TW200922998A - Composite material, process for preparing the composite material, and use thereof - Google Patents

Abstract

Composite material comprising rubber, a sulfur-containing vulcanizing agent, a layered double hydroxide comprising hydroxyl and/or an organic ion as charge-balancing organic(s), and less than 1.5 phr ZnO.

Description

200922998 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composite material comprising a rubber and a sulfur-containing vulcanizing agent. [Prior Art] The rubber composition usually contains an activator which accelerates the solidification of sulfur. Zinc oxide is the most widely used activator in combination with stearic acid, as appropriate. Lead and magnesium oxides also act as activators, but are not used often. f' However, the release of ecotoxic zinc substances into the environment is a concern. Resignation ‘The release of rubber into the environment occurs during the production of rubber products, during handling and recycling, and due to tire wear. Therefore, there is interest in its possible alternatives. However, to date, no viable alternatives have been found to completely remove Zn0 from the rubber compound without significantly impairing handling and performance characteristics. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a Zn0 substitute. Another object of the present invention is to provide a composite material comprising rubber having improved gas permeability, greater flexibility, and reduced amount of conventional activators such as Zn0. It is also an object of the present invention to provide a zinc-free composite. Glue · 'Sulphur-containing vulcanizing agent, right right emergency 4曰 _ η / upper, 丄,.,,.u.

This object is achieved by a composite material of the invention comprising an oak containing hydroxide and/or organic ions as a charge leveling agent, and less than 0.5 Phr (per hundred parts of rubber). The layered double hydroxide (LHD) can be a suitable substitute for ZnO in the sulfur complex. Curing 椽 复 134 134 913.doc 200922998 and although a rubber composite comprising a layered double hydroxide has been disclosed in U.S. Patent No. 2003/01583, the sulfur-curable composite disclosed therein contains a layered double in the form of a calcined form. Niobium oxide (so-called solid solution that is no longer layered) and a large amount of ZnO (1.82 phr). The recognition of the significant reduction in ZnO content when using LDH in sulfur-curable compositions is not disclosed or recognized in this document. The composite of the present invention can be converted to a cured composite by vulcanization. The cured composites have good thermal stability, dimensional stability, tear strength, scratch resistance, flame retardancy, and/or strength-to-weight ratio. The material further exhibits low gas and/or liquid permeability, such as nitrogen, anaerobic anaerobic, milk, water vapor, and hydrocarbons. The LDH present in the composite of the present invention can further adsorb and/or absorb additives or by-products of the initiator used in the polymerization of the polymer. In addition, the cured composite of the present invention exhibits improved elongation at break and breaking strength as compared to pure rubber materials without LDh. In addition, the composite exhibits good dynamic properties (e.g., low tan5) during deformation under constant force. This is due to tires having low heat build-up and rolling resistance. As is known to those skilled in the art, the term "tanS" is defined as the ratio of the loss modulus (G,) to the storage modulus (G'〇. Among the rubber compositions, the layered double hydroxide may be partially or It completely replaces the activator conventionally used such as zinc oxide. Therefore, it is allowed to prepare less than 1.5 phr Zn0, preferably less than i phr Zn 〇, more preferably less than 〇5 coffee, and 敢佳元王 does not contain Zn 〇 Rubber composite. In an even more preferred embodiment, the composite of the invention does not contain any substance. 134913.doc 200922998 In addition, the composite may contain less than 1.5 phr of any activator or better free of activation. Examples of conventional activators other than zinc oxide are zinc stearate, lactic acid, zinc 2-ethylhexanoate, lead oxide (e.g., Pb〇 and Pt> 3〇4), oxidized, and mixtures thereof. Further details can be found in Chapter 3 of the Rubber Chemicals, Kirk-Othmer Encyclopedia of Chemical 7Vc/mo/og>; (j〇hn Wiley & Sons, online mailing date: December 4, 2000) "Activators and Retarders Medium ° & use the present invention The layered double hydroxide further reduces the amount of accelerator conventionally used in the rubber vulcanization process. The sulfur-containing vulcanizing agent used in the composite of the present invention can be any sulfur-containing vulcanizing agent known in the art' Λ:Ζ>Α:_ Othmer Encyclopedia of Chemical Technology (J〇hn Wiley & Sons, online mailing: December 4, 2000) Chapter i "Accelerators of Vulcanization" and Chapter 2 "Cross- The linking agents are described in the following. Suitable sulfur-containing vulcanizing agents include accelerators and cross-linking I; agents. Examples of suitable sulfur-containing accelerators are thiazoles (including benzothiazepines). A bismuth citrate (including a dithioaminyl citrate), a thiuram sulfide, a guanidine, a thiourea, a xanthogen, a thiol thiol, a triazine thione, a disulfide Phosphonates and their metal derivatives "Also - a combination of a sulfur-free accelerator with a sulfur-containing accelerator and/or a sulfur-containing crosslinker may be considered. An example of a sulfur-free accelerator is an amine' which includes hexamethylene Tetraamine, mono- and monodecylamine, N-ethyl hexylamine, off a combination of tallow amine, amine isophthalate and aniline; and an aldehyde and an amine such as butyraldehyde-aniline, butyrate-monobutylamine and heptane-aniline; and quaternary ammonium compounds, including isophthalic acid Acid 134913.doc 200922998 Hydrogen dimethyl ammonium. Further details of such accelerators can be found in 舳 "π Chemicals, Kirk-Othmer Encyclopedia 〇f Chemical Tec/mo/o phantom; (John Wiley & s〇ns, online mailing period: 2 annihilation December 4 Day) Chapter 1 rAccelerat〇rs〇fVulcanizati〇n". Examples of suitable sulfur-containing crosslinkers are sulfur, insoluble sulfur, sulfur donors (including 4'4-thiodimorphine and N,N,_caprolactam disulfide), polyfunctional sulfur compounds (including Alkyl phenol disulfide, 2,5-dioxa" "supplemented thiadiazole derivative, and hexamethylene-Lb dithiosulfate". It is also possible to consider cross-linking of sulfur-free crosslinker with sulfur. A combination of a solvent and/or a sulfur-containing accelerator. Examples of the sulfur-free crosslinking agent are a peroxide, a hydrazine, a phenol formaldehyde reaction product, a diamine, a methylene diphenylamine, a tri-ethyltetramine, and a UK. Kangniuminomethyl)benzene. Further details of such crosslinkers can be found in Chemicals, Kirk-Othmer Encyclopedia 〇f Chemical 7>c/m0/0 illusion; (j〇hn Wiley & Sons' online Mailing date: December 4, 2010) Chapter 2 "Cross-linking agents". The layered double hydroxide present in the composite of the present invention has a layered structure corresponding to the following formula: [M: +Mr(〇H)2m+2n]X-.bH20 (1) wherein the lanthanide is a metal ion 'eg Zn2+, Mn2+, 2+, c〇2+ W, CV+, Sf, Ba2, Ca2+, and Mg2+; m3+ is a trivalent gold ion such as Al3+, Cr3+, C〇3+, Mn3+, such as + , cf, and Ga3+ ; mAn has a value of m/n=n〇' and 6 has a value ranging from 〇 to 1〇. X. is a charge-balanced anion. The charge-balancing anion is selected from the group consisting of hydroxides, organic anions, and (1) a combination of two or more of the ions 134913.doc 200922998 (8) - a combination of one or more ion species such as carbonic acid (iv) other anions. Since LDH typically has a layered structure, the charge balancing anions can be located on the interlayer, edge and outer surfaces of the stacked LDH layer. These ions located between the stacked retarded layers are referred to as intercalated ions. LDH containing charge-balanced organic ions exhibits organophilicity and is also known as "organic clay." Stacked (four) or organic clay may also be layered or flaked, as in a polymer matrix. In the context of the present specification, the term "layering" is defined as the reduction in the average degree of stacking of the granules due to at least partial delamination of the LDH structure, thus resulting in a material comprising significantly more individual LDH sheets per volume. The term "peeling" is defined as complete delamination, i.e., periodic ablation in the direction perpendicular to the LDH sheet, which results in random dispersion between the individual in the medium, thereby leaving a completely disordered stack. These LDH swells or swells (also known as LDH embedding) can be observed by X-ray diffraction (XRD) because the position of the bottom surface reflection (i.e., reflection) indicates the distance between the layers, which increases with embedding. As the XRD reflection broadens until it disappears or the asymmetry of the bottom reflection (00/) increases, a decrease in the average stacking degree can be observed. The characterization of complete stratification (ie, flaking) is still an analytical challenge, but can usually be inferred from the complete disappearance of the non-reflection of the initial LDH. Therefore, the order of the layers and thus the degree of stratification can be further observed by a transmission electron microscope (TEM). In an embodiment of the invention, the LDH comprises hydroquinone as a charge balancing anion. As indicated above, the LDH can be used only as a charge balancing anion by hydroxide as a charge balancing anion or by combining hydroxy hydroxide with at least one inorganic and/or organic anion 134913.doc -10- 200922998. Compared with other snails, there is a vulcanization property of the LDH as a charge balancing anion. "Alternatively," in the composite material of the present invention, the total amount of charge-balanced ions in the Cong to v 1 0 mol% is a hydroxide, preferably the total charge balance ion % 2 is better than at least 60 mol % and Preferably at least 9° mole % is hydrogen. In another embodiment, the LDH comprises a mixture of hydroxide and carbonate: a mixture of hydroxide and organic anion. In the LDH containing both hydroxide and carbonium anion, the amount of charge-balanced hydroxide anion is measured by the following method. The LDh is treated in boiling water under a hydrocarbon stream, and the discharged carbon dioxide is absorbed into acetone and chlorinated. In the ruthenium solution, the passed solution is titrated with a gas oxidized steel, and the result is used to calculate the contribution of the carbonate and thus the hydroxide to the total amount of charge balance anions in the LDH. The amount of LD-charge-balanced chloride anion, which also contains an organic charge-balancing anion, can be calculated from the hydroxide concentration of the initial LDH and the amount of organic anion added thereto. For example, LDH containing both hydroxide and carbonate as the equilibrium anion can be prepared by drying the oxygenated LDH aqueous (IV) in the presence of atmospheric or carbon dioxide. The (4) may be hydrotalcite-like material, through the town of Shaoshi, Shuizhen Mingshi, carbon town iron ore, water town iron, carbon town rock, Babu road ore ((4) (10) ^ (4), Aluminite, Nickel ore, or hydrated manganite. The preferred LDH has a layered structure corresponding to the following formula:

NrAi: +(〇H)2ro+jx:.bH2〇(II) which has a value of m/n=U10, preferably ..., and b has a value ranging from 〇134913.doc 200922998 to 10, usually 2 To the value of 6. X is a charge balancing ion as defined above. m/n should preferably have a value of 2 to 4, more specifically a value close to 3. The LDH can be any crystalline form known in the art (eg, by

Cavani et al. Γθί/ay, 11 (1991), pp. 173-301) or by Bookin et al. (JLDHs and LDH Minerals, (\993), pp. A\(5), pp. 55 8·564) Said), and any polytype such as 3H!, 3H2, 3Rd3R2 stack. In another embodiment of the invention, the LDH comprises one or more organic anions as charge balancing anions and is therefore an organic clay. The / charge balancing organic anion can be any organic anion known in the art. The organic anion usually has at least 2 carbon atoms, preferably at least 6 carbon atoms, even more preferably at least 8 carbon atoms, and most preferably at least one carbon atom, and usually at most 1, one carbon atom, It is preferably at most 5 carbon atoms, and most preferably at most 1 carbon atom. In this organic clay, the distance between individual [1:) 1^ layers is usually greater than the distance between the conventional LDH layers without organic anions. Preferably, the distance between the layers in the lDH present in the composite of the invention is > 1.0 nm, more preferably at least 1.5 nm and most preferably at least 2 nm. The distance between individual layers can be measured by X-ray diffraction. Suitable organic anions include mono- and poly-carboxylates, sulfonates, phosphonates, nitrates, borates, phosphates, thiols, malonates, 1,3-dioxes, and sulfates. Two or more organic anions can also be considered. Preferred examples of the organic anion of the present invention are monocarboxylic acids such as the lipid 13 acid and based on rosin 134913.doc •12·200922998 ions. Particularly preferred organic anions have from 8 to 22 carbon', soil = monthly fat. Suitable examples of such fatty acids are caprylic acid, citric acid, ^^^^^^^^^ Μ. ' ^ ^ acid, palmitic acid 'oleic acid, linoleic acid, linoleic acid and mixtures thereof. Further - preferred organic anion is rosin. Rosin is derived from natural sources and is readily available' and relatively inexpensive compared to synthetic organic anions. Typical examples of natural origins are gum rosin, wood rosin and tall oil rosin. Rosin is usually a mixture of various isomers of monoterpenic acid monocyclic abietic acid, usually containing about 20 carbon atoms. The three ring structure of various rosin acids differ mainly in the position of the double bond. Usually, rosin is a mixture of various substances, including levofloxacin, neo-abietic acid, long-leafed acid, rosin acid, dehydroabietic acid, dehydroabietic acid, tetrahydroabietic acid, dichloroabietic acid, sea pine. Acid and isopimaric acid. Rosin derived from natural sources also includes rosin substances, ie rosin mixtures, which are polymerized, isomerized, disproportionated, hydrogenated and with Diurs-Alder (9) in the presence of acrylic acid, acetamidine and propylene (4). · ^ (4) The reaction was significantly modified. The product obtained by these methods may be referred to as modified rosin. Natural rosin can also be chemically altered by any of the methods known in the art. For example, the thiolate on the rosin reacts with a metal oxide, a metal oxychloride or a salt to form a rosin soap or salt (so-called resinate). Such chemically altered rosins may be referred to as rosin derivatives. The rosin can be used! The human organic group, the anionic group or the cationic group is modified or chemically altered. The organic group may be a substituted or unsubstituted aliphatic or aromatic hydrocarbon having from 丨 to 4 碳 carbon atoms. Anion 1349I3.doc 13 200922998 Subgroups can be any anionic group well known to those skilled in the art, such as carboxylate or sulfonate. Further details of such rosin-based materials are available from D.f. Zinkel and J.

RuswW [in Naval Stores, pr〇ducti〇n-chemistry-utilization, 1989, New York, Part II, Chapter 9), and j B Class ("Resins, Natural," Chapter 1: "R〇sin and Modified

Rosms, "Kirk-Othmer Encyclopedia of Chemical Online Mailing Day: December 4, 2, 2008" was collected. In one embodiment of the invention, the charge balancing organic ion comprises a first functional group and a second functional group. The first functional group is capable of interacting with an anionic group. Examples of such first functional groups are carboxylates, sulfates, sulfonates, nitrates, borates, phosphates and phosphonates. The second official month & group can form a chemical bond with the rubber, which is optionally combined with the sulfur-containing vulcanizing agent of the present invention. Examples of such second functional groups are acrylates, mercapto acrylates, hydroxyl groups, gas groups, bromine groups, amines, epoxy groups, thiols, vinyl groups, di- and polysulfides, urethanes, ammonium groups. , sulfonic acid, sulfinic acid, sparing, scaly, phosphinic acid, isocyanate, hydrogen, quinone, nitrosophenyl, dinitrosophenyl, phenol, ethoxylated and anhydride. According to this embodiment, suitable examples of the organic anion include 8-aminooctanoic acid, 12-aminododecanoic acid, 3-(acryloxy)propionic acid, 4-vinylbenzoic acid, 8_(3_octyl) 2_Ethylene bromide) octanoic acid and unsaturated fatty acids such as oleic acid and unsaturated tallow. The composite material may also include a decane coupling agent. In a preferred embodiment, the LDH is modified with the coupling agent. The decane coupling agent preferably has at least 134913.doc •14-200922998 an alkoxyfluorenyl group and at least one reactive group, the alkoxy oxime group being chemically bonded to the layered double hydroxide, the reaction The group is chemically attached to the rubber. The LDH can be modified during or after LDH synthesis in the presence or absence of rubber. The reactive group may be the same group as the second functional group defined above. Examples of such decane coupling agents are bis-3_(ethoxy methoxypropyl) tetrasulfide (Si69® from Degussa), bis(3-diethoxysulfonylpropyl) disulfide. , γ-mercaptopropyltrimethoxysulfonium (SiSiB® PC2300 from PCC) and 3-octylthio-1-propyltriethoxydecane (from NXTtm from GE). The advantage of the presence of the decane coupling agent is that a chemical bond can be formed between the layered double hydroxide and the rubber during vulcanization, which improves dynamic properties and mechanical properties. The amount of decane coupling agent is such that at least a portion of the LDH in the composite is chemically bonded to the rubber. If the rubber is a rubber other than the polyoxyxene rubber, the amount of the decane coupling agent is usually at least 0.5% by weight based on the total weight of the LDH, preferably at least 1 weight/〇 and optimally at least 5% by weight, and the decane couple The amount of the mixture is usually up to 50% by weight, preferably up to 40% by weight and most preferably up to 30% by weight based on the total weight of the LDH. /〇. If the rubber is a polyoxyxene rubber, the amount of the decane coupling agent is usually at least 1% by weight, preferably at least 20% by weight and most preferably at least 30% by weight based on the total weight of the LDH, and the amount of the decane coupling agent is usually LdH. The total weight is up to 99% by weight, preferably up to 90% by weight and optimally up to 80% by weight. In one embodiment of the invention, the LDH comprises an alkyl coupling agent and one or more charge balancing organic anions, particularly comprising an organic anion of the first and 134913.doc -15-200922998 difunctional groups as defined above. The amount of LDH in the composite of the present invention is preferably from 0.01 to 75% by weight, more preferably from 5 to 6 % by weight, and most preferably from 0.1 to 50% by weight, based on the total weight of the composite. Combinations of two or more LDHs can be considered for use in such composite materials. Examples of the rubber present in the composite of the present invention include natural rubber (NR), styrene-butene rubber (SBR), polyisoprene (ir), polybutadiene or butyl rubber (BR), polyisobutylene. (IIR), halogenated polybutadiene rubber, _ polyisobutylene rubber, nitrile butadiene rubber (NBr), hydrogenated nitrile butadiene rubber, styrene-isoprene-styrene (SIS) and the like ( Hydrogenated styrene block copolymer (SBS, hydrogenated SIS, hydrogenated SBS), poly(epichlorohydrin) rubber (CO, ECO, GPO), polyoxyxene rubber (q), chloroprene rubber (CR), Ethylene propylene rubber (EPM), ethylene propylene diene rubber (EpDM), fluororubber (FKM), ethylene vinyl acetate rubber (EVA), vinyl butadiene rubber, halogenated butyl rubber, polyacrylic rubber (ACM) ), polynorbornene (PNR), polyurethane, and polyester/polyether thermoplastic elastomer. Preferred rubbers are natural rubber, SBR, EPDM, toothed butyl rubber, and butadiene rubber. The composite of the present invention may further comprise additives commonly used in the art. Examples of such additives are pigments, dyes, anti-reversion agents, debonders, UV stabilizers, heat stabilizers, antioxidants, fillers (such as hydroxyapatite, cerium oxide, decane coupling agents, compatibilizers, Oil, wax, carbon black, glass fiber, polymer fiber, non- & π 八 eight clay and other inorganic materials), flame retardant, plasticizer, rheology modifier, cross-linking agent and deaerator. Alternatively - the additives commonly used are extender oils. It is also conceivable to mix the modified 134913.doc 200922998 shell LDH with the additional oil and then add this mixture to the rubber. This has the advantage that the LDH is dispersed in the oil and can be easily and uniformly mixed in the rubber. These optional addenda and their corresponding amounts can be selected as desired. The composite of the present invention also contains a vulcanization rate retarder or retarder to adjust the rate of vulcanization. Examples of such vulcanization rate retardants are acid needles such as maleic anhydride, dilute succinic anhydride and phthalic acid needles; acids such as benzoic acid and salicylic acid; tetraisobutyl thiuram monosulfide; And quinone imine, such as Ν-(cyclohexylthio) phthalimide. The amount of such rate retarders required will generally depend on the desired rate of cure. Typically, the weight ratio of the vulcanization rate retarder to the layered double hydroxide is between 5 〇:1 and 1:50, preferably between 3G:1#1: between 观 and optimally between 2〇:ι and Between 1:20. The composite material of the present invention may be a so-called "nano composite material", i.e., a composite material having a composition of inorganic matter and having at least one dimension in the range of 〇 1 to 1 奈 nanometer. The invention further relates to a masterbatch, ie a highly concentrated addition premix comprising, based on the total weight of the masterbatch: (1) 30 and 90% by weight, preferably 25 and 8% by weight of a rubber knee or cured rubber, (8) 9 And 69% by weight, and 15% by weight of the layered double hydroxide, which contains wind oxides and/or organic anions as charge balance anions, and ((1)) 1 and 20 weight /. Preferably, 5 and i 5% by weight of a vulcanizing agent. The masterbatch shirt contains ZnQ. More preferably, (4) contains any ^ and any other conventional accelerators. These parent materials contain a layered or (4) letter. "If the LDH of the masterbatch 134913.doc 200922998 is not completely layered, then (if blended to obtain the oak base composite, it can be =) will be (four) _ with the rubber layer. _ - The step-by-step and the organic cross-ion of the first functional group, at least a portion of the organic anion of the LDH can be attached to the rubber or rubber precursor. -^aMt Learning The present invention *纟 relates to the layer defined above A rubber-free mixture of a double oxychloride and a sulfur-containing vulcanizing agent. The mixture can be suitably used in a method for preparing a rubber composite. In this way, the LDH and the sulfur-containing vulcanizing agent can be added to the rubber. The total weight of the mixture is at least 0.5% by weight, preferably 重量 〇/〇, optimally 5% by weight, and usually the amount of coffee is up to 99% by weight, preferably up to 9% by weight, and most 80% by weight. The invention further relates to a process for the preparation of the composite of the invention comprising the steps of: VIII a 1) layered double hydroxide optionally mixed with a first solvent and comprising one or more polymerizations And the second solvent of the rubber Contacting; or a2) contacting the layered double hydroxide, optionally mixed with the first solvent, with a composition comprising one or a rubber monomer and optionally a second solvent, and polymerizing the monomers to form a rubber; b> contacting the sulfur-containing vulcanizing agent with the rubber or the monomers before, during or after step a) or step a2); c) removing as appropriate during or after any of steps a), a2) 4b) The first and / or second solvent. 134913.doc • 18·

200922998 The method of the invention comprises two alternative steps a) & a2). In the step, LDH mixed with the first solvent as appropriate may be added to the rubber, and the particulate matter does not react with the rubber. Further, the addition of the ldh is carried out under the condition that a part of the anion reacts with the rubber by, for example, a second functional group. When the composition obtained in the step a) is cured, the remaining anion which is not reacted with the rubber can be chemically bonded to the rubber. In step a2), ldh mixed as appropriate with the first solvent is added to one or more rubber monomers. The monomers are subsequently polymerized. Depending on the polymerization conditions and the selected anion, a portion of the organic anion can be reacted, for example, via the second functional group with the isomeric monomer during its polymerization, which chemically bonds the LDH to the rubber. Alternatively, when the precursor is cured in step b), at least a portion of the anion can react with the rubber, which causes the LDH to be chemically bonded to the rubber. It should be noted that flaking and/or delamination of LDH can occur in any of the steps of steps Sichuan, u) and C). In an embodiment of the method of the invention, the LDH is added to the rubber while the rubber knee is maintained at its temperature at the fluid. In this way it is ensured that the LDH is easy to mix with the oak, which allows the LDH particles to be evenly distributed throughout the rubber in a very short time' which makes the process more economically attractive. The mixing and/or compounding steps can be batch processed (for example in B-uiTy, in a combined machine, or in a dual light mill) or in a continuous mode (for example in a tubular reactor, extruder, such as ( Co-rotation) double or single-screw extrusion: or kneading machine (reciprocating single-screw extruder) and lift mixer. In the context of this statement, the term "composite" refers to the movement of 134913.doc. 19- 200922998, in the case of an LDH comprising an organic anion and/or a decane coupling agent, the mixing can be carried out under application of sufficient shear stress to the polymer-based mixture to convert at least a portion of the micron-sized LDH particles to nanometer dimensions. particle. The shear stress can be applied by mixing the polymer based mixture in, for example, a Banburry mixer or in an extruder. If individual components (LDH and sulfur-containing vulcanizing agent) are not mixed with the rubber or its monomers, the compound combinations may be added to the rubber; via a rubber-free mixture or the above-mentioned masterbatch. The LDH used in the process of the invention can be reduced in size prior to step 31) or 32). The LDH can have a d50 value of less than 20 microns and a d90 value of less than 50 microns. Preferably, the d50 value is less than 15 microns and the d90 value is less than 40 microns, more preferably the d50 value is less than 1 〇 microns and the d9 〇 value is less than 30 microns, even more preferably the d5 〇 value is less than 8 microns and the d90 value is less than 20 microns, And optimally the d5 〇 value is less than 6 microns and the d90 value is less than 1 〇 microns. The particle size distribution can be measured by methods well known in the art, such as by laser diffraction in accordance with DIN 13320. The LDH having this smaller particle size distribution enables the LDH to be well mixed with the entire rubber and to facilitate flaking and/or delamination of the LDH. Desirable particle size distribution can be obtained by any method known in the art for reducing the particle size of inorganic materials such as L D η. Examples of such methods are wet milling and dry abrasion. Or 'by these LDHs can be produced during preparation, as exemplified by WO 02/085787. The first and second solvents used in the process of the invention may be any solvent suitable for use in any of the methods of the present invention and are well known to those skilled in the art. The first and/or second solvents may be the same or different and are preferably compatible with the 134913.doc -20.200922998 LDH and the rubber, its monomer and/or the resulting (cured) rubber composite. Solvent. The far first and/or second solvent includes alcohols such as decyl alcohol, ethanol 'isopropanol and n-butanol; ketones such as methyl amyl ketone, decyl ethyl ketone, decyl isobutyl hydrazine and cyclohexane Esters, such as ethyl acetate and butyl acetate; unsaturated acrylates such as butyl acrylate, decyl decyl acrylate, hexamethylene methacrylate and trimethylolpropane triacrylate; aromatic and non-aromatic Hydrogen compounds such as hexane, petroleum ether, terpene and xylene; and bonds such as dibutyl, tetrahydrofuran (THF) and methyl tert-butyl ether (MTBE). The composite of the present invention can be used to prepare a cured (i.e., sulfurized) rubber by a vulcanization step. This vulcanization can be carried out before or after the steps of the method of the invention. The composite of the present invention and/or its cured form can be suitably used in tire manufacturing (such as car tires, truck tires, tractor tires, construction machinery tires and aviation tires), winter tires, latex products (including gloves, condom balloons, Guide, glue line, foam, carpet back and coconut fiber and hair treated with rubber knees), shoe machine 'Civil engineering products (such as bridge support, rubber-metal laminate support), Belts and hoses, non-tire automotive applications including engine bases, rubber supports, seals, insulation rings, loops and protective covers), wire and electric and f-channel seals, f-study closures, sticks, small solid tires , accessories for household and commercial appliances, rubber balls and tubes, milk inflators and other agricultural-based applications. If it is present in the composite material, the rubber compound 134913.doc 200922998 is suitable for coating composition, pressure sensitive adhesive composition, plastic hard coating and paper release coating combination. Materials, fiber finishing applications (including fabric and hair care applications), sealants, adhesives, packaging and solar cells. The composite of the present invention can be used in any part of the tire which is usually used, such as carbon black or cation dioxide. Specifically, the rubber composition can be used for a bottom tread or tread base, a tread, a side wall, a rim pad, an inner layer, a carcass 'apex, a bead, and a belt. Combinations of the composite materials of the present invention with conventional inorganic fillers such as carbon black or precipitated dioxo may also be considered. The use of the layered double hydroxide can reduce the total amount of inorganic filler in the rubber composition while maintaining similar or improved mechanical properties. The use of the organic composite of the present invention in a tire improves the mechanical and dynamic properties of the tire; it can further enhance the bonding or adhesion between different rubbers, such as in different parts of the tire or between rubber and metal (eg, in metal) In the curtain) or between rubber and fiber. The rubber used in the tread is typically a solution SBR rubber which can be replaced by a less expensive rubber such as an emulsion sbr rubber without loss of mechanical or dynamic properties of the tread. The 〇11 also gives the rubber an improved puncture resistance. In a preferred embodiment, the layered double hydroxide is modified with a coupling agent containing a vulcanizable group or with an organic anion having a sulfurizable group. The coupling agent may be a decane coupling agent such as bis(3-triethoxycarbamidopropyl)tetrasulfide (Si69® available from DegUssa), bis(3-triethoxydecylpropyl) Disulfide, γ-mercaptopropyltrimethoxydecane (sold from PCC, S)B® PC2300) and 3-octylthiopropyltriethoxydecane (purchased from 134913.doc -22- 200922998) GE's NXTtm). Examples of vulcanizable organic anions are 12-hydroxystearic acid, 12-gas stearic acid, 12-aminedodecanoic acid, epoxidized fatty acid, mercaptopropionic acid, oleic acid, conjugated unsaturated fatty acid, dithio-di Propionic acid, p-hydroxybenzoic acid and maleic imine propionic acid. The advantage of the modified layered double hydroxide is that it reduces the time required to manufacture the tire, especially the green tire. In addition, the dimensional stability of the uncured tire and the final tire will be improved. In a conventional method, a precipitated silica stone is added to a rubber together with a coupling agent such as bis(3-diethoxyl/amp; syl-propyl) tetralithium dangerous compound to make the rubber composition at a high temperature. The reaction is carried out, the ethanol produced is removed, and an uncured tire is obtained, which is then cured at a higher temperature to start vulcanization and form a tire. The use of such modified layered double hydroxides in the preparation of tires has the advantage that the coupling agent has adhered to the particulate matter and does not form ethanol, which results in a reduction in processing time which can increase the production rate of the (green) tire. If a combination of the layered double-layer hydroxide and a conventional filler such as precipitated silica is used, the coupling agent may be separately added to the composition so that it can react with the dioxane. The layered double hydroxide may be present in a suitable solvent containing or containing almost no water (in the form of a glue-floating liquid added to the material, or it may be added to the extender oil, or as a solid. In increments In the case of oil or solids, there is no need to remove the solvent, which reduces the processing time and improves the safety of the method. Door Progress The composite of the present invention can also be used in solar cells. For this purpose, the rubber knee in the composite Examples are polyaminocarbamic acid: B: B: transparent, styrene-ethylene S owed vinyl ester rubber and polyfluorene 134913.doc -23· 200922998 氡 rubber. Preferably, the transparent rubber is a polyoxyethylene rubber. The solar cell unit can be any solar cell unit known in the art. Examples of the solar cell unit are a crystalline Si solar cell, an amorphous shi solar cell, a crystalline shi solar photovoltaic cell, a cell, and based on, for example, CdTe. ,

CuInSe2, Cu(In,Ga)(Se,S)2 (so-called CIGS) composite semiconductor solar cells and Gratzel cells. Further details can be obtained from F. pfisterer ("Photovoltaic CeUs", Chapter 4: "Types 〇f ph〇t〇v〇ltaic

Cells, j Ullmann's Encyclopedia of Industrial Technology, online mailing period: June 15th, 2000). The composite material used in the solar cell unit can be used to connect two parallel layers in the cell. The rubber composite and/or cured rubber composite of the present invention is advantageous in that it is transparent to visible light, which enables application at a position where the light passes through the adhesive composition before the light reaches the portion of the battery which converts the light to the energy. The rubber (tetra) compound can also be used to connect solar cells to a substrate (such as a board or roof tile). In these cases, the rubber composition does not need to be transparent. Generally, the rubber composition exhibits improved mechanical properties superior to conventional rubber compositions. In an embodiment, the solar cell unit comprises a back electrode, a photovoltaic layer, a pole and a transparent top layer, wherein the composite layer of the invention is between the Φ electrode and the transparent top layer. As described above, the rubber slave of the composite material is a transparent rubber, and preferably the rubber is a polyoxymethylene rubber. The rubber composition can be used as a bonding layer or a bonding layer for reading, and, the top layer of the moon and the front electrode. Since the above-mentioned changes have been made from the mechanical scallops of Tu. . _ ^ ^ ^ ^, the adhesion and tear strength of the composites increase, and it is better for the 13b4 &#d month b battery soap element (in use). Resist the environment 134913.doc -24· 200922998 士i or /, other mechanical forces of the road. Therefore, the solar cell unit is 7 卩 θ plus, if the composite material of the present invention is transparent to visible light, and the inclusion band has a size in the visible wavelength (ie, between 4 GG nm and 800 nm) or exceeds The solar composition of the wavelength of the particulate rubber composition of the solar cell produces improved light yield and solar recovery compared to the early enthalpy of the battery. The solar cell comprising the back electrode, the photovoltaic layer, the front electrode and the transparent top layer has been Those familiar with the art are well known. Typically, the back electrode photovoltaic layer, the front electrode, and the transparent top layer are provided in layers of layers. A more detailed description of such solar cells can be found in European Patent No. 1 397 837 and European Patent! Detailed descriptions of the back electrode, the photovoltaic layer, the front electrode, and the transparent top layer are incorporated herein by reference. EXAMPLES In the experiments set forth below, a commercially available fatty acid blend (Kortacid® PH05) was used. This material is used in the state it receives. In addition to fatty acids, stabilized rosin is used. The stabilized rosin is prepared by melting Chinese rosin and heating it to 2351. During the melting period, 3.5% of Vultac®-2 (Arkema) was added with rosin weight. The molten rosin was stirred at 235 C for 15 hours, after which the resin was cooled for use. Preparation of layered double hydroxide 68.2 grams of magnesium oxide (z〇litho 40, purchased from Martin Marietta ^^1^士1^(:) and 43.6 grams of aluminum hydroxide (eight 1 丨 11? 505) In 840 grams of demineralized water and ground to an average particle size (d5 〇) of 25 microns. The slurry 134913.doc -25- 200922998 is fed to an oil-heated autoclave equipped with a high-speed stirrer and heated to 80 ° C. Then, within 15 minutes, the high pressure dad was added a mixture of 132 grams of Kortacid® PH05 and a 50/50 mixture of stabilized rosins prepared as above (by weight). The acid mixture was heated to 80 before the addition. After the acid addition, the autoclave was closed and heated to I 70. (: and kept at this temperature for a few hours. Then the autoclave was cooled to about 4 (TC and the resulting slurry was taken out. Then the slurry was taken at 2, rpm Centrifuge for about ίο minutes. Pour out the liquid and dry the solid in an oven at 8 rc under vacuum overnight. In the resulting LDH, 20 mol% charge balance anion oxygen chloride anion

Examples A and B First, LDH was mixed with natural rubber (§ cv) on a dual light mill at 4 GC to form a 50/50 masterbatch. The remaining mixing procedure in i 6 i Banbury with a load factor of 7〇% is as follows: - At the initial temperature of 6 (TC, the natural rubber is kneaded for a minute. - Add the 5 0/5 0 masterbatch And mix for 5 minutes - to sweep, 1 minute. The final temperature of the 'dumped' mixture is up to 14 〇t. After cooling, the vulcanized components are added to the two-roll mill. The final composition is shown in Table 1. 134913.doc -26- 200922998 Table 1 Ingredient A1) B1) Natural rubber SMR-CV 100 100 LDH 10 n-Cyclohexyl-2-benzothiazole sulfinamide 1.5 1.5 Sulfur 1.5 1.5 υ The amount of these ingredients is The parts per phr of rubber (phr) indicate that the A example is a comparative example, and the b example is an example of the present invention. According to 〖s 〇 6502:1999, at 15 〇. (: The Rheocord MDR2000E (with a curvature of 0.5 and a torque axis of 〇·5 Nm) was used to record the rheological curves of the samples for 3 minutes. The results of the measurements indicate that the composite of the A example has a much longer scorch time than the composite. B, the activation and/or acceleration of the vulcanization process of the composite B is remarkable.

Example C-G First, LDH was mixed with natural rubber (SMR cv) to form a 5〇/5〇 masterbatch. The remaining mixing procedure was performed in 1.6 1 Banbury with a load factor of 70% as follows: _ at an initial temperature of 60. (: Next, masticate the natural rubber for 丨 minutes. - Add the 50/50 masterbatch and mix for 5 minutes. _ Add the final amount - half of the carbon black and all the retarders, mix for 2 minutes. Add the rest of the All the other ingredients except the vulcanizing agent are mixed for 1 minute. - Scrape for 1 minute. - Dump, the final temperature of the mixture is up to 14 (rc. After cooling, 'the sulphurization is red, 夭The chemical damage was added to the two-roll mill. 134913.doc -27- 200922998 The compositions are shown in Table 2. Examples C, E and G are not in accordance with the invention. Examples D and F are in accordance with the invention. Table 2 Ingredient C1 ) D1) E1) F1) G1) Natural rubber SMR-CV 100 100 100 100 100 LDH 10 10 10 10 Carbon black HAF-N339 55 55 55 55 55 Incremental oil (Sunthene 4240) 8 8 8 8 8 Zinc oxide 3 3 3 stearic acid 2 2 2 2 2 N-(l,3-dimercaptobutyl)-N'-phenyl-p-phenylenediamine 2 2 2 2 2 2,2,4-tridecyl- 1,2-dihydroquinoline polymer 1 1 1 1 1 n-cyclohexyl-2-benzothiazole sulfinamide 1.5 1.5 1.5 1.5 1.5 Sulfur 1.5 1.5 1.5 1.5 1.5 O-phthalic anhydride 2 2

The amount of these ingredients is expressed in parts per hundred parts of rubber (phr). HK ϋ According to the procedure described in Example CG above, LDH is mixed with bromobutyl rubber (bromobutyl hydrazine 2) to 50/50 masterbatch. gum. The final composition is shown in Table 3. Examples Η and I are not in accordance with the present invention. Examples J and Κ are in accordance with the present invention. 134913.doc •28- 200922998 Table 3 Composition H1) I1) J1) K1) Bromobutyl X2 100 100 90 90 LDH 20 20 Carbon Black GPF-N666 60 60 60 60 Incremental Oil (Sunthene 4240) 8 8 8 8 Escorez 1102 (aliphatic hydrocarbon resin) 7 7 7 7 tackifying resin (SP 1068) 4 4 4 4 Magnesium oxide (Maglite DE) 0.15 0.15 0.15 Oxidation 1 1 1 Stearic acid 2 2 2 2 MBTS 1.2 1.2 1.2 1.2 Sulfur 0.5 0.5 0.5 0.5 υ The amount of these components is expressed in parts per hundred parts of rubber (phr). The standard test method for measuring the oxygen transmission rate of plastic film and sheet by Coulometric sensor (Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using t./ a Coulometric Sensor) (ASTM D3985) measures the gas permeability of the above-mentioned composite CK. The degree of crosslinking is measured from these rheological curves according to ISO 6502:1999. " The results show that when ZnO is replaced by LDH, the crosslink density is lowered, which gives greater flexibility. The gas permeability of the rubber is also reduced as opposed to what was originally expected from the low crosslink density. In other words, the replacement of ZnO by LDH results in greater flexibility and reduced gas permeability of the rubber. 134913.doc -29-

Claims (1)

200922998, the scope of patent application: a double composite material comprising a rubber, a sulfur-containing vulcanizing agent, a hydroxide-containing and/or β-anion as a layered double hydroxide of a charge-balanced anion, and less than 1.5 phr ΖηΟ. 2. As requested by Composite #, it contains Shi Xi Shao coupling agent. A composite material according to any one of items 1 to 2, wherein the rubber is selected from the group consisting of natural rubber, SBR, EPDM, halogenated butyl rubber, butadiene rubber, and polyoxyethylene rubber. A composite material according to any one of the preceding claims, wherein at least 1 mole % of the total amount of counter ions in the layered double hydroxide is a helium anion. "" 5. A cured composite material obtainable by curing a composite material as claimed in any of the items 丨 to 々. 6. The cured composite of claim 5, wherein the layered double hydroxide comprises a charge-balanced organic anion having a first functional group and a second functional group, and a part of the organic anion is neutralized by the second functional group. Chemically attached to rubber. a seeding composite material obtainable by curing the composite material of claim 2, wherein the coupling agent has at least one alkoxyalkyl group and at least one reactive group, at least one alkoxyalkyl group Chemically linked to the layered double argon oxide and at least one reactive group is chemically bonded to the rubber. 8. The composite material of the cured composite material according to any one of item 5 to 7 is a nano composite material. 134913.doc 200922998 9. A masterbatch comprising 3 Torr and 9 Torr by weight of the masterbatch. / 〇 rubber or cured rubber, 9 and 69% by weight of a layered double hydroxide containing hydroxide and/or an organic anion as a charge-balancing anion, and 1 and 20% by weight of a sulfur-containing vulcanizing agent. 1 〇 A rubber-free mixture which is a mixture of a sulfur-containing vulcanizing agent and a layered double hydroxide containing a hydroxide and/or an organic ion as a charge-balancing anion. The method of preparing the composite material 11 according to any one of claims 1 to 4, comprising the steps of: a1) layered double hydroxide mixed with the first solvent as appropriate, and comprising the polymer or polymers and optionally The rubber of the two solvent contacts or a2) contacts the layered double hydroxide optionally mixed with the first solvent with a composition comprising one or more rubber monomers and optionally a second solvent and polymerizes the monomers Forming a rubber; b) c) contacting the sulfur-containing vulcanizing agent with the rubber or the monomers before, during or after the step or step a2); and in step a), a2), or b) The first and/or second solvent is removed as appropriate during or after the process. 12. The use of a composite material as claimed in claims 1 to 4 to 8 and/or the use of a cured composite material as claimed in claim 5 in a tire. 134913.doc 200922998 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please disclose the best indication of the characteristics of the invention. Chemical formula: (none) ( 134913.doc