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    • 专利摘要:
    RUBBER MIXTURES The invention relates to mixtures of rubbers comprising: (A) at least one rubber selected from the group of ethylene-propylene-diene copolymer (EPDM), ethylene-propylene copolymer (EPM), chloroprene rubber (CR ), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (CIIR), chlorosulfonyl polyethylene (CSM), ethylene-vinyl acetate copolymer (EAM), alkyl acrylate copolymer (ACM), polyurethane polyester ( AU), polyether polyurethane (EU), bromo-isobutene-isoprene (bromobutyl) rubber (BIIR), polychloro-trifluorethylene (CFM), isobutene-isoprene rubber (butyl rubber, IIR), isobutene rubber (IM), polyisoprene (IR ), thermoplastic polyurethane polyester (YAU), thermoplastic polyurethane polyether (YEU), silicone rubber with methyl groups on the polymer chain (MQ), hydrogenated acrylonitrile-butadiene rubber (HNBR), acrylonitrile-butadiene rubber (NBR) or rubber acrylonitrile-butadiene carboxy (XNBR), (B) at least one oxide charge, and (C) at least one azodicarbamide containing silicon of general formula I (R1) 3-a (R2) aSi-R'-NH-C (O) -N = NC (O) -NH-R'-Si (R1) 3-a (R2) to (I). The rubber mixture is produced by mixing at least one rubber, at least one oxide charge, and at least one azodicarbamide containing silicon of general formula I. This mixture can be used for (...).
    公开号:BR102012006916B1
    申请号:R102012006916-4
    申请日:2012-03-28
    公开日:2020-10-13
    发明作者:Anke Blume；Oliver Klockmann；Dörte Kellerhof
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    [0001] The invention relates to mixtures of rubbers, their production, and their use.
    [0002] DE 102010003387.1 describes a process for the production of azodicarbamides containing silicon by reaction of R3-X1- C (O) -N = NC (O) -X1-R4 and (R1) 3-a (R2) aSi -R'-NH2.
    [0003] DE 2704506 describes compounds of General Formula Y-X-CO-N = N-CO-X1-Z and their use in filler-containing rubber compounds.
    [0004] US 20090234066 A1, moreover, describes compounds of General Formula A-CO-N = N-CO-Z-G, which are used together with sulfur containing isoprene rubber.
    [0005] US 20090186961 A1 describes compounds of General Formula A-CO-N = N-CO-Z-G, which are used together with isoprene rubber coating agents.
    [0006] A disadvantage of known rubber mixtures, comprising organo (alkyl polyethersilanes), is poor dynamic behavior, including a high loss of hysteresis.
    [0007] It is an object of the invention to provide rubber mixtures which exhibit improved dynamic behavior, including a noticeable low loss of hysteresis after vulcanization.
    [0008] The invention provides mixtures of rubbers characterized by the fact that they comprise: (A) at least one rubber selected from the group of ethylene-propylene-diene copolymer (EPDM), ethylene-propylene copolymer (EPM) , chloroprene rubber (CR), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (CIIR), chlorosulfonyl polyethylene (CSM), ethylene-vinyl acetate copolymer (EAM), copolymer of acrylate acrylate alkyl (ACM), polyurethane polyester (AU), polyurethane polyurethane (EU), bromo-isobutene-isoprene (bromobutyl) rubber (BIIR), polychloro-trifluorethylene (CFM), isobutane-isoprene rubber (butyl rubber, IIR ), isobutene rubber (IM), polyisoprene (IR), thermoplastic polyurethane polyester (YAU), thermoplastic polyurethane polyether (YEU), silicone rubber with methyl groups on the polymer chain (MQ), hydrogen acrylonitrile-butadiene rubber (HNBR), acrylonitrile-butadiene rubber (NBR) or rubber of acrylonitrile-butadiene carboxylated (XNBR), preferably ethylene-propylene-diene copolymer (EPDM), (B) at least one oxide charge, and (C) at least one azodicarbamide containing silicon of general formula I (R1) 3- a (R2) aSi-R1-NH-C (O) -N = NC (O) -NH-R1-Si (R1) 3-a (R2) to (I), where,
    [0009] R1 are, independently of one another, C1-C18-, preferably C1-C10-, more preferably, C1-C6-, even more preferably C1-, alkyl groups, C5-C18-, preferably C6-, groups cycloalkyl, or C6-C18-aryl groups, preferably substituted or unsubstituted phenyl,
    [00010] R2 is, independently of one another, an -OH group, a substituted or unsubstituted C1-C18-alkoxy group, preferably CH3-O-, C2H5-O-, C3H7-O-, C12H25-O- , C14H29-O-, C16H33-O-, C18H37-O-, more preferably, C2H5-O-, a C5-C18-cycloalkoxy group, or an alkyl polyether group O (CH2-CH2-O) n-R3 or O (CH (CH3) -CH2-O) n-R3, where the mean of n is 1 to 18 and,
    [00011] R3 is mutually and independently a monovalent branched or unbranched, saturated or unsaturated C1-C32 hydrocarbon chain,
    [00012] R1 is a divalent branched or unbranched, saturated or unsaturated, aliphatic, aromatic or aliphatic / aromatic mixed C1-C30 hydrocarbon, preferably C1-C20 hydrocarbon -, more preferably, C1-C10 hydrocarbon -, still more more preferably, C1-C7 - hydrocarbon, which can be substituted with F-, Cl-, Br-, I-, -CN or HS-, if necessary, a = 1.2 or 3 independently of each other.
    [00013] R1 can preferably be,

    [00014] Azodicarbamide containing silicon of General Formula I may preferably be: (EtO) 3Si-CH2-NH-CO-N = N-CO-NH-CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2- NH-CO-N = N-CO-NH-CH2-CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2 - Si (OEt) 3, (EtO) 3Si-CH2-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-CH2-Si (OEt) 3, (EtO) 3Si - (CH2) ii-NH-CO-N = N-CO-NH- (CH2) ii-Si (OEt) 3, (EtO) 3Si- (CH2) i2-NH-CO-N = N-CO-NH - (CH2) i2-Si (OEt) 3, (EtO) 3Si-CH2CH (CH3) CH2-NH-CO-N = N-CO-NH-CH2CH (CH3) CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-C6H4-CH2-NH-CO-N = N-CO-NH-CH2-C6H4-CH2-CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-C6H4-NH-CO -N = N-CO-NH-C6H4-CH2- CH2-Si (OEt) 3, (MeO) 3Si-CH2-NH-CO-N = N-CO-NH-CH2-Si (OMe) 3, (MeO ) 3Si-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-Si (OMe) 3, (MeO) 3Si-CH2-CH2-CH2-NH-CO-N = N-CO- NH-CH2-CH2-CH2-Si (OMe) 3, (MeO) 3Si-CH2-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-CH2-Si (OMe ) 3, (MeO) 3Si- (CH2) ii-NH-CO-N = N-CO-NH- (CH2) ii-Si (OMe) 3, (MeO) 3Si- (CH2) i2-NH-CO- N = N-CO-NH- (CH2) i2-Si (OMe) 3, (MeO) 3Si-CH2CH (CH3) CH2-NH-CO-N = N-CO-NH-CH2CH (CH3) CH2-Si ( OMe) 3, (MeO ) 3Si-CH2-CH2-C6H4-CH2-NH-CO-N = N-CO-NH-CH2-C6H4-CH2-CH2-Si (OMe) 3> (MeO) 3Si-CH2-CH2-C6H4-NH- CO-N = N-CO-NH-C6H4-CH2-CH2-Si (OMe) 3, (EtO) (RO) 2Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2- CH2- CH2-Si (EtO) (RO) 2or (RO) (EtO) 2Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2- Si (RO) (EtO ) 2 with Me = methyl, Et = ethyl and R = CI3H27 (OCH2CH2) S.
    [00015] Azodicarbamide containing silicon of formula I (R1) 3-a (R2) aSi-R1-NH-C (O) -N = NC (O) -NH-R1-Si (R1) 3-a (R2 ) (I) can be produced by reacting azo-biscarboxy compounds of General Formula II R5-X1-C (O) -N = NC (O) -X1-R4 (II) with aminosilanes of General Formula III ( R1) 3-a (R2) aSÍ-R'-NH2 (III), where
    [00016] R1, R2, R1 and a have the same meaning as mentioned above and,
    [00017] X1 are mutually and independently O, NH or N-A1, where A1 is C1-C12-alkyl group or aryl group and
    [00018] R4 and R5 are, mutually and independently, an H group, a C1-C18-alkyl group, a benzyl group (-CH2-C6H5) or an alkyl polyether group (CH2-CH2-O) m-R5 or (CH (CH3) -CH2-O) m-R5, where the average of m is from 1 to 18. The reaction conditions are described inDE 10 2010 003 387.1.
    [00019] General Formula III aminosilanes with R2 = O (CH2-CH2-O) n-R3 or O (CH (CH3) -CH2-O) n-R3 alkyl group can be produced by transesterification of aminosilanes of General Formula III with R2 = -OH, a substituted or unsubstituted C1-C18-alkoxy group or a C5-C18-cycloalkoxy group with HO (CH2-CH2-O) n-R3 or HO (CH (CH3) - CH2-O) n-R3. The reaction conditions of transesterification are, for example, described inEP 1 285 926 A1.
    [00020] Azodicarbamide containing Formula I silicon may alternatively be produced by transesterification of Formula I silicon containing azide dicarbamides from DE 10 2010 003 387.1. The reaction conditions of transesterification are, for example, described inEP 1 285 926 A1.
    [00021] Azodicarbamide containing silicon may be a mixture composed of azodicarbamides containing silicon of General Formula I.
    [00022] The rubber mixtures of the invention may additionally contain oligomers, which are generated by hydrolysis or condensation of azodicarbamides containing General Formula I silicon.
    [00023] Azodicarbamide containing silicon of General Formula I can be added in pure form to the mixing process, or added in an absorbed form in an inert organic or inorganic vehicle, or else, a pre-reacted form with an organic vehicle or inorganic. Preferred carrier materials can be precipitated or smoked silicas, waxes, thermoplastics, natural or synthetic silicates, natural or synthetic oxides, such as aluminum oxide, or smokes. Azodicarbamide containing silicon of General Formula I can also be added to the mixing process in a pre-reacted form with the oxide charge that must be used.
    [00024] Preferred waxes can be waxes with melting points, melting bands, or softening bands from 50 ° to 200 ° C, preferably from 70 ° to 180 ° C, particularly and preferably, from 90 ° to 150 ° C , very particularly and preferably, from 100 ° to 120 ° C.
    [00025] The waxes used can be olefinic waxes.
    [00026] Waxes used may contain saturated and unsaturated hydrocarbon chains.
    [00027] The waxes used may comprise polymers or oligomers, preferably, SBR emulsion or / and SBR solution.
    [00028] The waxes used may comprise long chain alkanes or / and long chain carboxylic acids.
    [00029] The waxes used may comprise ethylene vinyl acetate and / or polyvinyl alcohols.
    [00030] Azodicarbamide containing General Formula I silicon can be added to the mixing process in a form physically mixed with an organic substance, or physically mixed with a mixture of organic substance.
    [00031] The organic substance or mixture of organic substance can comprise polymers or oligomers.
    [00032] Polymers or oligomers can be polymers or oligomers containing hetero atoms, for example, ethylene-vinyl alcohol or / and polyvinyl alcohols.
    [00033] The following oxide charges can be used for the rubber mixtures of the invention: - Amorphous silicas, prepared by example via precipitation of silicate solutions (precipitated silicas) or flame hydrolysis of silicon halides (smoked silicas). The specific surface areas of amorphous silicas can be from 5 to 1,000 m2 / g, preferably from 20 to 400 m2 / g (BET surface area) and their primary particle sizes can be from 10 to 400 nm. Silicas may be appropriate, also taking the form of mixed oxides with other metal oxides, such as Al oxides, Mg oxides, Ca oxides, Ba oxides, Zn oxides and titanium oxides. - Synthetic silicates, such as aluminum silicate or alkaline earth metal silicates, such as magnesium silicate or calcium silicate. The BET surface areas of synthetic silicates can be from 20 to 400 m2 / g and their primary particle diameters can be from 10 to 400 nm. - Synthetic or natural aluminum oxides and synthetic or natural aluminum hydroxides. - Natural silicates, such as kaolin and other naturally occurring silicas. - Fiberglass and fiberglass products (mats, filaments) or glass microspheres.
    [00034] It may be preferable to use amorphous silicas prepared via precipitation of silicate solutions (precipitated silicas) with BET surface areas of 20 to 400 m2 / g. The amounts that can be used of the amorphous silicas are from 5 to 150 parts by weight, based on each case, in 100 parts of rubber (phr).
    [00035] The mentioned loads can be used separately or in a mixture.
    [00036] In a particularly preferred embodiment, rubber mixtures may comprise from 10 to 150 parts by weight of oxide fillers, if appropriate, together with from 0 to 100 parts by weight of carbon black, and also from 1 to 20 parts by weight of azodi-carbamide containing silicon of General Formula I, based on each case in 100 parts by weight of rubber.
    [00037] Additional fillers that can be used are carbon black, such as flame black, furnace black, gas black, or thermal black, or synthetic or natural calcium carbonates, such as precipitated calcium carbonate. The BET surface area of carbon blacks can be from 20 to 200 m2 / g. Carbon blacks may be appropriate, they may also contain heteroatoms, such as Si.
    [00038] The preferred material for preparing inventive rubber mixtures is ethylene-propylene-diene copolymer (EPDM) which can contain a third monomer (ethylene-propylene terpolymer).
    [00039] Mixtures of inventive rubbers may additionally contain natural rubbers or synthetic rubbers. Preferred synthetic rubbers are described by way of example inW. Hofmann, Kautschuktechnologie [Rubber technology], Genter Verlag, Stuttgart 1980. These comprise inter alia: - polybutadiene (BR); - polyisoprene (IR); -styrene-butadiene (SBR) polymers, such as SBR emulsion (E-SBR) or SBR solution (S-SBR). The styrene-butadiene copolymers can have a styrene content of 1 to 60% by weight, preferably from 2 to 50% by weight, particularly and preferably, from 10 to 40% by weight, very particularly and preferably, from 15 to 35% by weight; - chloroprene (CR); - isobutylene-isoprene (HR) copolymers; - butadiene-acrylonitrile copolymers whose contents of acrylonitrile are from 5 to 60% by weight, preferably from 10 to 50% by weight (NBR), particularly and preferably from 10 to 45% by weight (NBR), very particularly and preferably, from 19 to 45% by weight (NBR); - partially hydrogenated or fully hydrogenated (HNBR) NBR rubber; - aforementioned rubbers that also have functional groups, for example, carboxy groups, silanol groups or epoxy groups, for example, epoxidized NR, NBR with carboxy function or SBR with silanol function (-SiOH) or with silylalkoxy function (-Si-OR ); or a mixture of these rubbers.
    [00040] The inventive rubber mixtures can comprise other rubber auxiliaries, such as reaction accelerators, anti-oxidants, thermal stabilizers, stabilizers against the action of light, anti-zonants, processing aids, plasticizers, tackifiers, blowing agents , dyes, pigments, waxes, extenders, organic acids, retardants, metal oxides, and also activators, such as triethanolamine or hexanotriol.
    [00041] The rubber mixture of the invention may additionally comprise silanes. Additional silanes that can be added to the rubber mixtures of the invention are ethoxysilyl groups containing mercapto-organylsilanes, or / and ethoxysilyl groups containing thiocyanate-organylsilanes, or / and ethoxysilyl groups containing mercapto-organylsilanes, or / and ethoxysilyl groups containing alkoxysilanes polysulfides.
    [00042] Additional silanes that can be added to the rubber mixtures of the invention are mercapto-organyl (alkoxysilanes) having groups CsHi7-O-, C10H21-O-, C12H25-O-, C14H29-O-, C16H33-O-, or C18H37-O- on silicon.
    [00043] Additional silanes that can be added to the rubber mixtures of the invention are thiocyanate-organyl (alkoxysilanes) having groups CeHi7-O-, C10H21-O-, C12H25-O-, C14H29-O-, C16H33-O-, or C18H37-O- on silicon.
    [00044] Additional silanes that can be added to the rubber mixtures of the invention are blocked mercapto-organyl (alkoxysilanes) having groups CSH-RO-, C10H21-O-, C12H25-O-, C14H29-O-, C16H33-O-, C16H33-O-, or C18H37-O- on silicon.
    [00045] Additional silanes that can be added to the rubber mixtures of the invention are blocked mercapto-organyl (alkoxysilanes) featuring difunctional alcohols (diols) on silicon (e.g., NXT LowV or NXT Ultra-LowV from General Electric).
    [00046] Additional silanes that can be added to the rubber mixtures of the invention are polysulfidic alkoxysilanes having CsHi7-O-, C10H21-O-, C12H25-O-, C14H29-O-, C16H33-O-, or C18H37-O- groups in silicon.
    [00047] Additional silanes that can be added to the rubber mixtures of the invention are polysulfidic alkoxysilanes of formulas: EtO-Si (Me) 2-CH2-CH2-CH2-S2-CH2-CH2-CH2-Si (Me) 2 (OEt ), EtO-Si (Me) 2-CH2-CH2-CH2-S3-CH2-CH2-CH2-Si (Me) 2 (OEt), or EtO-Si (Me) 2-CH2-CH2-CH2-S4- CH2-CH2-CH2-Si (Me) 2 (OEt).
    [00048] Additional silanes that can be added to the rubber mixtures of the invention are 3-mercaptopropyl (triethoxysilane) (eg Si 263 from Evonik Degussa GmbH), 3-thiocyanatopropyl (triethoxysilane) (eg Si 264 from Evonik De- gussa GmbH), Bis (triethoxysilylpropyl) polysulfide (for example, Si 69 from Evonik Degussa GmbH), Bis disulfide (triethoxysilylpropyl) (for example, Si 266 from Evonik Degussa GmbH).
    [00049] Additional silanes that can be added to the rubber mixtures of the invention are mercapto-organylsilanes containing alkylpolyether alcohol (such as Si 363 from Evonik Degussa GmbH), or / and thiocyanate-organylsilanes containing alkylpolyether alcohol, or / and blocked mercapto-organylsilanes containing alkylpolyether alcohol, or / and polysulfidic silanes containing alkylpolyether alcohol.
    [00050] It may be desirable for reasons of economy or rubber technology to minimize the necessary or desirable proportion of additional silanes.
    [00051] The amounts used of the rubber auxiliaries can be known quantities, depending inter alia on the intended purpose. As a function of the processing aid used, conventional amounts may be amounts from 0.001 to 50% by weight, preferably from 0.001 to 30% by weight, particularly and preferably, from 0.01 to 30% by weight, very particularly and preferably , from 0.1 to 30% by weight, based on rubber (phr).
    [00052] The rubber mixtures of the invention can be mixtures of vulcanizable sulfur rubbers.
    [00053] The rubber mixtures of the invention can be mixtures of peroxidically crosslinkable rubbers.
    [00054] Crosslinking agents that can be used are sulfur substances or sulfur donors. The amounts of sulfur used can be from 0.1 to 10% by weight, preferably from 0.1 to 5% by weight, based on rubber.
    [00055] Azodicarbamide containing General Formula I silicon can be used as an adhesion promoter between inorganic materials (for example, glass beads, glass shards, glass surfaces, glass fibers, metals, oxide charges, silica) and polymers organic (for example, thermosets, thermoplastics, elastomers); or as a crosslinking agent and surface modifiers for oxidic surfaces. Azodicarbamide containing silicon of General Formula I can be used as coupling reagents in filler rubber mixtures, one example being seals.
    [00056] It may be desirable for reasons of savings or rubber technology to minimize the necessary or desirable proportion of rubber auxiliaries.
    [00057] The rubber mixtures of the invention may additionally comprise vulcanization accelerators.
    [00058] Amounts that can be used for vulcanization accelerators are 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the rubber used. The rubber mixtures of the invention may comprise: (D) a thiuram sulfide accelerator and / or a carbamate accelerator and / or a mercaptobenzothiazole and / or a dithiophosphate and / or the corresponding zinc salts, (E) if appropriate, a nitrogen-containing co-activator, and (F) if appropriate, additional rubber auxiliaries.
    [00059] The invention additionally provides a process for producing the rubber mixtures of the invention, a process which is characterized by the fact that the process comprises mixing at least one rubber selected from the group of ethylene-propylene-diene copolymer (EPDM) , ethylene-propylene (EPM) copolymer, chloroprene rubber (CR), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (ClIR), polyethylene chlorosulfonyl (CSM), ethylene-vinyl acetate copolymer ( EAM), alkyl acrylate (ACM) copolymer, polyurethane polyester (AU), polyurethane polyether (EU), bromo-isobutene-isoprene rubber (bromobutyl) (BIIR), polychlorotrifluorethylene (CFM) rubber, isobutene-isoprene rubber (butyl rubber, IIR), isobutene rubber (IM), polyisoprene (IR), thermoplastic polyurethane polyester (YAU), thermoplastic polyurethane polyether (YEU), silicone rubber with methyl groups in the polymer chain (MQ), rubber acrylic hydrogenated nitrile-butadiene (HNBR), acrylonitrile-butadiene rubber (NBR) or carboxylated acrylonitrile-butadiene rubber (XNBR), preferably ethylene-propylene-diene copolymer (EPDM), at least one oxidizing charge, and at least one azodicarbamide containing General Formula I silicon.
    [00060] The process of the invention can be carried out at temperatures> 25 ° C.
    [00061] The process of the invention can be carried out in the temperature range of 80 ° C to 220 ° C, preferably from 100 ° C to 200 ° C, particularly and preferably, from 110 ° C to 180 ° C.
    [00062] The process can be carried out continuously or discontinuously (by batch).
    [00063] The addition of the azodicarbamide containing silicon of General Formula I, and also the addition of fillers, can occur when the temperatures of the composition are from 100 to 220 ° C. However, it can also occur at lower temperatures, from 40 to 100 ° C, for example, together with additional rubber auxiliaries.
    [00064] The combination of rubbers with filler and, if appropriate, with rubber auxiliaries and with azodicarbamide containing General Formula I silicon can occur in, or in conventional mixing sets, such as rollers, internal mixers, and extruders of mixture. These mixtures of rubbers can usually be produced in internal mixers, starting with one or more successive thermomechanical mixing stages in which rubbers, filler, azodicarbamide containing Formula I silicon and rubber auxiliaries are incorporated through mixing, from 100 to 180 ° C. The addition sequence and addition addition of the individual components here can have a decisive effect on the properties resulting from the mixture. The crosslinking chemicals can usually be mixed in an internal mixer or on a roller, under 40 to 110 ° C with the rubber mixture thus obtained, and processed to provide what is known as a crude mixture for subsequent process steps , for example, formation and vulcanization.
    [00065] Vulcanization of the rubber mixtures of the invention can occur at temperatures of 80 to 220 ° C, preferably from 130 to 190 ° C, if appropriate, under a pressure of 1 MPa to 20 MPa (10 to 200 bar).
    [00066] The rubber mixtures of the invention can be used for the production of seals, vibrators, channels for sliding glass, radiators, garden hoses and appliances, pipes, windshield washer, belts, electrical insulation, and conical edges from loudspeakers, at electrical cable junctions, contours, external wire covers, roofing membranes, geomembranes, mechanical rubber products, plastic impact modifications, thermoplastics, vulcanized products and many other applications. The rubber mixtures of the invention can be used for weather seals on all vehicles. These include door seals, window seals, trunk seals and hood seals.
    [00067] The rubber mixtures of the invention can be used in hoses of the cooling system circuit in an automobile. In addition, they can be used as turbocharging air lines in turbocharged engines.
    [00068] The invention additionally provides moldings obtainable from the rubber mixture of the invention, via vulcanization.
    [00069] The rubber mixtures of the invention have the advantage of improved dynamic behavior with a noticeable low loss of hysteresis. Examples:
    [00070] The following compounds are used in rubber mixtures: Compounds for comparative examples: Compound 1: Corax® N 550 carbon black from Evonik Carbon Black GmbH. Compound 2: Bis disulfide (triethoxysilylpropyl) is obtainable as Si 266 ® by Evonik Degussa GmbH. Compound for the example of the invention: Compound 3: (EtO) (RO) 2Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-Si ( EtO) (RO) 2 with Et = ethyl and R = CI3H27 (OCH2CH2) 5 prepared by a method based on the process described inDE 10 2010 003 387.1:
    [00071] Under argon, 100 g of 3-aminopropyl (triethoxysilane) (451 mmoles) and ethoxylated isotridecanol (903 mmoles) are mixed and heated to 130 ° C. Under vacuum (40 kPa abs.), Ethanol (903 mmoles) is completely distilled. The product is dissolved in n-pentane and cooled to 0 ° C. With stirring, DIAD (Diisopropylazodicarboxylate; molar ratio 1: 2 DIAD / silane) is dosed in the solution while maintaining the temperature between -5 ° C and 5 ° C. After that, the solution is stirred for 30 minutes at 0 ° C, and then for 180 minutes at room temperature. Volatiles (pentane, isopropanol) are removed on a rotary evaporator under vacuum (up to 0.6 kPa abs.).
    [00072] The product is obtained in> 99% yield as a bright red viscous liquid with a target substance purity> 85 mol% (NMR). Example 1: Mixtures of rubbers
    [00073] The main mix specification used for rubber mixtures is set out in Table 1 below. The phr unit used is weight proportions, based on 100 parts of the raw rubber used.
    [00074] The general process for the production of mixtures of rubbers and their vulcanized products is described in the book: “Rubber Technology Handbook ', W. Hofmann, Hanser Verlag 1994. Table 1: Main specification of mixture

    [00075] Buna® EP G 5455 polymer is an ethylene-propylene terpolymer with an unsaturation medium (ENB content = 4.3) containing 50 phr of Lanxess paraffinic oil. Its Mooney viscosity (UML (1 + 4) 125 ° C) is 46.
    [00076] ULTRASIL® 7000 GR is a highly dispersible silica from Evonik Degussa GmbH, its BET surface area being 170 m2 / g.
    [00077] Lipoxol 4000 from Saso / is a polyethylene glycol 4000, Sunpar 150 from Holly Corporation is a paraffinic oil, Vulkacit Mercapto C from Lanxess is 2-mercaptobenzothiazole (MBT), Perkacit TBzTD (tetrabenziltiuramo tetrasulfide) is a product of Flexs NV, Rhenocure TP / S from RheinChemie is 67% zinc dialkylthyldithiophosphate bound to 33% silica.
    [00078] Rubber mixtures are produced in an internal mixer according to the mix specification in table 2. Table 2


    [00079] Table 3 intersperses the rubber testing methods.

    [00080] Table 4 shows the results of the test compounds. Table 4

    [00081] As can be seen, from the data in table 4, mixture 3 containing an azodicarbamide containing silicon of General Formula I leads to an improved dynamic behavior enhanced with a significant lower hysteresis loss. Mooney pre-vulcanization is improved compared to the carbon black compound. Mixture 3 containing a Formula I azodicarbamide also shows an improvement in reinforcement with an improved tensile strength, a modulus greater than 500% and an elongation at break at a high level.
    权利要求:
    Claims (12)
    [0001]
    1. Rubber mixture, characterized by the fact that it comprises: (A) at least one rubber selected from the group of ethylene-propylene-diene copolymer (EPDM), ethylene-propylene copolymer (EPM), chloroprene rubber (CR) , chloropolyethylene (CM), chloro-isobutene-isoprene rubber (chlorobutyl) (CIIR), chlorosulfonyl polyethylene (CSM) copolymer, ethylene vinyl acetate (EAM) copolymer, alkyl acrylate copolymer (ACM), polyester polyurethane (AU), polyurethane polyurethane (EU), polyurethane polyurethane rubber (EU), bromo-isobutene-isoprene (bromobutyl) rubber (BlIR), polychlorinated fluoroethylene (CFM), isobutene-isoprene rubber (butyl rubber, IIR ), isobutene rubber (IM), thermoplastic polyester polyurethane (YAU), thermoplastic polyether polyurethane (YEU), silicone rubber with methyl groups in the polymer chain (MQ), hydrogenated acrylonitrile-butadiene rubber (HNBR), rubber acrylonitrile-butadiene (NBR) or acrylic rubber carboxylated itrila-butadiene (XNBR), (B) at least one oxidized filler, and (C) at least one silicone containing azodicarbamide of General Formula (I) (R1) 3-a (R2) aSi-Rl-NH- C (O) -N = NC (O) -NH-R1-Si (R1) 3-a (R2) to (I), in which R1 are independent of each other substituted or of unsubstituted C1 -C8-alkyl groups , Cs-Cis-cycloalkyl groups, or C6-C18-aryl groups, R2 is independent of each other, -OH one, a substituted or unsubstituted C1 group-Cis-alkoxy group, a C5-C18-cycloalkoxy group, or one alkyl polyether group O (CH2-CH2-O) n-R3 or O (CH (CH3) -CH2-O) n-R3, the mean of n being 1 to 18 and R3 independently representing a mutually branched or unbranched , saturated or unsaturated monovalent C1-C32 hydrocarbon chain, R1 is a mixed aliphatic / aromatic C1-C30 hydrocarbon, aliphatic, branched or unbranched, saturated or unbranched, which can be replaced by F, Cl, Br , I, CN or HS, if necessary, a = 1,2 or 3, independently of each other.
    [0002]
    2. Rubber mixture, according to claim 1, characterized by the fact that the rubber is ethylene-propylene-diene copolymer.
    [0003]
    3. Rubber mixture, according to claim 1, characterized by the fact that it contains other polymers, such as natural rubber or synthetic rubber.
    [0004]
    4. Rubber mixture according to claim 1, characterized by the fact that azodicarbamide containing silicon is a mixture composed of azodicarbamides containing silicon of General Formula I.
    [0005]
    5. Rubber mixture, according to claim 1, characterized by the fact that the azodicarbamide containing silicon of the General Formula I was absorbed in an inert organic or inorganic vehicle.
    [0006]
    6. Rubber mixture according to claim 1, characterized by the fact that it comprises an additional silane.
    [0007]
    7. Rubber mixture according to claim 1, characterized by the fact that it comprises (D) a tiuram sulfide accelerator and / or a carbamate accelerator and / or a mercapto-benzothiazole and / or a dithophosphate and / or the corresponding zinc salts.
    [0008]
    8. Rubber mixture according to claim 7, characterized by the fact that it comprises (E) a nitrogen-containing co-activator.
    [0009]
    9. Rubber mixture, according to claim 1, characterized by the fact that it contains preferably chemical compounds of General Formula I: (EtO) 3Si-CH2-NH-CO-N = N-CO-NH-CH2-Si ( OEt) 3, (EtO) 3Si-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-CH2-NH-CO- N = N-CO-NH-CH2-CH2-CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2 -CH2-Si (OEt) 3, (EtO) 3Si- (CH2) ii-NH-CO-N = N-CO-NH- (CH2) ii-Si (OEt) 3, (EtO) 3Si- (CH2) i2-NH-CO-N = N-CO-NH- (CH2) i2-Si (OEt) 3, (EtO) 3Si-CH2CH (CH3) CH2-NH-CO-N = N-CO-NH-CH2CH ( CH3) CH2-Si (OEt) 3, (EtO) 3Si-CH2-CH2-C6H4-CH2-NH-CO-N = N-CO-NH-CH2-C6H4-CH2-CH2-Si (OEt) 3, ( EtO) 3Si-CH2-CH2-C6H4-NH-CO-N = N-CO-NH-C6H4-CH2-CH2-Si (OEt) 3, (MeO) 3Si-CH2-NH-CO-N = N-CO -NH-CH2-Si (OMe) 3, (MeO) 3Si-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2- Si (OMe) 3, (MeO) 3Si-CH2-CH2 -CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-Si (OMe) 3, (MeO) 3Si-CH2-CH2-CH2-CH2-NH-CO-N = N-CO- NH-CH2- CH2-CH2-CH2-Si (OMe) 3, (MeO) 3Si- (CH2) ii-NH-CO-N = N-CO-NH- (CH2) ii-Si (OMe) 3, ( MeO) 3Si- (CH2) i2-NH-CO-N = N-CO-NH- (CH2) i2-Si (OMe) 3, (Me O) 3Si-CH2CH (CH3) CH2-NH-CO-N = N-CO-NH-CH2CH (CH3) CH2-Si (OMe) 3, (MeO) 3Si-CH2-CH2-C6H4-CH2-NH-CO -N = N-CO-NH-CH2- CeH4-CH2-CH2-Si (OMe) 3 (MeO) 3Si-CH2-CH2-C6H4-NH-CO-N = N-CO-NH-C6H4-CH2- CH2 -Si (OMe) 3, (EtO) (RO) 2Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-Si (EtO) (RO) 2, (RO ) (EtO) 2Si-CH2-CH2-CH2-NH-CO-N = N-CO-NH-CH2-CH2-CH2-Si (RO) (EtO) 2 with Me = methyl, Et = ethyl and R = Ci3H27 (OCH2CH2) s-
    [0010]
    10. Process for producing rubber mixtures, as defined in any one of claims 1 to 9, characterized by the fact that it comprises mixing at least one rubber selected from the group of ethylene-propylene-diene copolymer (EPDM), ethylene copolymer -propylene (EPM), chloroprene rubber (CR), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (CIIR), chlorosulfonyl polyethylene (CSM), ethylene-vinyl acetate (EAM) copolymer, copolymer alkyl acrylate (ACM), polyester polyurethane (AU), polyurethane polyurethane (EU), polyurethane polyurethane rubber (EU), bromo-isobutene-isoprene rubber (bromobutyl)), polychloro-trifluoroethylene (CFM), isobutene-isoprene rubber (butyl rubber, IIR), isobutene rubber (IM), thermoplastic polyester polyurethane (YAU), thermoplastic polyether polyurethane (YEU), silicone rubber with methyl groups in the polymer chain (MQ), hydrogenated acrylonitrile-butadiene rubber (HNB R), acrylonitrile-butadiene rubber (NBR) or carboxylated acrylonitrile-butadiene rubber (XNBR), preferably ethylene-propylene-diene copolymer (EPDM), at least one oxidative filler and at least an azodicarbamide containing silicon of General Formula I.
    [0011]
    11. Use of rubber mixtures, as defined in any of claims 1 to 9, characterized by the fact that it is for the production of moldings.
    [0012]
    12. Use of rubber mixtures, as defined in any one of claims 1 to 9, characterized by the fact that it is in seals, seals, door seals, window seals, trunk seals, trunk seals hood, vibrators, glass channels, radiators, hoses, garden and appliance hoses, pipes, washers, belts, electrical insulation, speaker cone edges, electrical cable connections, profiles, outer wire jacket, roof membranes , geomembranes, pneumatic spring systems, roller covers, conveyor belts, mechanical rubber products, mechanical impact modifications, thermoplastic, cooling system circuit hoses and charge air pipes in turbocharged engines.
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    同族专利:
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    PL2508559T3|2014-04-30|
    JP2012214758A|2012-11-08|
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    法律状态:
    2013-07-23| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-10-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11160838.6|2011-04-01|
    EP11160838.6A|EP2508559B1|2011-04-01|2011-04-01|Rubber mixtures|
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