Amine derivatives as rubber additives

Abstract

This invention relates to the use of amine derivatives as rubber additives, with the aim of improving vehicle tire performance.

Description

[0001] This invention relates to the use of various amine derivatives as rubber additives, with the aim of improving vehicle tire performance.

[0002] Modern vehicle tires face higher performance requirements, especially in terms of sustainability. In particular, they require low rolling resistance to reduce fuel consumption and related emissions, as well as high wear resistance to reduce tire wear emissions into the environment and extend tire life, while maintaining the tire's grip on the ground under different conditions (such as temperature, weather conditions, and road conditions).

[0003] To improve these properties, tire rubber compounds can contain various fillers and vulcanization accelerators. Fillers are typically inorganic materials such as carbon black, silicates, or zinc oxide, while rubber is a non-polar polymer; therefore, due to the difference in polarity, the miscibility and compatibility of these components are often poor. Other additives, such as vulcanization accelerators and activators, antioxidants, and plasticizers, need to be uniformly distributed within the rubber to ensure they exert their effects evenly.

[0004] Therefore, there is a need for an additive that allows fillers (such as carbon black, silicates, or zinc oxide) and other additives mentioned above to be better incorporated into rubber and to function in the rubber or during its preparation, for example, as an antioxidant, activator, or plasticizer.

[0005] Furthermore, in the preparation of tire rubber compounds, silanes are often used as processing aids to better mix carbon black or silica. These silanes release alcohols, particularly ethanol, during processing. From the perspective of occupational health regulations and environmental protection, this is an emission that should be avoided or reduced.

[0006] US 2008 / 0214718 A1 describes the use of polyisobutylene derivatives in the dispersion of metal oxides (such as zinc oxide) in polymers (e.g., polychloroprene, polyurethane-acrylic, or acrylic latex). An example of such polyisobutylene derivatives is the reaction product of polyisobutylene-substituted succinic acid (PIBSA) with a polyamine (such as triethylenetetramine) for the hydrophobic treatment of zinc oxide in the dispersion. Its use in rubber is not described.

[0007] The difference between rubber and the aforementioned dispersions is evident in this point alone: ​​rubber is a continuous hydrophobic organic matrix, while in dispersions, the aqueous and organic phases alternate and are separated from each other by phase interfaces.

[0008] The object of this invention is achieved by using amine derivatives of the following general formula:

[0009]

[0010] in,

[0011] X is a single bond or an organic spacer group.

[0012] R 1 The molecular weight Mn is from 104 g / mol to 100,000 g / mol, preferably from 104 g / mol to 10,000 g / mol, particularly preferably from 156 g / mol to 5,000 g / mol, and even more particularly preferably from 500 g / mol to 2,500 g / mol of straight-chain or branched alkenyl groups.

[0013] R 2 and R 3 Independent of each other, another single bond between the organic spacer group X, hydrogen, C1 to C4 alkyl, -R-NR 4 R 5 Group or repeating group

[0014] –[–R–NH–] x –H

[0015] x is a positive integer from 1 to 4

[0016] R is a divalent organic group containing 2 to 6 carbon atoms, optionally interrupted by an oxygen atom, preferably free from the group consisting of 1,2-ethylene, 1,2-propylene, and 1,3-propylene.

[0017] R 4 and R 5 It is independently hydrogen or C1 to C4 alkyl.

[0018] Used to improve at least one of the following properties of rubber-containing tires:

[0019] - Dispersion coefficient

[0020] -particle size

[0021] -Wetland adhesion

[0022] - Abrasion resistance

[0023] - Rolling resistance

[0024] - Vulcanization rate.

[0025] In a preferred embodiment, the spacer base X comprises structural units of the following general formula:

[0026] , or

[0027] Each binding site is associated with a nitrogen atom and R, respectively. 1 Group linkage.

[0028] In another preferred embodiment, the spacer base X is a single bond.

[0029] Group R 1 It is a straight-chain or branched alkenyl group with a molecular weight Mn of 104 g / mol to 100000 g / mol, preferably 104 g / mol to 10000 g / mol, particularly preferably 156 g / mol to 5000 g / mol, and even more particularly preferably 500 g / mol to 2500 g / mol, preferably a branched alkenyl group.

[0030] R 1 Examples are

[0031] -C 10 To C 30 straight-chain alkyl

[0032] -C9 to C 30 Branched alkyl groups can be obtained through the polymerization of C3 and / or C4 olefins.

[0033] - A branched alkenyl group, derived from homopolymers and copolymers containing isobutylene in polymeric form, wherein the number average molecular weight Mn of the alkenyl group is from 104 g / mol to 100,000 g / mol, preferably from 104 g / mol to 10,000 g / mol, particularly preferably from 156 g / mol to 5,000 g / mol, and even more particularly preferably from 500 g / mol to 2,500 g / mol.

[0034] In a preferred embodiment, R 1 It includes structural units polymerized from isobutylene or a mixture of isobutylene-containing monomers as described below.

[0035] Ideally, R in homopolymers 1 Therefore, it is the following group

[0036]

[0037] Where n is 0 to 960, preferably 0 to 94, particularly preferably 1 to 46, and even more particularly preferably 3 to 22.

[0038] In another preferred embodiment, R 1 It includes structural units polymerized from 1-butene and / or 2-butene, especially 1-butene, or mixtures of butene-containing monomers.

[0039] In another preferred embodiment, R 1 It includes structural units polymerized from propylene or a mixture of propylene-containing monomers.

[0040] In this application, unless otherwise expressly specified, C1 to C4 alkyl groups are preferably methyl, ethyl, n-propyl or n-butyl, preferably methyl, ethyl or n-butyl, particularly preferably methyl or n-butyl, and even more particularly preferably methyl.

[0041] In a preferred embodiment, X is a single bond, and R 2 and R 3 It is also hydrogen.

[0042] In another preferred embodiment, the amine derivative conforms to the general formula:

[0043]

[0044] in,

[0045] R, R 1 x has the above meaning.

[0046] In this preferred embodiment, X is an organic spacer group derived from succinic acid, and R 2 For another single bond between it and the organic spacer group X, and R 3 For repeated –[–R–NH–] x –H group, wherein R is preferably 1,2-ethylene, and x is a positive integer from 1 to 4.

[0047] In another preferred embodiment, the amine derivative conforms to the general formula:

[0048]

[0049] or

[0050]

[0051] or

[0052]

[0053] Or a mixture thereof,

[0054] in,

[0055] R is a divalent alkylene group, which may optionally be interrupted by an oxygen atom.

[0056] R 1 Alkenes with 9 to 200 carbon atoms, either straight-chain or branched.

[0057] R 4 and R 5 They are independently hydrogen or C1 to C4 alkyl groups.

[0058] In this embodiment, X is an organic spacer group, and R 2 For hydrogen, R 3 -R-NR 4 R 5 Group, wherein R is preferably 1,3-propylidene, and R 4 and R5 Each is a methyl group.

[0059] In the last embodiment, the product is also typically present as a mixture with a compound in which X is an organic spacer group and R... 2 For another single bond between R and the organic spacer group X, 3 -R-NR 4 R 5 Group, wherein R is preferably 1,3-propylidene, and R 4 and R 5 Each is a methyl group.

[0060] The present invention will be described in detail below:

[0061] rubber

[0062] In vehicle tire compounds, particularly in tread compounds, exemplarily a mixture of butyl rubber and diene elastomer, along with other components, is used.

[0063] Such mixtures are described, for example, in paragraphs

[0008] to

[0070] of WO2019 / 199839 A1, the contents of which are incorporated herein by reference.

[0064] In this document, rubber is understood as a diene elastomer, i.e., homopolymers and copolymers of diene monomers, preferably natural rubber, polybutadiene, styrene-butadiene copolymers and polyisoprene and mixtures thereof, such as mixtures of natural rubber and styrene-butadiene copolymers, mixtures of natural rubber and polybutadiene or mixtures of natural rubber and polyisoprene.

[0065] Diene elastomers typically have a glass transition temperature (Tg) ranging from -75°C to 0°C.

[0066] polybutadiene

[0067] This refers to polymers of 1,3-dienes, preferably but-1,3-dienes, with cis-1,4-bonding of at least 90%, preferably at least 95%.

[0068] Other comonomers can be polymerized in small quantities.

[0069] The elastomer used is preferably polybutadiene with greater than 90% cis-1,4-bonding, which is obtained by known catalytic methods using transition metal compounds, such as those described in French patent application FR-A-1436607.

[0070] Examples of suitable conjugated dienes are particularly 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Aromatic vinyl compounds may also be polymerized, particularly styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, or commercially available mixtures of "vinyltoluene".

[0071] Styrene-butadiene copolymer

[0072] Typical styrene-butadiene copolymers contain styrene content of 5% to 60% by weight, preferably 20% to 50% by weight, wherein the remaining comonomer is mainly 1,3-butadiene. The content of 1,2-units is typically 4 mol% to 80 mol%, and the content of cis-1,4-units is greater than 80 mol%.

[0073] One could also think of styrene-butadiene-isoprene terpolymer.

[0074] Polyisoprene

[0075] This is understood as homopolymers and copolymers of isoprene, which can be of natural or preferably synthetic origin.

[0076] The proportion of cis-1,4-unit is at least 90 mol%, preferably at least 98 mol%.

[0077] Butyl rubber

[0078] It refers to 85 mol% to 99.5 mol%, preferably 90 mol% to 99.5 mol%, particularly preferably 95 mol% to 99.5 mol% of C4-C7 isoolefins and 0.5 mol% to 15 mol%, preferably 0.5 mol% to 10 mol%, particularly preferably 0.5 mol% to 5 mol% of C4-C7 isoolefins. 14 Copolymers of conjugated dienes.

[0079] The preferred isoolefin is isobutene, the preferred conjugated diene is 1,3-butadiene and isoprene, and isoprene is particularly preferred.

[0080] The viscosity-average molecular weight of the butyl rubber is 100,000 to 1,500,000, preferably 250,000 to 800,000.

[0081] The raw materials for synthetic rubber, preferably 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, styrene and / or isobutylene, particularly preferably 1,3-butadiene, isoprene and / or isobutylene, may be at least partially, preferably entirely, derived from renewable sources. As determined according to ASTM D 6866 (see below), their proportion in all monomers used is advantageously at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 10% by weight, more particularly preferably at least 25% by weight, especially at least 50% by weight. The proportion of monomers from renewable sources may be up to 100% by weight, preferably up to 95% by weight, particularly preferably up to 90% by weight, more particularly preferably up to 85% by weight, especially up to 80% by weight.

[0082] plasticizer

[0083] Plasticizers (process oils) improve the processability of the composition, most of which are esters of aliphatic acids, such as fatty acid esters and fatty acid glycerides, preferably naturally occurring oils such as sunflower oil or rapeseed oil, or hydrocarbons such as paraffin oil, aromatic oil, naphthenic oil and polybutene oil.

[0084] In addition, resins known as tackifiers in adhesives and coatings are also suitable as plasticizers. These resins are preferably copolymers of the C5 fraction of naphtha or steam cracking effluent with vinyl aromatics, particularly copolymers of 1,3-butadiene, 1-butene, 2-butene, 1,2-butadiene, 3-methyl-1-butene, 1,4-pentadiene, 1-pentene, 2-methyl-1-butene, 2-pentene, isoprene, cyclopentadiene (which may also exist in the form of dicyclopentadiene), isoprene, cyclopentene, 1-methylcyclopentene, 1-hexene, methylcyclopentadiene, or cyclohexene. Copolymers of cyclopentadiene and / or dicyclopentadiene with vinyl aromatics (especially styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, or p-methylstyrene or divinylbenzene) are particularly suitable. These vinyl aromatics are components of the C9 fraction of naphtha or steam cracking effluent.

[0085] Preferred resins as plasticizers are cyclopentadiene and / or dicyclopentadiene copolymers, cyclopentadiene and / or dicyclopentadiene-styrene copolymers, polylimonene, limonene-styrene copolymers, limonene-cyclopentadiene and / or dicyclopentadiene copolymers, C5 fraction-styrene copolymers, and C5 fraction-C9 fraction copolymers.

[0086] filler

[0087] Examples of fillers include calcium carbonate, clay, mica, silica, silicates, talc, bentonite, titanium dioxide, alumina, zinc oxide, and carbon black, with zinc oxide, silicates, and carbon black being preferred.

[0088] Typical particle size ranges from 0.0001 μm to 100 μm.

[0089] Silicates are understood herein to be derivatives of silicic acid, including their calcium or aluminum compounds. Silicates can be obtained from solution or by gas-phase methods and exist in colloidal or precipitated form. Highly dispersible silicates are preferred.

[0090] BET surface area is typically less than 450m² 2 / g, preferably 30 to 400, particularly preferably 100 to 250m 2 / g, more preferably 130 to 220m 2 / g; CTAB surface area is 100 to 250m² 2 / g and preferably 150 to 200m 2 / g; DBP oil absorption value is 150 to 250 ml / 100g; average projected area of ​​aggregates before use is greater than 8500 nm. 2 And preferably 9000 to 11000 nm 2 When thermomechanically mixed with elastomers, the nm size is 7000 to 8400 nm. 2 The selected silica can be used alone or in combination with other fillers, such as carbon black or another conventional silica.

[0091] As a particularly suitable silica, silica obtained, for example, by the method described in European patent application EP-A-157703 is applicable.

[0092] The BET surface area, CTAB surface area, and oil absorption value were determined according to the method described in European patent application EP-A-157703. The average projected area of ​​silica was determined according to the method described in the last paragraph on page 8 to the first paragraph on page 9 of DE 69206445 T2.

[0093] antioxidants

[0094] Antioxidants are used to prevent oxidative degradation, especially p-phenylenediamines, such as N,N'-alkyl or aryl disubstituted p-phenylenediamines, with N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine being particularly preferred.

[0095] Curing agent, crosslinking agent, activator

[0096] The rubber composition is reacted with at least one curing agent and at least one crosslinking agent known to those skilled in the art.

[0097] Examples include organic peroxides and polyamines.

[0098] In particular, sulfur is used as a sulfiding agent for this purpose.

[0099] As activators for the vulcanization process, amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenylimides, thiocarbamates, and xanthate esters are used. N-cyclohexylbenzothiazole-2-sulfenamide (CBS) is particularly suitable.

[0100] Sulfur, metal oxides, fatty acids (especially stearic acid), and especially organosilane crosslinking agents (see silane coupling agents) can be used as crosslinking agents, such as vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, methacryloyloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc.

[0101] In one particular embodiment, bis(3-triethoxysilylpropyl)tetrasulfide is used.

[0102] ZnO, CaO, MgO, Al2O3, CrO3, TiO2, FeO, Fe2O3, and NiO can be used as metal oxides. These can be used as oxides or corresponding fatty acid compounds, preferably as stearates.

[0103] Zinc oxide is preferred.

[0104] Silane coupling agent

[0105] Typical coupling agents ensure stable chemical and / or physical interactions between components (e.g., between fillers and rubber).

[0106] They are usually sulfur-containing compounds, organosilanes, or polysiloxanes.

[0107] Coupling agents containing polysulfides and alkoxysilyl groups are preferred, with silane polysulfides being particularly preferred, such as bis((C1-C4)alkoxy(C1-C4)alkylsilyl(C1-C4)alkyl) polysulfides (especially disulfides, trisulfides, or tetrasulfides), such as bis(3-trimethoxysilylpropyl) polysulfides or bis(3-triethoxysilylpropyl) polysulfides. More examples are bis(3-triethoxysilylpropyl)tetrasulfide (TESPT) of the formula [(C2H5O)3Si(CH2)3S2]2, or bis(triethoxysilylpropyl)disulfide (TESPD) of the formula [(C2H5O)3Si(CH2)3S]2. Other examples are bis(mono(C1-C4)alkoxybis(C1-C4)alkylsilylpropyl) polysulfides (especially disulfides, trisulfides or tetrasulfides), particularly bis(monoethoxydimethylsilylpropyl) tetrasulfides.

[0108] composition

[0109] Butyl rubber, for example, accounts for 5 to 40 phr, preferably 5 to 25 phr, in the tread compound of vehicle tires. “phr” (parts per hundred rubber) indicates the composition based on 100 parts by weight of the polymer blend.

[0110] Polybutadiene may comprise 30 to 50 phr, styrene-butadiene copolymer 40 to 70 phr, and polyisoprene 0 to 20 phr, provided that the total of these polymers is 100 phr. All non-rubber components are calculated based on the total of these polymers.

[0111] The filler, especially carbon black and silicate, typically accounts for 20 to 200 phr, preferably 30 to 150 phr.

[0112] The proportion of plasticizer is usually 10 phr to 30 phr.

[0113] According to the present invention, the above-mentioned amine derivative is added to these rubbers, and in a preferred embodiment, the amine derivative may be polyisobutylene-substituted:

[0114] The polyisobutylene constituting the chain base is a homopolymer and copolymer of isobutylene in polymeric form, having a number average molecular weight Mn of 500 to 50,000, preferably 550 to 40,000, particularly preferably 650 to 30,000, even more particularly preferably 750 to 20,000, especially 900 to 15,000.

[0115] In a preferred embodiment, polyisobutylene refers to polyisobutylene with a Mn value of 950 to 1050. Among these polyisobutylenes, those having a high content of terminally arranged ethylene double bonds (α-double bonds) are preferred, particularly those having an α-double bond content of at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, and even more particularly preferably at least 80 mol%. These are referred to as highly reactive polyisobutylenes.

[0116] In another preferred embodiment, polyisobutylene refers to polyisobutylene with a Mn value of 2300 to 10000.

[0117] For the preparation of homopolymers or copolymers containing isobutylene in polymeric form, suitable sources of isobutylene include pure isobutylene and isobutylene-containing C4 hydrocarbon streams, such as C4 residues, particularly "Residue 1", C4 fractions from isobutane dehydrogenation, and C4 fractions from steam crackers and FCC crackers (fluidized catalytic cracking), provided they substantially do not contain 1,3-butadiene present therein. C4 hydrocarbon streams from FCC refining units are also referred to as "b / b" streams. Other suitable isobutylene-containing C4 hydrocarbon streams are, for example, product streams from propylene-isobutane co-oxidation or product streams from metathesis units, which are typically used after routine purification and / or concentration. Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene, as well as cis- and trans-2-butene, is largely unimportant. Typically, the isobutylene concentration in the C4 hydrocarbon stream is in the range of 40-60% by weight. Therefore, residual liquid 1 typically consists essentially of 30% to 50% by weight isobutylene, 10% to 50% by weight 1-butene, 10% to 40% by weight cis- and trans-2-butene, and 2% to 35% by weight butane; in the polymerization method according to the invention, the unbranched butene in residual liquid 1 is generally practically inert, and only isobutylene is polymerized. In a preferred embodiment, the isobutylene content is 1% to 100% by weight, particularly 1% to 99% by weight, mainly 1% to 90% by weight, and especially preferably 30% to 60% by weight of industrial C4 hydrocarbon streams, particularly residual liquid 1 stream, b / b streams from FCC refining units, product streams from propylene-isobutane co-oxidation, or product streams from metathesis units, which are used as monomer sources for polymerization.

[0118] In particular, when using residual liquid stream 1 as the isobutylene source, it has been shown that using water as the sole or other initiator is useful, especially when polymerization is carried out at temperatures ranging from -20 °C to +30 °C, particularly from 0 °C to +20 °C. However, at temperatures ranging from -20 °C to +30 °C, particularly from 0 °C to +20 °C, when using residual liquid stream 1 as the isobutylene source, the use of an initiator can also be omitted.

[0119] Isobutylene or isobutylene-containing C4 hydrocarbon streams may be at least partially, preferably entirely, derived from renewable sources, as described, for example, in WO 2012 / 40859 A1, particularly on page 5, line 9 to page 6, line 24. As determined by ASTM D 6866, as described in WO 2012 / 40859 A1, the proportion of isobutylene from renewable sources in all isobutylene used is advantageously at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 10% by weight, more particularly preferably at least 25% by weight, and especially at least 50% by weight. The proportion of isobutylene from renewable sources may be up to 100% by weight, preferably up to 95% by weight, particularly preferably up to 90% by weight, more particularly preferably up to 85% by weight, and especially up to 80% by weight.

[0120] Isobutylene obtained from renewable feedstocks can be measured... 14 C / 12 Characterized by carbon isotope ratio, preferably determined according to ASTM D 6866 ("Determination of bio-based content in natural range materials using radiocarbon and isotope ratio mass spectrometry").

[0121] According to this test method, the sample's... 14 C / 12 C isotope ratio, and compared with that in standardized 100% bio-based materials. 14 C / 12 The carbon isotope ratios were compared. As a result, the proportion of bio-based components in the samples was obtained.

[0122] The application of ASTM-D6866 to derive "biobased content" is based on the same theory as radiocarbon dating, but without the need for age calculation formulas. This analysis determines the radiocarbon content in an unknown sample. 14 C) The ratio of the amount to a modern reference standard is used for the analysis. This indicator is given as a percentage in "pMC" (percentage of modern carbon). If the material being analyzed is a mixture of modern radioactive carbon and fossil carbon (containing trace amounts of radioactive carbon), the obtained pMC value is directly related to the amount of biomass material present in the sample.

[0123] "Bio-based materials" are organic materials whose carbon originates from CO2 fixed from the atmosphere via solar energy (photosynthesis) in the recent past (measured on a human timescale). On land, this CO2 is absorbed or fixed by plants (e.g., crops or forestry). In the ocean, this CO2 is bound or fixed by the photosynthesis of bacteria or phytoplankton. Therefore, bio-based materials have a carbon content greater than 0. 14 C / 12 C isotope ratio. In contrast, fossil materials have a ratio of approximately 0. 14 C / 12 C isotope ratio.

[0124] A small number of carbon atoms in atmospheric carbon dioxide are radioactive isotopes. 14 C is produced when neutrons from cosmic rays collide with nitrogen atoms in the atmosphere, causing the nitrogen atom to lose a proton and thus forming carbon with an atomic mass of 14. 14 (C), the carbon atom is then oxidized to carbon dioxide. The small but measurable proportion of atmospheric carbon is... 14 Atmospheric carbon dioxide exists in the form of CO2. Atmospheric carbon dioxide is assimilated by green plants in a process called photosynthesis to produce organic molecules. Almost all life forms on Earth rely on these organic molecules produced by green plants to generate chemical energy, which enables growth and reproduction. Therefore, carbon dioxide forms in the atmosphere... 14 C ultimately becomes part of all life forms and their biological products, which are enriched in biomass and those containing... 14 C is found in organisms that feed on biomass. In contrast, carbon from fossil sources (especially oil or coal) does not possess the characteristic renewable organic molecules derived from atmospheric carbon dioxide. 14 C: 12 C ratio.

[0125] In a preferred embodiment of the invention, the isobutylene used in the polyisobutylene has the properties according to ASTM-D6866. 14 C: 12 The bio-based content determined by the C ratio is greater than 0%, preferably at least 1%, particularly preferably at least 5%, even more particularly preferably at least 10%, especially at least 20%, and especially at least 25%.

[0126] Advantageously, the bio-based content can be at least 30%, preferably at least 40%, particularly preferably at least 50%, especially preferably at least 66%, particularly at least 75%, and especially at least 85%.

[0127] When the proportion is at least 90%, preferably at least 95%, particularly preferably at least 98%, or even 100%, it can be called significantly dominant or completely bio-based isobutylene.

[0128] According to this implementation method, resources are saved, and the product is made from at least some of the renewable raw materials.

[0129] In another embodiment of the invention, the isobutylene used for polymerization may be obtained entirely from renewable feedstocks or may consist of a mixture of isobutylenes from renewable and fossil sources.

[0130] This implementation method is particularly preferred as long as isobutylene from renewable sources cannot be obtained in sufficient quantities and economically on an industrial scale.

[0131] The isobutylene-containing monomer mixture may contain small amounts of contaminants, such as water, carboxylic acids, or inorganic acids, without causing a critical loss in yield or selectivity. Advantageously, the enrichment of these contaminants is avoided by removing them from the isobutylene-containing monomer mixture, for example, by adsorption onto solid adsorbents such as activated carbon, molecular sieves, or ion exchangers.

[0132] Although less preferred, isobutylene or a mixture of isobutylene-containing hydrocarbons may also be reacted with a mixture of olefinically unsaturated monomers that can copolymerize with isobutylene. If isobutylene is to be copolymerized with a mixture of suitable comonomers, the monomer mixture preferably contains at least 5% by weight, particularly preferably at least 10% by weight, especially at least 20% by weight of isobutylene, and preferably at most 95% by weight, particularly preferably at most 90% by weight, especially at most 80% by weight of comonomers.

[0133] In a preferred embodiment, the amine derivative that can be used according to the invention is a polyisobutylene derivative, which contains at least one amino group (-NR). 2 R 3 ).

[0134] in

[0135] R 2 and R 3 Each of them is independently hydrogen or C1 to C4 alkyl or (although less preferred) can form a five- to seven-membered ring with the central nitrogen atom, which may optionally contain another heteroatom.

[0136] Preferably, R 2 and R 3 They are individually hydrogen, methyl, ethyl, n-propyl or n-butyl, or together 1,4-butylene, 1,5-pentylene or 3-oxo-1,5-pentylene, particularly preferably hydrogen or methyl, and even more particularly preferably hydrogen.

[0137] In a preferred embodiment, the present invention relates to so-called polyisobutyleneamine (PIBA), which can be produced by hydroformylation of highly reactive polyisobutylene and reductive amination using ammonia, a monoamine, or a polyamine (such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine), as is known particularly from EP-A 244 616. Here, ammonia is preferably used for the reaction. Therefore, the group R... 1 It contains one more carbon atom than basic polyisobutylene, which is introduced through a hydroformylation reaction.

[0138] Due to its manufacturing process, polyisobutylene is a mixture of double bond isomers, and these isomers determine the properties of polyisobutylene, especially its chemical reactivity. Most importantly...

[0139] Isomers with α-double bonds ,as well as

[0140] Isomers with β-double bonds ,

[0141] in,

[0142] The group PIB represents the remaining portion of polyisobutylene without the indicated substructure.

[0143] In addition, other isomers may be conceived, such as those shown in WO 2023 / 152258, but these play only a minor role according to the invention.

[0144] In a preferred embodiment of the invention, the polyisobutylene used for the hydroformylation reaction has an α-double bond content of at least 70%, preferably at least 75%, particularly preferably at least 80%, more particularly preferably at least 85%, and especially at least 90%. Such polyisobutylene is also known as highly reactive polyisobutylene.

[0145] The content of β-double bonds can be as high as 25%, preferably as high as 20%, particularly preferably as high as 15%, even more particularly preferably as high as 10%, and especially as high as 5%.

[0146] Except for isomers with α- or β- double bonds, the content of other isomers is usually no more than 5%.

[0147] Isomer content by means of 1 The sensitivity of H-NMR spectroscopy is determined by the frequency of the measuring instrument. It is preferably performed at 700 MHz at 25°C. 1 H-NMR spectroscopy is preferred for isomer determination. The method described by Guo et al. in Journal of Polymer Science, Part A: Polymer Chemistry, 2013, Vol. 51, pp. 4200-4212 is particularly preferred for isomer identification.

[0148] In a preferred embodiment, the polyisobutylene has a number-average molecular weight Mn of 104 g / mol to 10000 g / mol and has the above-mentioned α- and β- double bond content, preferably 156 g / mol to 5000 g / mol, and particularly preferably 500 g / mol to 2500 g / mol.

[0149] In another less preferred embodiment, the polyisobutylene (A) has a number-average molecular weight Mn of greater than 10,000 g / mol to 100,000 g / mol, preferably 11,000 g / mol to 90,000 g / mol, particularly preferably 12,000 g / mol to 80,000 g / mol, even more particularly preferably 13,000 g / mol to 75,000 g / mol, especially preferably 14,000 to 70,000, and the α-double bond content is at least 20% to 60%, preferably at least 25% to 45%, particularly preferably at least 30% to 40%. This type of polyisobutylene is also called medium molecular weight polyisobutylene.

[0150] Although not the preferred choice, it is conceivable to use high molecular weight polyisobutylene with a number average molecular weight greater than 100,000 g / mol to 5,000,000 g / mol, and whose α-double bond content is generally no more than 50%, preferably no more than 40%, and particularly preferably no more than 30%.

[0151] The molecular weight was determined by gel permeation chromatography using polystyrene as a standard.

[0152] The idealized structure of polyisobutyleneamine is

[0153]

[0154] The number of repeating units, n, is defined above.

[0155] For the preferred basic polyisobutylene, when the number average molecular weight Mn is 168 to 2300, n is 1 to 39; when Mn is 224 to 1500, n is 2 to 25; when Mn is 550 to 1300, n is 8 to 21; when Mn is 700 to 1300, n is 10 to 21; and when Mn is 950 to 1050, n is 15 to 17.

[0156] If the base polyisobutylene is made from a C4 hydrocarbon stream containing isobutylene (see above), and that hydrocarbon stream contains other monomers besides isobutylene, then the polymer backbone includes other monomers in polymerized form, such as 1-butene and cis- and trans-2-butene, especially 1-butene.

[0157] Such polyisobutylene amines can be obtained by polymerizing isobutylene into polyisobutylene with (idealized) terminal double bonds, followed by hydroformylation and then amination with ammonia in a subsequent step. This method is exemplarily described in Example 1 of US 4832702. Here, the parameter n corresponds to the degree of polymerization of isobutylene in the polyisobutylene minus 2; the molecular weight of the polyisobutylene used is preferably about 1000 g / mol.

[0158] In another preferred embodiment, the present invention relates to compounds containing free amino and imine groups, such as reaction products of alkyl or alkenyl-substituted succinic anhydrides with aliphatic polyamines (polyalkylimides), particularly with ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.

[0159] This type of polyisobutylene succinimide has the following general formula.

[0160]

[0161] in

[0162] R 1 The polyisobutylene group has a number average molecular weight (Mn) of 10⁴ to 100,000 g / mol, preferably 10⁴ to 10,000 g / mol, particularly preferably 156 to 5,000 g / mol, and even more particularly preferably 500 to 2,500 g / mol.

[0163] x is a positive integer, such as 1 to 4, preferably 2 to 4, and especially preferably 3 or 4.

[0164] Preferably, the group R 1 The molecular weight is from 550 g / mol to 2300 g / mol, preferably from 650 g / mol to 1500 g / mol, and particularly preferably from 750 g / mol to 1300 g / mol.

[0165] In another preferred embodiment, the amine derivative that can be used according to the invention is the reaction product of an alkyl or alkenyl-substituted succinic anhydride with an N-monosubstituted or disubstituted 1,ω-alkylene diamine, preferably 1,3-propanediamine.

[0166] Examples of this include: N-cyclohexyl-1,3-propanediamine; N-2-ethylhexyl-1,3-propanediamine; N-dodecyl-1,3-propanediamine; N-octadecyl-1,3-propanediamine; N-oleyl-1,3-propanediamine; N-3-aminopropyl tallow amine; N-arachidoyl-1,3-propanediamine; N-benzyl-1,3-propanediamine; N-phenyl-1,3-propanediamine; 2-aminoethyloctadecylamine; 2-aminoethylbenzylamine; 2-aminoethyloleylamine ; 2-Aminoethyl tallow amine; N-octadecyl-1,6-hexamethylenediamine; N-octadecyldipropyltriamine; N-dodecyldipropyltriamine; N,N-dimethylaminopropylamine-1,3; N,N-tetrazyl-1,3-propanediamine; N,N-bis(2-ethylhexyl)-3-aminopropylamine; bis-aminopropyl tallow amine; bis-aminopropyl laurylamine, 1-(2-aminopropyl)-octadecylamine; 1-(2-aminopropyl)-piperazine; N-2-aminoethyl-piperidine; N-3-aminopropylimidazolium.

[0167] N,N-dimethylaminopropylamine-1,3 is preferred.

[0168] Typically, the corresponding amide is first formed when the functional group of the acid anhydride opens the ring, or a cyclization reaction occurs at a higher reaction temperature to generate the corresponding imide.

[0169] The manufacturing method is described, for example, in WO 2012 / 004300. If the reaction temperature of an alkyl or alkenyl-substituted succinic anhydride with an N-monosubstituted or disubstituted 1,ω-alkylene diamine is kept below about 80°C, an amide is mainly formed, with a small amount of imide also formed under these reaction conditions.

[0170] The compounds available according to the invention, containing a spacer group X derived from succinic acid, are typically based on polyisobutylene-substituted succinic anhydride (PIBSA), which can be obtained by reacting highly reactive polyisobutylene with an alkene of maleic anhydride, and serve as starting compounds for amides or imides.

[0171] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride used is a highly reactive polyisobutylene having the above-mentioned number-average molecular weight Mn.

[0172] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride (PIBSA) used also contains more than one monosubstituted product.

[0173] The ratio of highly maleicized to monomaleicized components can be expressed by the "degree of bismaleidation" (BMG). BMG itself is known (see also US 5,883,196) and can be determined using the following formula:

[0174] BMG = 100% × [(wt-%(BM PIBSA) / (wt-%(BM PIBSA)+wt-%(PIBSA))]

[0175] Where wt-%(X) represents the weight percentage of component X (X = PIBSA (monomaleyl polyisobutylene) or BM PIBSA (polymaleyl polyisobutylene)) in the reaction product of polyisobutylene and maleic anhydride.

[0176] The degree of bismaleidation is preferably calculated based on the saponification value of the sample according to DIN 53401: 1988-06. The sample must be dissolved in a suitable solvent, preferably a 2:1 mixture of toluene and ethanol, if necessary.

[0177] It is important to note that only the ratio of highly maleicinated components to monomaleicinated components is considered, and unreacted polyisobutylene present in the reaction mixture, such as polyisobutylene without reactive double bonds, is not included in the determination of the degree of bismaleidation. Therefore, the reaction mixture may also contain unreacted polyisobutylene, which typically corresponds to the proportion of polyisobutylene used that does not contain reactive double bonds, while the proportion of polyisobutylene containing reactive double bonds is preferably completely or almost completely reacted.

[0178] In a preferred embodiment, the degree of bismaleidation of PIBSA is at least 5%, preferably at least 8%, and particularly preferably at least 10%.

[0179] More advantageously, the reaction product of polyisobutylene with a degree of bismaleidation of at least 12%, preferably at least 15%, particularly preferably at least 20% can be used.

[0180] The degree of bismaleidation can be as high as 60%, preferably as high as 55%, particularly preferably as high as 50%, especially as high as 45%, and especially as high as 40%. Under suitable reaction conditions, especially with a large excess of maleic anhydride, the degree of bismaleidation can be increased to as high as 80% or even as high as 100%.

[0181] The best results are obtained when the degree of bismaleidation is 10% to 50%, preferably 12% to 45%, and particularly preferably 15% to 40%.

[0182] The amine derivatives according to the invention are typically added to rubber mixtures in amounts of 2 to 20 phr, preferably 4 to 14 phr, and particularly preferably 5 to 10 phr.

[0183] Typically, these compounds are added to the rubber compound along with other components and heated in a kneader or extruder to initiate vulcanization. It is also advantageous to first thoroughly mix the rubber compound and fillers with the amine derivatives before adding other components, particularly antioxidants, activators, and / or plasticizers.

[0184] Therefore, another embodiment of the present invention is a method for reducing the viscosity of rubber compound when manufacturing rubber-containing tires, in which the rubber compound is reduced by...

[0185] -at least one rubber and

[0186] - Carbon black and / or silicates and

[0187] - At least one processing aid and / or additive for improving at least one performance characteristic of the tire.

[0188] Mix in a kneader and / or extruder.

[0189] At least one amine derivative as described above is added to the rubber compound before and / or during processing.

[0190] The vulcanization and manufacturing methods of rubber compounds are known and can be directly applied to the application of amine derivatives.

[0191] One advantage of amine derivatives is that they have a beneficial effect on improving at least one of the following properties of rubber-containing tires.

[0192] - Dispersion coefficient

[0193] -particle size

[0194] -Wetland adhesion

[0195] - Abrasion resistance

[0196] - Rolling resistance.

[0197] Amine derivatives are particularly suitable for improving the dispersion of fillers, especially silica, in rubber compounds.

[0198] In addition, they exhibit a particular advantage in reducing rolling resistance.

[0199] During the manufacture of rubber compounds, the application of amine derivatives has also shown the advantage of significantly reducing the viscosity of rubber compounds during the processing and manufacture of rubber-containing tires.

[0200] Therefore, another subject of the present invention is a method for reducing the viscosity of rubber compounds during the manufacture of rubber-containing tires, in which the rubber compound is reduced by...

[0201] -at least one rubber and

[0202] - Carbon black and / or silicates and

[0203] - At least one processing aid and / or additive for improving at least one performance characteristic of the tire.

[0204] Mix in a kneader and / or extruder.

[0205] In this method, at least one amine derivative as described above is added to the rubber compound before and / or during processing.

[0206] Furthermore, these compounds exhibit advantages in terms of wet grip and / or rolling resistance and / or abrasion resistance at low temperatures (-10°C) in tires containing them. Preferably, amine derivatives improve at least two of these three properties. A particular advantage of amine derivatives is that they simultaneously offer advantages in wet grip, rolling resistance, and abrasion resistance at low temperatures (-10°C) in tires.

[0207] By improving tire wear resistance, the amount of microplastics released during tire wear in motor vehicle operation can be reduced.

[0208] Another topic is rubber compounds, including

[0209] - At least one type of rubber, said rubber being selected from the group consisting of isobutylene-isoprene rubber, styrene-butadiene rubber, and natural rubber.

[0210] - At least one filler, said filler being selected from the group consisting of calcium carbonate, clay, mica, silica, silicates, talc, bentonite, titanium dioxide, alumina, zinc oxide, and carbon black.

[0211] - At least one antioxidant, preferably p-phenylenediamine,

[0212] - At least one peroxide and / or polyamine as a curing agent and / or crosslinking agent

[0213] - At least one vulcanization process activator, said vulcanization process activator being selected from the group consisting of amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenamides, thiocarbamates, and xanthates.

[0214] - At least one silane crosslinking agent, selected from the group consisting of bis((C1-C4)alkoxy(C1-C4)alkylsilyl(C1-C4)alkyl)polysulfides (especially disulfides, trisulfides or tetrasulfides), bis(3-trimethoxysilylpropyl)polysulfides, bis(3-triethoxysilylpropyl)polysulfides, bis(3-triethoxysilylpropyl)tetrasulfide of the formula [(C2H5O)3Si(CH2)3S2]2 and bis(triethoxysilylpropyl)disulfide of the formula [(C2H5O)3Si(CH2)3S]2 (TESPT), and at least one amine derivative conforming to the following general formula.

[0215] .

[0216] Another subject of this invention is for R 2 and R 3 Compounds that conform to the following general formula in the case where at least one of the two groups is hydrogen, preferably both of them, are of this type.

[0217] R 1 -X-NR 3 -Si(OC2H5)2-(CH2)3-S4-(CH2)3-Si(OC2H5)3 and

[0218] R 1 -X-NR 3 -Si(OC2H5)2-(CH2)3-S2-(CH2)3-Si(OC2H5)3,

[0219] Where R 1 X and R 3 Having the above meaning,

[0220] And rubber compounds containing at least one such compound, their use in rubber-containing tires, particularly for improving the compatibility of silicates in rubber-containing tires, and their use for improving at least one of the following properties of rubber-containing tires:

[0221] - Dispersion coefficient

[0222] -particle size

[0223] -Wetland adhesion

[0224] - Abrasion resistance

[0225] - Rolling resistance

[0226] - Vulcanization rate.

[0227] Another subject of this invention is a derivative of polyisobutyleneamine with a silane coupling agent, the idealized structure of which is as follows:

[0228]

[0229] in,

[0230] The number of repeating units n is as defined above, and

[0231] Y represents –(S) x –R 25 –Si(OR 26 )3,

[0232] y represents 1, 2, 3 or 4.

[0233] and

[0234] R 25 It is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms, and more particularly preferably selected from the group consisting of methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 5-oxa-1,5-pentene, and 1,6-hexene, especially 1,3-propylene.

[0235] R 26 Represents C1 to C6 alkyl, preferably C1 to C4 alkyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, even more particularly preferably methyl, ethyl or n-butyl, especially methyl or ethyl, specifically representing methyl.

[0236] These compounds, and rubber compounds containing at least one such compound, are used in rubber-containing tires, particularly for improving silicate compatibility or as coupling agents in rubber-containing tires, and for improving at least one of the following properties of rubber-containing tires:

[0237] - Dispersion coefficient

[0238] -particle size

[0239] -Wetland adhesion

[0240] - Abrasion resistance

[0241] - Rolling resistance

[0242] - Vulcanization rate,

[0243] This is also the subject of this invention.

[0244] Another subject of this invention is for R 2 and R 3 In cases where at least one of the two groups is hydrogen, preferably both are hydrogen, the amine compound and a fatty acid, particularly a derivative of stearic acid, used as an activator, have the following structure:

[0245] R 1 -X-NR 3 -(C=O)-R 10

[0246] Where R 1 X and R 3 Having the above meaning, and

[0247] R 10 It represents a fatty acid group, preferably a saturated alkyl group or a monounsaturated or polyunsaturated alkenyl group having 9 to 19 carbon atoms.

[0248] Preferably, the group R 10 -(C=O)- is derived from fatty acids such as lauric acid, myristic acid, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and linolenic acid, or mixtures thereof.

[0249] Industrially available fatty acid mixtures preferably include tallow fatty acids, coconut oil fatty acids, fish oil fatty acids, palm kernel oil fatty acids, soybean oil fatty acids, turnip oil fatty acids, peanut oil fatty acids, or palm oil fatty acids, which contain oleic acid and palmitic acid as major components.

[0250] These compounds, and rubber compounds containing at least one such compound, are used in rubber-containing tires, particularly as vulcanization activators or vulcanization accelerators in rubber-containing tires, and for improving at least one of the following properties of rubber-containing tires:

[0251] - Dispersion coefficient

[0252] -particle size

[0253] -Wetland adhesion

[0254] - Abrasion resistance

[0255] - Rolling resistance

[0256] - Vulcanization rate,

[0257] This is also the subject of this invention.

[0258] Furthermore, the compounds according to the invention are suitable for combining released alcohols, particularly ethanol, during the manufacture of tire rubber compounds, thereby reducing emissions during manufacturing.

[0259] This reduces emissions during manufacturing.

[0260] Without being bound by theory, it is speculated that such alcohols R are released during the manufacturing process of tire rubber compounds. 6 OH, especially ethanol, reacts with the unreacted succinic anhydride or carboxylic acid group and is bound as a carboxylic acid ester. Similarly, it is conceivable that the released alcohol R...6 OH, especially ethanol, in transesterification or amide exchange reactions, displace alcohols or amines from existing carboxylic acid esters, carboxylic acid amides, or carboxylic acid imides.

[0261] Here, for example, the following compounds can be formed:

[0262] From compounds

[0263]

[0264] or

[0265]

[0266] or

[0267]

[0268] Can form

[0269]

[0270] or

[0271]

[0272] or

[0273] .

[0274] From compounds

[0275]

[0276] Can form

[0277]

[0278] or

[0279]

[0280] or

[0281] ,

[0282] Each variable has its own meaning as described above.

[0283] In the case of amine derivatives that conform to the following general formula

[0284]

[0285] in,

[0286] R 2 and R 3 Each is hydrogen, and the group R 2and R 3 One or two of them are R 6 The substituted substance is preferably substituted with an ethyl group.

[0287] These compounds, generated by the reaction with released alcohols, and rubber compounds containing at least one such compound, are used in rubber-containing tires, particularly for improving silicate compatibility or as coupling agents in rubber-containing tires, and for improving at least one of the following properties of rubber-containing tires:

[0288] - Dispersion coefficient

[0289] -particle size

[0290] -Wetland adhesion

[0291] - Abrasion resistance

[0292] - Rolling resistance

[0293] - Vulcanization rate,

[0294] This is also the subject of this invention.

[0295] The present invention is illustrated by the following embodiments, but is not limited thereto. Example

[0296] Preparation Examples

[0297] Compound 1

[0298] Polyisobutyleneamine with a number-average molecular weight (Mn) of approximately 1000 g / mol was purchased from BASFSE (Ludwigshafen) under the trade name Kerocom PIBA 03 and dissolved in Mihagol.

[0299] Compound 2

[0300] 150.20g BASF SE (Ludwigshafen) Glissopal ® 1000, number-average molecular weight Mn (determined by GPC) approximately 1000 g / mol, polydispersity approximately 1.6, α-double bond content (as determined by GPC) 13 (C NMR determination) approximately 88%, β-double bonds 6%, with 29.4 g (0.30 mol, 2 equivalents) of maleic anhydride, heated to 225 °C and stirred for 7 h in an autoclave. The reaction mixture was then cooled to 80 °C and 150 mL of heptane was added. The solution was stirred at 100 °C for 1 h and then filtered. The solvent was removed under vacuum (yield = 164.00 g). (SV: 175 mg KOH / g).

[0301] Polyisobutylene succinic anhydride (PIBSA) with a degree of bismaleidation of approximately 100% was obtained.

[0302] Compound 3

[0303] 122.2 g of polyisobutylene succinic anhydride (SV = 91.8 mg KOH / g), prepared similarly to compound 2, was dissolved in 100.60 g of toluene. 11.20 g (0.11 mol) of 3-dimethylaminopropylamine was added to the reaction mixture, and the mixture was stirred at 120 °C for 2 hours. The reaction mixture was then cooled to room temperature, and the solvent was removed under vacuum (yield = 130.50 g).

[0304] Compound 4

[0305] 126.10 g of polyisobutylene succinic anhydride (SV = 89.0 mg KOH / g), prepared similarly to compound 2, was dissolved in 100.00 g of toluene. 18.90 g (0.10 mol) of tetraethylenepentamine was added to the reaction mixture, and the mixture was stirred at 120 °C for 2 hours. The reaction mixture was then cooled to room temperature, and the solvent was removed under vacuum (yield = 142.10 g).

[0306] Method Description

[0307] Improvement of dispersion coefficient

[0308] Computer-aided analysis of at least 10 images at 125x magnification using an optical microscope was employed to determine the macroscopic dispersion of the particles by comparing the reflective area of ​​the undispersed filler aggregates (particles) with the total observed area (Dispersion Index Analysis System, DIAS). The dispersion (expressed as a percentage %) was then derived, taking into account the filler volume content and the void volume of the filler through a correction factor.

[0309] The goal is to achieve a high dispersion factor.

[0310] Particle size determination

[0311] The average diameter of the particles was determined together with the dispersion coefficient using optical methods.

[0312] Smaller particle size is advantageous.

[0313] Wet grip and rolling resistance at low temperatures (-10℃)

[0314] The prepared rubber compound was taken into strip-shaped samples (40×10×2mm) and tested using Rheometric Scientific. ™ Dynamic mechanical analysis (DMA) is performed using the company's ARES testing equipment.

[0315] Measurement parameters:

[0316] Temperature range -60℃ to 80℃

[0317] 1Hz frequency

[0318] Amplitude 0.5%

[0319] The tan(δ) value at -10℃ is considered a measure of traction on wet pavement at low temperatures, while the tan(δ) value at +60℃ is considered a measure of rolling resistance.

[0320] tan(δ) -10℃ A high value of tan(δ) indicates high wet grip, which is advantageous; 60℃ A low value indicates low rolling resistance, which is the desired target.

[0321] abrasion resistance

[0322] According to DIN ISO 4649 standard, on Frank's wear testing machine, under a load of 10N, a sliding distance of 40m, and a rotational speed of 40m... -1 Wear was measured under certain conditions.

[0323] The abrasion resistance index is expressed as a percentage [%], and the higher the value, the better.

[0324] Reduce viscosity during processing

[0325] The components of the rubber compound were mixed in a specified ratio, and the Mooney viscosity of the compound was measured in an Alpha Technologies MV 2000 E Mooney viscometer at 100°C and 2 rpm (Mooney ML (1+4) 100°C).

[0326] Viscosity is measured in Mooney units (ME).

[0327] Accelerated sulfidation

[0328] The silica-containing rubber compound described below was treated in a Rheometer MDR 2000E vulcanizer at a temperature of 160°C, an amplitude of 0.5%, and a frequency of 1.67 Hz, with the torque measured over time. An increase in torque reflects the progress of vulcanization.

[0329] In addition, the rubber compound was vulcanized in the Rucks Maschinenbau KV 207.00 equipment at a temperature of 160°C and a pressure of 280 bar to determine the t 90 value.

[0330] shorten t90 Time is favorable.

[0331] Application Examples

[0332] A rubber compound containing silica (“reference”) was prepared as a comparison, or a rubber compound containing the additives according to the present invention was prepared, the composition of which is as follows:

[0333]

[0334] 1) Nipol NS616 rubber (modified S-SBR, styrene content: 20% by weight, vinyl content: 67% by weight, SP value: 17.25 (J / cm³) 3 ) 1 / 2 Tg: -25℃, Mw: 510,000, non-oil-filled), manufactured by ZEON CORPORATION (SBR1 in EP3263360 A1, paragraph

[0054] ).

[0335] 2) Amorphous SiO2, Evonik's Ultrasil 7000 GR

[0336] 3) Bis(triethoxysilylpropyl)tetrasulfide

[0337] 4) IPPD: N-isopropyl-N'-phenyl-1,4-phenylenediamine

[0338] 5)DPG: N,N'-diphenylguanidine

[0339] 6) CBS: N-cyclohexylbenzothiazole-2-sulfenamide

[0340] The rubber compound according to the present invention

[0341] Silica-containing rubber compounds K1 to K5 are prepared by adding a specified amount of the compound according to the invention, similar to the method used for "reference" silica-containing reference rubber compounds. To balance this, the proportion of plasticizer is correspondingly partially reduced.

[0342]

[0343] Example 1 (Improvement of Dispersion Coefficient)

[0344]

[0345] Example 2 (Reducing Particle Size)

[0346]

[0347] Example 3 (Wet grip at low temperature (-10℃))

[0348]

[0349] Example 4 (Rolling Resistance)

[0350]

[0351] Example 5 (Abrasion Resistance)

[0352]

[0353] Example 6 (Shore A Hardness)

[0354] Shore A hardness was measured using a Zwick digitest instrument according to DIN ISO 48-4 standard.

[0355]

[0356] Example 7 (Accelerated Vulcanization)

[0357]

Claims

1. Use of an amine derivative of the following general formula, in X is a single bond or an organic spacer group. R 1 The molecular weight Mn is from 104 g / mol to 100,000 g / mol, preferably from 104 g / mol to 10,000 g / mol, particularly preferably from 156 g / mol to 5,000 g / mol, and even more particularly preferably from 500 g / mol to 2,500 g / mol of straight-chain or branched alkenyl groups. R 2 and R 3 Independent of each other, another single bond between the organic spacer group X, hydrogen, C1 to C4 alkyl, -R-NR 4 R 5 Groups or repeating –[–R–NH–] x -H group x is a positive integer from 1 to 4 R is a divalent organic group containing 2 to 6 carbon atoms, preferably free from the group consisting of 1,2-ethylene, 1,2-propylene, and 1,3-propylene. R 4 and R 5 Independently hydrogen or C1 to C4 alkyl, Used to improve at least one of the following properties of rubber-containing tires: - Dispersion coefficient -particle size -Wetland adhesion - Abrasion resistance - Rolling resistance - Vulcanization rate.

2. The use according to claim 1, characterized in that, The amine derivative is a polyisobutylene amine of the following general formula: Where n is a positive integer from 0 to 960, preferably from 0 to 94, particularly preferably from 1 to 46, and even more particularly preferably from 3 to 22.

3. The use according to claim 1, characterized in that, The amine derivative conforms to the following general formula. or or in R is a divalent alkylene group that can be interrupted by an oxygen atom when appropriate. R 4 and R 5 They are independently hydrogen or C1 to C4 alkyl groups.

4. The use according to claim 3, characterized in that, -R is 1,3-propylidene, and -R 4 and R 5 Each is a C1 to C4 alkyl group.

5. The use according to claim 1, characterized in that, The amine derivative conforms to the following general formula. in R is a divalent alkylene group, which can optionally be interrupted by an oxygen atom, and x is a positive integer from 1 to 4.

6. The use according to claim 5, characterized in that, -R is 1,2-ethylene, and -x is a positive integer from 1 to 4, preferably 2 or 3.

7. The use according to any one of claims 1 to 6, characterized in that, R 1 Choose from the following groups of components -C 10 To C 30 straight-chain alkenyl -C9 to C 30 Branched alkenes can be obtained through the polymerization of C3 and / or C4 olefins. - A branched alkenyl group, derived from homopolymers and copolymers containing isobutylene in polymeric form, wherein the number average molecular weight Mn of the alkenyl group is from 104 g / mol to 100,000 g / mol, preferably from 104 g / mol to 10,000 g / mol, particularly preferably from 156 g / mol to 5,000 g / mol, and even more particularly preferably from 500 g / mol to 2,500 g / mol.

8. The use according to any one of claims 1 to 6, characterized in that, Group R 1 For the following groups, Where n is 0 to 960, preferably 0 to 94, particularly preferably 1 to 46, and even more particularly preferably 3 to 22.

9. Use according to any one of the preceding claims for simultaneously improving at least two, preferably all three, of the following properties of a rubber-containing tire: -Wetland adhesion - Abrasion resistance - Rolling resistance.

10. Use for reducing microplastics generated by tire wear, according to any one of claims 1 to 9.

11. Use according to any one of claims 1 to 9 for reducing fuel consumption and related emissions by reducing the rolling resistance of rubber-containing tires.

12. The use according to any one of the preceding claims, characterized in that, The rubber is isobutylene-isoprene rubber.

13. The use according to any one of claims 1 to 11, characterized in that, The rubber is styrene-butadiene rubber.

14. A method for reducing the viscosity of rubber compound during the manufacture of rubber-containing tires, wherein in the method, the viscosity of the rubber compound is reduced by... -at least one rubber and - Carbon black and / or silicates and - At least one processing aid and / or additive for improving at least one performance characteristic of the tire. Mix in a kneader and / or extruder. Its features are, At least one amine derivative as described in any one of claims 1 to 8 is added to the rubber compound before and / or during processing.

15. Use of an amine derivative as described in any one of claims 1 to 8, for the purpose of reducing the viscosity of rubber compounds in the manufacture of rubber-containing tires.

16. A rubber compound comprising... - At least one type of rubber, said rubber being selected from the group consisting of natural rubber, polybutadiene, styrene-butadiene copolymer, and polyisoprene, preferably a mixture of natural rubber and styrene-butadiene copolymer, a mixture of natural rubber and polybutadiene, or a mixture of natural rubber and polyisoprene. - At least one filler, said filler being selected from the group consisting of calcium carbonate, clay, mica, silica, silicates, talc, bentonite, titanium dioxide, alumina, zinc oxide, and carbon black. - At least one antioxidant, preferably p-phenylenediamine, - At least one peroxide and / or polyamine as a curing agent and / or crosslinking agent - At least one vulcanization process activator, said vulcanization process activator being selected from the group consisting of amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenamides, thiocarbamates, and xanthates. - At least one silane crosslinking agent, said silane crosslinking agent being selected from the group consisting of bis((C1-C4)alkoxy(C1-C4)alkylsilyl(C1-C4)alkyl) polysulfides (especially disulfides, trisulfides or tetrasulfides), bis(3-trimethoxysilylpropyl), bis(3-triethoxysilylpropyl) polysulfides, bis(3-triethoxysilylpropyl) tetrasulfide of the formula [(C2H5O)3Si(CH2)3S2]2 and bis(triethoxysilylpropyl) disulfide of the formula [(C2H5O)3Si(CH2)3S]2 (TESPD), and at least one amine derivative as claimed in any one of claims 1 to 8.

Images