recited in the above specification and appended claims, such as those that represent a specific set of properties, units of measurement, conditions, physical state, or percentage, are included in such ranges. All numbers, such as any range or any sub-set of numbers contained within any such stated range, are intended to be explicitly or explicitly incorporated herein by reference or otherwise. doing.

  All documents mentioned herein, including all patent applications and / or test methods, are hereby incorporated by reference to the extent they do not conflict with the present application and claims. The principle, preferred embodiment, and operation mode of the present invention have been described in the above specification. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely examples of the principles and applications of the present invention. Accordingly, it will be understood that many modifications can be made to the example embodiments and other configurations can be devised without departing from the spirit and scope of the invention as defined in the appended claims. It should be.

Claims (6)

A method for reducing the melt viscosity of a dynamically cross-linked alloy to produce a stabilized thermoplastic elastomer composition comprising:
Obtaining a dynamically crosslinked alloy comprising an isobutylene elastomer component dispersed as domains in a continuous phase comprising at least one thermoplastic resin;
In order to heat the dynamically cross-linked alloy to at least partially melt the dynamic cross-linked alloy and to produce a thermoplastic elastomer composition, the dynamic cross-linked alloy is prepared on the basis of 100 parts by weight of the isobutylene elastomer component. by melting a stabilizer mixture comprising a low molecular weight aromatic amine stabilizer 20 parts by weight, seen including reducing the melt viscosity of the dynamic crosslinking alloy,
Low molecular weight aromatic amine stabilizers are general formulas

(Wherein R ₁ is a C ₁ -C ₂₀ hydrocarbyl group, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is individually, H, or C ₁ -C ₂₀ hydrocarbyl group.)
In represented by a method (unless low molecular weight aromatic amine stabilizer is N-(1,3-dimethylbutyl)-N'-phenyl -p- phenylenediamine.).   The tensile strength of the composition after aging is greater than the tensile strength of the composition determined before aging, or the elongation at break of the composition after aging is determined for the composition determined before aging. The method of claim 1, wherein the method is greater than the elongation at break.   The said isobutylene elastomer component comprises 95-25 weight part, the said thermoplastic resin comprises 5-75 weight part, and the total weight part of the said isobutylene elastomer component and a thermoplastic resin is set to 100 in total. 2. The method according to 2. The method according to any one of claims 1 to 3 , wherein the molecular weight of the low molecular weight aromatic amine stabilizer is 500 g / mol or less. The low molecular weight aromatic amine stabilizer comprises a diaryl -p- phenylenediamine A method according to any one of claims 1-4. The at least one thermoplastic resin is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 69, nylon 12, nylon 610, nylon 612, nylon 48, nylon MXD6, nylon 6/66, and copolymers thereof. at least a one polyamide, the method according to any one of claims 1 to 5 to be.