Polyisobutylene derivatives as rubber additives

Abstract

This invention relates to the use of various polyisobutylene derivatives as rubber additives, particularly for the dispersion and compatibilization of additives in vehicle tire rubber, such as carbon black, zinc oxide, and silicates.

Description

describe

[0001] This invention relates to the use of polyisobutylene containing double bonds and various polyisobutylene derivatives as rubber additives, particularly for the dispersion and compatibilization of additives in vehicle tire rubber.

[0002] Modern vehicle tires face higher performance requirements, especially in terms of sustainable development. In particular, they require low rolling resistance to reduce fuel consumption and related emissions, as well as high wear resistance to reduce tire wear (e.g., in the form of microplastics) and extend tire life, while maintaining tire adhesion to the ground under different conditions (e.g., temperature, weather conditions, 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] As known from WO 2007 / 70063, polyisobutylene succinic anhydride (PIBSA) is incorporated as a processing aid into brominated butyl rubber to obtain a viscosity and curing time that facilitates processing. The given molecular weight range for PIBSA is 400 to 5000, and the anhydride functionality is 0.5 mol% to 2.0 mol%, with a number-average molecular weight reaching 10000, but no commercially available products are provided.

[0007] The other functions of polyisobutylene succinic anhydride besides its role as a processing aid are not given, and cannot be derived from the examples.

[0008] The role of polyisobutylene succinic anhydride in improving grip and abrasion resistance in rubber compositions is known from DE 19941166 A1.

[0009] WO 2009 / 158604 describes the use of metal salts of polyisobutylene succinic acid with a number average molecular weight of 250 to 100,000 in rubber compounds to improve the properties of the rubber compounds.

[0010] The object of this invention is to use a material having at least one double bond.

[0011] - Polyisobutylene (A) or

[0012] - Polyisobutylene derivative (B)

[0013] This can be achieved to improve at least one of the following properties of rubber-containing tires.

[0014] - Dispersion coefficient

[0015] -particle size

[0016] -Wetland adhesion

[0017] - Abrasion resistance

[0018] - Rolling resistance,

[0019] Or it can be used to capture alcohols released during tire manufacturing.

[0020] The polyisobutylene derivative (B) contains at least one, preferably at least two, isolated double bonds, and is capable of being made...

[0021] -At least one polyisobutylene-substituted succinic anhydride (PIBSA) and

[0022] - at least one formula

[0023] HO-R 15 -CR 16 =CR 17 R 18

[0024] Unsaturated alcohols and / or

[0025] - at least one formula

[0026] H2N-R 19 -CR 20 =CR 21 R 22

[0027] or

[0028] HN(-R 19 -CR 20 =CR 21 R 22 It is obtained by reacting monounsaturated amines with 2.

[0029] The present invention will be described in detail below:

[0030] rubber

[0031] In vehicle tire compounds, particularly in tread compounds, exemplarily a mixture of butyl rubber and diene elastomer, along with other components, is used.

[0032] Such mixtures are described, for example, in paragraphs

[0008] to

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

[0033] 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.

[0034] Diene elastomers typically have a glass transition temperature (Tg) ranging from -75°C to 0°C.

[0035] polybutadiene

[0036] 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%.

[0037] Other comonomers can be polymerized in small quantities.

[0038] 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.

[0039] 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".

[0040] Styrene-butadiene copolymer

[0041] 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%.

[0042] One could also think of styrene-butadiene-isoprene terpolymer.

[0043] Polyisoprene

[0044] This is understood as homopolymers and copolymers of isoprene, which can be of natural or preferably synthetic origin.

[0045] The proportion of cis-1,4-unit is at least 90 mol%, preferably at least 98 mol%.

[0046] Butyl rubber

[0047] 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.

[0048] The preferred isoolefin is isobutene, the preferred conjugated diene is 1,3-butadiene and isoprene, and isoprene is particularly preferred.

[0049] The viscosity-average molecular weight of the butyl rubber is 100,000 to 1,500,000, preferably 250,000 to 800,000.

[0050] 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.

[0051] plasticizer

[0052] 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.

[0053] 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.

[0054] 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.

[0055] filler

[0056] 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.

[0057] Typical particle size ranges from 0.0001 μm to 100 μm.

[0058] 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.

[0059] BET surface area is typically less than 450m² 2 / g, preferably 30m 2 / g to 400m 2 / g, with a particularly high selection of 100m 2 / g to 250m 2 / g, more preferably 130m 2 / g to 220m 2 / g; CTAB surface area is 100m² 2 / g to 250m 2 / g and preferably 150m 2 / g to 200m 2 / g; DBP oil absorption value is 150ml to 250ml / 100g; average projected area of ​​aggregates before use is greater than 8500nm. 2 And preferably 9000nm 2 Up to 11000nm 2 When thermomechanically mixed with elastomers, the nanometer size is 7000 nm. 2 Up to 8400nm 2 The selected silica can be used alone or in combination with other fillers, such as carbon black or another conventional silica.

[0060] As a particularly suitable silica, silica obtained, for example, by the method described in European patent application EP-A-157703 is applicable.

[0061] 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.

[0062] antioxidants

[0063] 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.

[0064] Curing agent, crosslinking agent, activator

[0065] The rubber composition is reacted with at least one curing agent and at least one crosslinking agent known to those skilled in the art.

[0066] Examples include organic peroxides and polyamines.

[0067] In particular, sulfur is used as a sulfiding agent for this purpose.

[0068] 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.

[0069] 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.

[0070] In one particular embodiment, bis(3-triethoxysilylpropyl)tetrasulfide is used.

[0071] 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.

[0072] Zinc oxide is preferred.

[0073] Silane coupling agent

[0074] Typical coupling agents ensure stable chemical and / or physical interactions between components (e.g., between fillers and rubber).

[0075] They are usually sulfur-containing compounds, organosilanes, or polysiloxanes.

[0076] 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.

[0077] composition

[0078] 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.

[0079] 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.

[0080] The filler, especially carbon black and silicate, typically accounts for 20 to 200 phr, preferably 30 to 150 phr.

[0081] The proportion of plasticizer is usually between 10 phr and 30 phr.

[0082] According to the invention, polyisobutylene (A) or a specific polyisobutylene derivative (B) having at least one double bond, preferably one to four double bonds, particularly preferably one to three double bonds, and even more particularly preferably one or two double bonds are added to these rubbers.

[0083] This double bond is an isolated double bond and is not considered in conjunction with other C=C double bonds or carbonyl conjugated double bonds.

[0084] Polyisobutylene and its derivatives are described in detail below:

[0085] 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.

[0086] 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.

[0087] In another preferred embodiment, polyisobutylene refers to polyisobutylene with a Mn value of 2300 to 10000.

[0088] 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, an industrial C4 hydrocarbon stream, particularly residual liquid 1 stream, b / b stream from an FCC refining unit, product stream from propylene-isobutane co-oxidation, or product stream from a metathesis unit, containing 1% to 100% by weight, particularly 1% to 99% by weight, particularly 1% to 90% by weight, particularly 30% to 60% by weight, is used as the monomer source for polymerization.

[0089] 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.

[0090] 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.

[0091] 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").

[0092] 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.

[0093] 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.

[0094] "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.

[0095] 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 consume 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.

[0096] 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%.

[0097] 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%.

[0098] 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.

[0099] According to this implementation method, resources are saved, and the product is made from at least part of renewable raw materials.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] In one embodiment, according to the invention, polyisobutylene (A) having at least one, preferably exactly one, double bond is used.

[0105] 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...

[0106] Isomers with α-double bonds ,as well as

[0107] Isomers with β-double bonds ,

[0108] in,

[0109] The residue PIB represents the remaining portion of polyisobutylene without the indicated substructure.

[0110] 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.

[0111] In a preferred embodiment of the invention, the polyisobutylene (A) has a number-average molecular weight Mn of 300 g / mol to 10000 g / mol, preferably 500 g / mol to 5000 g / mol, particularly preferably 700 g / mol to 2500 g / mol, and an α-double bond content of at least 70%, preferably at least 75%, particularly preferably at least 80%, even more particularly preferably at least 85%, and especially at least 90%. This type of polyisobutylene is also known as low molecular weight, highly reactive polyisobutylene.

[0112] 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%.

[0113] Except for isomers with α- or β- double bonds, the content of other isomers is usually no more than 5%.

[0114] 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.

[0115] In another 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 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.

[0116] 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%.

[0117] The molecular weight was determined by gel permeation chromatography using polystyrene as a standard.

[0118] In another preferred embodiment, the added compound is a polyisobutylene derivative (B), wherein these polyisobutylene derivatives (B) contain at least one, preferably at least two, isolated double bonds, and are capable of being made...

[0119] -At least one polyisobutylene-substituted succinic anhydride (PIBSA) and

[0120] - at least one formula

[0121] HO-R 15 -CR 16 =CR 17 R 18

[0122] Unsaturated alcohols and / or

[0123] - at least one formula

[0124] H2N-R 19 -CR 20 =CR 21 R 22

[0125] or

[0126] HN(-R 19 -CR 20 =CR 21 R 22 It is obtained by reacting monounsaturated amines with 2.

[0127] In a preferred embodiment, for these polyisobutylene-substituted succinic anhydrides, highly reactive polyisobutylene with a number-average molecular weight Mn of 300 g / mol to 10000 g / mol, preferably 500 g / mol to 5000 g / mol, and particularly preferably 700 g / mol to 2500 g / mol is used.

[0128] In another preferred embodiment, the number-average molecular weight M can also be used. n Polyisobutylene in the range of 10,000 to 100,000, as described in WO 2017 / 216022.

[0129] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride (PIBSA) used also contains more than one monosubstituted product.

[0130] 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:

[0131] BMG = 100% × [(wt-%(BM PIBSA) / (wt-%(BM PIBSA)+wt-%(PIBSA))]

[0132] 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.

[0133] 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.

[0134] 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.

[0135] In a preferred embodiment, the degree of bismaleidation of PIBSA is at least 5%, preferably at least 8%, and particularly preferably at least 10%.

[0136] 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.

[0137] 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%.

[0138] The best results are obtained when the degree of bismaleidation is 10% to 50%, preferably 12% to 45%, and particularly preferably 15% to 40%.

[0139] In one embodiment of the present invention, to prepare polyisobutylene derivative (B), polyisobutylene succinic anhydride can be reacted with formula...

[0140] HO-R 15 -CR 16 =CR 17 R 18

[0141] The reaction of monounsaturated or polyunsaturated, preferably monounsaturated, alcohols.

[0142] in,

[0143] R 15 The residue is a divalent organic residue optionally interrupted and / or substituted by a heteroatom, preferably an aliphatic organic residue optionally interrupted and / or substituted by a heteroatom, particularly preferably an alkylene residue 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 methylene.

[0144] R 16 R 17 and R18 Each of them is independently hydrogen or C1 to C6 alkyl, preferably hydrogen or C1 to C4 alkyl, particularly preferably hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and even more particularly preferably hydrogen or methyl, ethyl or n-butyl.

[0145] Preferred unsaturated alcohols are allyl alcohol, methyl allyl alcohol, but-2-en-1-ol, but-3-en-1-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, geraniol, farnesol, and linalool, especially allyl alcohol.

[0146] Ideally, these reaction products include

[0147] -At least one of the following compounds derived from monomaleyl PIBSA

[0148]

[0149] or

[0150]

[0151] -A compound derived from bismaleidized PIBSA

[0152]

[0153] or

[0154]

[0155] in,

[0156] PIB, R 15 R 16 R 17 and R 18 Each has the aforementioned meaning, and

[0157] The interconnected dashed key system each represents a double bond on one of these keys.

[0158] And the corresponding isomers, of which alcohols

[0159] HO-R 15 -CR 16 =CR 17 R 18

[0160] It is linked to another carboxyl group in the succinate structure.

[0161] One can also think of the two carboxyl groups in the succinate structure and the formula HO-R. 15 -CR 16 =CR 17 R 18 Compounds linked to alcohols.

[0162] In another preferred embodiment of the preparation of polyisobutylene derivative (B), polyisobutylene succinic anhydride is reacted with a monounsaturated or polyunsaturated, preferably monounsaturated, amine. This amine can be a primary or secondary amine.

[0163] Preferred unsaturated amines have the formula

[0164] H2N-R 19 -CR 20 =CR 21 R 22

[0165] or

[0166] HN(-R 19 -CR 20 =CR 21 R 22 )2,

[0167] in,

[0168] R 19 It is a divalent alkylene residue 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, and 1,6-hexylene, especially methylene.

[0169] R 20 R 21 and R 22 Each of them is independently hydrogen or C1 to C6 alkyl, preferably hydrogen or C1 to C4 alkyl, particularly preferably hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and even more particularly preferably hydrogen or methyl, ethyl or n-butyl.

[0170] Preferred unsaturated amines are allylamine, methylallylamine, and diallylamine.

[0171] Ideally, amine H2N-R 19 -CR 20 =CR 21 R 22 The reaction products include

[0172] -At least one of the following compounds derived from monomaleyl PIBSA

[0173]

[0174] or

[0175]

[0176] -A compound derived from bismaleidized PIBSA

[0177]

[0178] or

[0179]

[0180] in,

[0181] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning, and

[0182] The interconnected dashed key system each represents a double bond on one of these keys.

[0183] And the corresponding isomers, of which amines

[0184] H2N-R 19 -CR 20 =CR 21 R 22

[0185] It is linked to another carboxyl group in the succinate structure.

[0186] One can also think of the two carboxyl groups in the succinate structure and the formula H2N-R. 19 -CR 20 =CR 21 R 22 Amine-linked compounds.

[0187] Ideally, amine HN-(-R) 19 -CR 20 =CR 21 R 22 The reaction products of )2 include

[0188] -At least one of the following compounds derived from monomaleyl PIBSA

[0189]

[0190] or

[0191]

[0192] -A compound derived from bismaleidized PIBSA

[0193]

[0194] or

[0195]

[0196] in,

[0197] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning.

[0198] z represents 2, and

[0199] The interconnected dashed key system each represents a double bond on one of these keys.

[0200] And the corresponding isomers, of which amines

[0201] HN-(-R 19 -CR 20 =CR 21 R 22 )2

[0202] It is linked to another carboxyl group in the succinate structure.

[0203] One can also think of the two carboxyl groups in the succinate structure and the formula HN-(-R) 19 -CR 20 =CR 21 R 22 Compounds with amine linkages of 2.

[0204] The polyisobutylene (A) or polyisobutylene derivative (B) according to the invention is typically added to the rubber mixture in an amount of 2 phr to 20 phr, preferably 4 phr to 14 phr, and particularly preferably 5 phr to 10 phr.

[0205] Typically, compounds (A) and (B) 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 compounds (A) and (B) before adding other components, particularly antioxidants, activators, and / or plasticizers.

[0206] 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...

[0207] -at least one rubber and

[0208] - Carbon black and / or silicates and

[0209] - At least one processing aid and / or additive for improving at least one performance characteristic of tires.

[0210] Mix in a kneader and / or extruder.

[0211] Wherein, at least one polyisobutylene and / or at least one polyisobutylene (A) or polyisobutylene derivative (B) described above are added to the rubber compound before and / or during processing.

[0212] The vulcanization and preparation methods of rubber compounds are known in themselves and can be transferred to the application of compounds (A) and (B).

[0213] One advantage of compounds (A) and (B) is that they have a beneficial effect on improving at least one of the following properties of rubber-containing tires.

[0214] - Dispersion coefficient

[0215] -particle size

[0216] -Wetland adhesion

[0217] - Abrasion resistance

[0218] - Rolling resistance.

[0219] Compound (A) is particularly suitable for improving the dispersion of fillers, especially silica, in rubber compounds.

[0220] In addition, they exhibit a particular advantage in reducing rolling resistance.

[0221] During the manufacture of rubber compounds, compound (A) also exhibits the advantage of significantly reducing the viscosity of the compound during processing.

[0222] Compound (B) is particularly suitable for improving the dispersion of fillers, especially silica, in rubber compounds and / or reducing filler particle size.

[0223] Furthermore, compound (B) exhibits advantages in terms of wet grip and / or rolling resistance and / or abrasion resistance at low temperatures (-10°C) in tires containing it. Preferably, compound (B) improves at least two of these three properties. A particular advantage of compound (B) is that it simultaneously improves wet grip, rolling resistance, and abrasion resistance in tires at low temperatures (-10°C).

[0224] In addition, compound (B) also showed the advantage of significantly reducing the viscosity during processing of rubber compounds during manufacturing.

[0225] By improving tire wear resistance, the amount of microplastics released during tire wear in motor vehicle operation can be reduced.

[0226] In addition, compounds (A) and (B), especially (B), are suitable for combining released alcohols, particularly ethanol, during the manufacture of tire rubber compounds, thereby reducing emissions during the manufacturing process.

[0227] Without being bound by theory, it is speculated that such alcoholic ROH, especially ethanol, released during tire rubber compound manufacturing, reacts with unreacted succinic anhydride or carboxylic acid groups and is bound as a carboxylic acid ester. It is also conceivable that the released alcoholic ROH, especially ethanol, will undergo transesterification to convert alcohol HO-R... 15 -CR 16 =CR 17 R 18 Or, in the amide exchange reaction, the amine H2N-R 19 -CR 20 =CR 21 R 22 or HN(-R) 19 -CR 20 =CR 21 R 22 )2. Displaced from existing carboxylic acid ester bonds or amide bonds.

[0228] From the above-mentioned source, HO-R 15 -CR 16 =CR 17 R 18 The structure of the reaction will result in the following reaction products:

[0229] -At least one of the following compounds derived from monomaleyl PIBSA

[0230]

[0231] or

[0232]

[0233] -A compound derived from bismaleidized PIBSA

[0234]

[0235]

[0236]

[0237] or

[0238]

[0239] in,

[0240] PIB, R 15 R16 R 17 and R 18 Each has the aforementioned meaning.

[0241] R is a residue of the released alcohol, particularly an ethyl group, and

[0242] The interconnected dashed key system each represents a double bond on one of these keys.

[0243] And the corresponding isomers, of which alcohols

[0244] HO-R 15 -CR 16 =CR 17 R 18

[0245] It is linked to another carboxyl group in the succinate structure.

[0246] The above-mentioned origin is derived from monosubstituted amine H2N-R 19 -CR 20 =CR 21 R 22 The structure of the reaction will result in the following reaction products:

[0247] -At least one of the following compounds derived from monomaleyl PIBSA

[0248]

[0249] or

[0250]

[0251] -A compound derived from bismaleidized PIBSA

[0252]

[0253]

[0254]

[0255] or

[0256]

[0257] in,

[0258] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning.

[0259] R is a residue of the released alcohol, particularly an ethyl group, and

[0260] The interconnected dashed key system each represents a double bond on one of these keys.

[0261] And the corresponding isomers, of which amines

[0262] H2N-R 19 -CR 20 =CR 21 R 22

[0263] It is linked to another carboxyl group in the succinate structure.

[0264] The above-mentioned origin is derived from the disubstituted amine HN-(-R) 19 -CR 20 =CR 21 R 22 The structure of the reaction will lead to the following reaction products:

[0265] -At least one of the following compounds derived from monomaleyl PIBSA

[0266]

[0267] or

[0268]

[0269] -A compound derived from bismaleidized PIBSA

[0270]

[0271]

[0272]

[0273] or

[0274]

[0275] in,

[0276] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning.

[0277] R represents the residue of the released alcohol, particularly the ethyl group.

[0278] z represents 2, and

[0279] The interconnected dashed key system each represents a double bond on one of these keys.

[0280] And the corresponding isomers, of which amines

[0281] HN-(-R 19 -CR 20 =CR 21 R 22 )2

[0282] It is linked to another carboxyl group in the succinate structure.

[0283] In addition, compounds can be additionally formed through ester exchange or amide exchange reactions, wherein the two carboxyl groups of the succinic acid structure are linked to residues of the alcohol ROH.

[0284] Because of the presence of unsaturated groups in these structures, esters formed with alcohol ROH (especially ethanol) can also improve at least one of the following properties of rubber tires.

[0285] - Dispersion coefficient

[0286] -particle size

[0287] -Wetland adhesion

[0288] - Abrasion resistance

[0289] - Rolling resistance.

[0290] Another advantage of this invention is that compounds (A) and (B), especially (B), are capable of reacting with other components of the rubber compound, such as with the rubber itself, and particularly with silane coupling agents. This improves the compatibility between the components of the rubber compound.

[0291] Of particular advantage is the reaction product of highly reactive polyisobutylene (A) having at least one double bond with a silane coupling agent. Preferably, the following structure is formed:

[0292]

[0293]

[0294] and / or

[0295]

[0296] in,

[0297] The residue PIB represents the remaining portion of polyisobutylene without the indicated substructure.

[0298] X represents -(S) x -R 25 -Si(OR 26 )3,

[0299] x represents 1, 2, 3, or 4.

[0300] R 25 It is an alkylene residue 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.

[0301] 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.

[0302] From the above-mentioned source, HO-R 15 -CR 16 =CR 17 R 18 The structure of the reaction will result in the following reaction products:

[0303] -At least one of the following compounds derived from monomaleyl PIBSA

[0304]

[0305] or

[0306]

[0307] -A compound derived from bismaleidized PIBSA

[0308]

[0309]

[0310]

[0311] or

[0312]

[0313] in,

[0314] PIB, R 15 R 16 R 17 and R 18 Each has the aforementioned meaning.

[0315] X represents -(S) x -R 25 -Si(OR 26 )3,

[0316] x represents 1, 2, 3, or 4.

[0317] R 25 It is an alkylene residue 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.

[0318] R 26 Representing C1 to C6 alkyl groups, preferably C1 to C4 alkyl groups, 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, and

[0319] The interconnected dashed key system each represents a double bond on one of these keys.

[0320] And the corresponding isomers, of which alcohols

[0321] HO-R 15 -CR 16 =CR 17 R 18

[0322] It is linked to another carboxyl group in the succinate structure.

[0323] The above-mentioned origin is derived from monosubstituted amine H2N-R 19 -CR 20 =CR 21 R 22 The structure of the reaction will result in the following reaction products:

[0324] -At least one of the following compounds derived from monomaleyl PIBSA

[0325]

[0326] or

[0327]

[0328] -A compound derived from bismaleidized PIBSA

[0329]

[0330]

[0331]

[0332] or

[0333]

[0334] in,

[0335] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning.

[0336] X represents -(S) x -R 25 -Si(OR 26 )3,

[0337] x represents 1, 2, 3, or 4.

[0338] R 25 It is an alkylene residue 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.

[0339] R 26 Representing C1 to C6 alkyl groups, preferably C1 to C4 alkyl groups, 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, and

[0340] The interconnected dashed key system each represents a double bond on one of these keys.

[0341] And the corresponding isomers, of which amines

[0342] H2N-R 19 -CR 20 =CR 21 R 22

[0343] It is linked to another carboxyl group in the succinate structure.

[0344] The above-mentioned origin is derived from the disubstituted amine HN-(-R) 19 -CR 20 =CR 21 R 22 The structure of the reaction will lead to the following reaction products:

[0345] -At least one of the following compounds derived from monomaleyl PIBSA

[0346]

[0347] or

[0348]

[0349] -A compound derived from bismaleidized PIBSA

[0350]

[0351]

[0352]

[0353] or

[0354]

[0355] in,

[0356] PIB, R 19 R 20 R 21 and R 22 Each has the aforementioned meaning.

[0357] X represents -(S) x -R 25 -Si(OR 26 )3,

[0358] x represents 1, 2, 3, or 4.

[0359] R 25 It is an alkylene residue 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.

[0360] R 26 Representing C1 to C6 alkyl groups, preferably C1 to C4 alkyl groups, 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.

[0361] z represents 2, and

[0362] The interconnected dashed key system each represents a double bond on one of these keys.

[0363] And the corresponding isomers, of which amines

[0364] HN-(-R 19 -CR 20 =CR 21R 22 )2

[0365] It is linked to another carboxyl group in the succinate structure.

[0366] One advantage of these reaction products with silane coupling agents is that they can react with silicates contained in rubber compounds to form Si-O-Si bonds, thereby improving silicate incorporation and compatibility, and can additionally contribute to improving at least one of the following properties of rubber-containing tires.

[0367] - Dispersion coefficient

[0368] -particle size

[0369] -Wetland adhesion

[0370] - Abrasion resistance

[0371] - Rolling resistance.

[0372] Therefore, these reaction products and rubber compounds containing these reaction products are the subject of this invention.

[0373] Another topic is rubber compounds, including

[0374] - At least one type of rubber, selected from the group consisting of isobutylene-isoprene rubber, styrene-butadiene rubber, and natural rubber and mixtures thereof.

[0375] - At least one filler selected from the group consisting of calcium carbonate, clay, mica, silica, silicate, talc, bentonite, titanium dioxide, alumina, zinc oxide, and carbon black.

[0376] - At least one antioxidant, preferably p-phenylenediamine,

[0377] - At least one peroxide and / or polyamine as a curing agent and / or crosslinking agent

[0378] - At least one vulcanization process activator, wherein the vulcanization process activator is selected from the group consisting of amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenamides, thiocarbamates, and xanthates.

[0379] - 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 (TESPT) and bis(triethoxysilylpropyl)disulfide of the formula [(C2H5O)3Si(CH2)3S]2 (TESPD), and

[0380] -Having at least one double bond

[0381] - Polyisobutylene (A) or

[0382] - A polyisobutylene derivative (B), which contains at least one, preferably at least two, isolated double bonds and is capable of being made...

[0383] -At least one polyisobutylene-substituted succinic anhydride (PIBSA) and

[0384] - at least one formula

[0385] HO-R 15 -CR 16 =CR 17 R 18

[0386] Unsaturated alcohols and / or

[0387] - at least one formula

[0388] H2N-R 19 -CR 20 =CR 21 R 22

[0389] or

[0390] HN(-R 19 -CR 20 =CR 21 R 22 It is obtained by reacting monounsaturated amines with 2.

[0391] The present invention is illustrated by the following embodiments, but is not limited thereto. Example

[0392] Preparation Examples

[0393] Compound 1

[0394] Glissopal of BASF SE (Ludwigshafen)® 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%.

[0395] Compound 2

[0396] Glissopal of BASF SE (Ludwigshafen) ® 2300, number-average molecular weight Mn (determined by GPC) approximately 2300 g / mol, polydispersity approximately 1.8, α-double bond content (as determined by GPC) 13 (C NMR determination) Approximately 80%, β-double bonds 8%.

[0397] Compound 3

[0398] Commercially available polyisobutylene-substituted succinic anhydride, based on highly reactive polyisobutylene with a number-average molecular weight of approximately 1000 g / mol, can be used as a glycoside. ® SAF was purchased from BASF SE (Ludwigshafen), with a saponification value of 87 mg KOH / g.

[0399] Compound 4

[0400] 101.11 g of compound 3 was dissolved in 100.00 g of toluene. 13.21 g (0.13 mol) of diallylamine 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 = 112.30 g).

[0401] Compound 5

[0402] 122.48 g of compound 3 was dissolved in 100.00 g of toluene. 14.24 g (0.16 mol) of isopentenol 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 = 132.00 g).

[0403] Compound 6

[0404] 122.48 g of compound 3 was dissolved in 100.00 g of toluene. 10.73 g (0.12 mol) of isopentenol 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. 12.11 g (0.12 mol) of diallylamine was then added to the reaction mixture, and the mixture was stirred at 50 °C for 15 hours (yield = 122.00 g).

[0405] Method Description

[0406] Improvement of dispersion coefficient

[0407] 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.

[0408] The goal is to achieve a high dispersion factor.

[0409] Particle size determination

[0410] The average diameter of the particles was determined together with the dispersion coefficient using optical methods.

[0411] Smaller particle size is advantageous.

[0412] Wet grip and rolling resistance at low temperatures (-10℃)

[0413] 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.

[0414] Measurement parameters:

[0415] Temperature range -60℃ to 80℃

[0416] 1Hz frequency

[0417] Amplitude 0.5%

[0418] 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.

[0419] 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.

[0420] abrasion resistance

[0421] 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... -1Wear was measured under certain conditions.

[0422] The abrasion resistance index is expressed as a percentage [%], and the higher the value, the better.

[0423] Reduce viscosity during processing

[0424] 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).

[0425] The measured viscosity is expressed in Mooney units (ME), with a low value indicating low viscosity.

[0426] Capture ethanol released during processing

[0427] Mix silica and the test sample in a 1:1 ratio, and place the mixture into a 2g headspace vial, sealing it with a diaphragm. Heat the mixture to 140°C and maintain the temperature for 30 minutes. Analyze the gas phase using gas chromatography (Agilent 6890N).

[0428] Injector temperature: 140℃, column: 60m capillary column VF-5ms, column temperature: 40℃ isothermal for 4 minutes, then increased to 280℃ isothermal at a rate of 10℃ / min, detector: Agilent mass selection detector 5975C, carrier gas: helium.

[0429] Low values ​​are advantageous due to occupational health regulations.

[0430] Application Examples

[0431] 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:

[0432]

[0433] 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] ).

[0434] 2) Amorphous SiO2, Evonik's Ultrasil 7000 GR

[0435] 3) Bis(triethoxysilylpropyl)tetrasulfide

[0436] 4) IPPD: N-isopropyl-N'-phenyl-1,4-phenylenediamine

[0437] 5)DPG: N,N'-diphenylguanidine

[0438] 6) CBS: N-cyclohexylbenzothiazole-2-sulfenamide

[0439] The rubber compound according to the present invention

[0440] Silica-containing rubber compounds K4 to K6 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.

[0441]

[0442] These rubber compounds according to the invention are compared in specified application examples with a reference rubber compound containing silica.

[0443] Example 1 (Improvement of Dispersion Coefficient)

[0444]

[0445] Example 2 (Reducing Particle Size)

[0446]

[0447] Example 3 (Wet grip at low temperature (-10℃))

[0448]

[0449] Example 4 (Rolling Resistance)

[0450]

[0451] Example 5 (Abrasion Resistance)

[0452]

[0453] Example 6 (Reducing viscosity during processing)

[0454]

Claims

1. A compound having at least one double bond - Polyisobutylene (A) or - Use of polyisobutylene derivative (B) for improving at least one of the following properties of rubber-containing tires. - Dispersion coefficient -particle size -Wetland adhesion - Abrasion resistance - Rolling resistance, Or it can be used to capture alcohols released during tire manufacturing. The polyisobutylene derivative (B) contains at least one, preferably at least two, isolated double bonds, and is capable of being made by... -At least one polyisobutylene-substituted succinic anhydride (PIBSA) and - at least one formula HO-R 15 -CR 16 =CR 17 R 18 Unsaturated alcohols and / or - at least one formula H2N-R 19 -CR 20 =CR 21 R 22 or HN(-R 19 -CR 20 =CR 21 R 22 It is obtained by reacting monounsaturated amines with 2. in, R 15 The residue is a divalent organic residue optionally interrupted by a heteroatom, preferably an aliphatic organic residue optionally interrupted by a heteroatom, particularly preferably an alkylene residue having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms, and even 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-hexylene, especially methylene. R 16 R 17 and R 18 Each of the components is independently hydrogen or a C1 to C6 alkyl group, preferably hydrogen or a C1 to C4 alkyl group, particularly preferably hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and even more particularly preferably hydrogen or methyl, ethyl or n-butyl. R 19 It is a divalent alkylene residue 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, and 1,6-hexylene, especially methylene. R 20 R 21 and R 22 Each of them is independently hydrogen or C1 to C6 alkyl, preferably hydrogen or C1 to C4 alkyl, particularly preferably hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and even more particularly preferably hydrogen or methyl, ethyl or n-butyl.

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

3. The use according to any one of the preceding claims, characterized in that, The rubber comprises styrene-butadiene rubber.

4. The use according to any one of the preceding claims, characterized in that, The rubber includes natural rubber.

5. The use according to any one of the preceding claims, particularly the use of compound (B), for simultaneously improving at least two, preferably all three, of the following properties of a rubber-containing tire. -Wetland adhesion - Abrasion resistance - Rolling resistance.

6. The use according to any one of claims 1 to 5, particularly the use of said compound (B), for reducing microplastics generated by tire wear.

7. 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 polyisobutylene and / or at least one polyisobutylene (A) or polyisobutylene derivative (B) as described in claim 1 are added to the rubber compound before and / or during processing.

8. Use of the polyisobutylene (A) and / or polyisobutylene derivative (B) as described in claim 1 for reducing the viscosity of rubber compounds in the manufacture of rubber-containing tires.

9. The use and method according to any one of the preceding claims, characterized in that, The polyisobutylene (A) has a number-average molecular weight Mn of 300 g / mol to 10000 g / mol and an α-double bond isomer content of at least 70%.

10. The use and method according to any one of claims 1 to 8, characterized in that, The polyisobutylene (A) has a number-average molecular weight Mn of greater than 10,000 g / mol to 100,000 g / mol and an α-double bond isomer content of at least 20% to 60%.

11. The use and method according to any one of claims 1 to 8, characterized in that, The unsaturated alcohol is selected from the group consisting of allyl alcohol, methyl allyl alcohol, but-2-en-1-ol, but-3-en-1-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, geraniol, farnesol, and linalool.

12. The use and method according to any one of claims 1 to 8, characterized in that, The at least one unsaturated amine is selected from the group consisting of allylamine, methylallylamine, and diallylamine.

13. The use and method according to any one of claims 1 to 8, characterized in that, The degree of bismaleidation of the polyisobutylene-substituted succinic anhydride used in the preparation of the polyisobutylene derivative (B) is at least 5% to 100%, preferably 10% to 50%.

14. A rubber compound comprising... - At least one type of rubber, said rubber being selected from the group consisting of isobutylene-isoprene rubber, styrene-butadiene rubber, and natural rubber and mixtures thereof. - 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, and -Having at least one double bond - Polyisobutylene (A) or - A polyisobutylene derivative (B), said polyisobutylene derivative comprising at least one, preferably at least two, isolated double bonds, and capable of being made by... -At least one polyisobutylene-substituted succinic anhydride (PIBSA) and - at least one formula HO-R 15 -CR 16 =CR 17 R 18 Unsaturated alcohols and / or - at least one formula H2N-R 19 -CR 20 =CR 21 R 22 or HN(-R 19 -CR 20 =CR 21 R 22 )2 It is obtained by reacting a monounsaturated amine, as defined in claim 1.

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