Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F136/06—Butadiene
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/005—Cores
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
  • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/06—Polystyrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/18—Homopolymers or copolymers of nitriles
  • C08L33/20—Homopolymers or copolymers of acrylonitrile
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/907—Specified means of reacting components of transition metal catalyst

Definitions

• the present invention relates to a high-molecular-weight, linear, neodymium-catalysed polybutadiene having a high proportion, >95%, of cis-1,4 units and having a low proportion, ⁇ 1%, of vinyl units, and also having a small molar-mass-distribution index (MDI), and to processes for producing these and to use thereof.
• MDI small molar-mass-distribution index
• Polybutadienes are used as important constituents of rubber mixtures in the tyre industry, and it is desirable here to improve final properties, for example to reduce rolling resistance and abrasion.
• Another application sector is provided by golf-ball cores or shoe soles, where high rebound resilience is a prime concern.
• Polybutadienes having a high proportion of cis-1,4 units have been produced for a long time on a large industrial scale, and are used for producing tyres and other rubber products, and also for impact-modifying polystyrene.
• the catalyst systems used play an important part in the production of polybutadienes.
• the neodymium catalyst used in industry is a Ziegler/Natta system, which is formed from a plurality of catalyst components. Formation of the catalyst mostly involves formation of differing catalyst centres, and these can be discerned in an at least bimodal molar-mass distribution within the polymer.
• the known 3 catalyst components in the Ziegler/Natta catalyst system mostly composed of a neodymium source, a chloride source and an organoaluminium compound, are mixed in a very wide variety of ways under certain temperature conditions, and the catalyst system here is prepared, with or without an ageing process, for the polymerization reaction.
• the prior art reveals a plurality of production processes for Ziegler/Natta catalyst systems used for producing polybutadienes.
• EP 0 375 421 B1 describes a process for producing a catalyst for polymerizing butadiene, where an aluminium hydrocarbyl or aluminium hydrocarbyl hydride, neodymium neodecanoate or neodymium naphthenate, and a halogen source, are mixed in solution in a hydrocarbon (hexane) at a temperature of from ⁇ 15° C. to ⁇ 60° C., and the catalyst system here is aged for a period of at least 8 hours before it is used for the polymerization reaction.
• the ageing process is preferably carried at ⁇ 20° C.
• U.S. Pat. No. 5,686,371 discloses a process for polymerizing one or more conjugated dienes by forming the catalyst system via mixing of a salt of a rare earth, an organoaluminium compound and a silicon halide or organosilicon halide in the presence of a diene at a temperature of from 0 to 30° C. The catalyst is then aged at room temperature before it is used for the polymerization reaction.
• WO 02/068484 describes a process in which the known catalyst components, as described above, are directly introduced at a temperature of from ⁇ 20° C. to 80° C., without any prior preformation process, into a butadiene-hexane solution, and the polymerization reaction takes place in a continuous process.
• EP 1 055 659 describes a process for producing neodymium neodecanoate with high water content, above 10 000 ppm, as catalyst constituent for the solution polymerization of butadiene, where the said neodymium decanoate is combined with an alkylaluminium compound or hydride derivatives thereof, preferably diisobutylaluminium hydride (DIBAH), at a temperature of from 0 to 18° C. tert-Butyl chloride, as chloride source, is added at room temperature. The ageing process lasts for 30 minutes at the sable temperature, before these materials are used for the polymerization reaction.
• DIBAH diisobutylaluminium hydride
• EP 0 076 535 likewise describes the production of a neodymium catalyst, where the known catalyst components are combined at a temperature of 80° C. tert-Butyl chloride is used as chlorine component. Ageing is mentioned, without any explicit statement of the ageing conditions.
• EP 0 127 236 is likewise known from the prior art, and here the catalyst is produced via mixing of neodymium oxides, neodymium alcoholates and carboxylates with an organometallic halide, and also with an organic compound, at a temperature of from 20° C. to 25° C. It is also possible to carry out the mixing of the said 4 components at from 50° C. to 80° C. In this variant, the mixture is cooled to from 20 to 25° C., and then DIBAH is added. Ageing is not mentioned.
• EP 1 176 157 B1 discloses a process for producing polybutadienes with reduced solution viscosity/Mooney viscosity ratio, where a preformation process is used during catalyst production.
• the heodymium versatate is first mixed with DIBAH and isoprene at 50° C., and the said mixture is then cooled to 5° C., and then ethylaluminium sesquichloride (EASC) is added.
• the ageing period at a temperature of from 10 to ⁇ 80° C., can be from a plurality of minutes to a plurality of days.
• Comonomers an example being a bisdiene
• Comonomers are added during the polymerization reaction in order to increase the degree of branching of the polymer and also therefore to obtain the very narrow solution viscosity/Mooney viscosity ratio.
• the resultant branched polymer has at least 4 free chain ends per molecule, whereas linear molecules possess only 2 chain ends.
• the number of chain ends within the polymer has a positive correlation with energy dissipation. As the number of free chain ends increases, the amount of energy dissipation via the polymer increases. However, as the amount of energy dissipated by the polymer decreases, rolling resistance decreases and the rebound resilience of the polymer improves, for example. Accordingly, the final properties of a linear polymer having only 2 chain ends per molecule are always better than those of a branched polymer, for identical molar mass.
• Polymers having high molar mass are moreover preferable to polymers having low molar mass.
• Number-average molar masses Mn below 100 000 g/mol are particularly disadvantageous, since statistically, because of their small molar mass, they give poor binding into the polymer network, thus additionally impairing energy absorption, where this results from an increased level of free movement of the entire polymer chain.
• a polybutadiene of the type mentioned in the introduction is proposed in order to achieve the object, its Mooney viscosity (ML 1+4 100° C.) being from 70 to 90, and its molar-mass-distribution index (MDI) being ⁇ 10.
• polybutadienes have been catalysed by neodymium-containing systems.
• Systems of this type are Ziegler-Natta catalysts based on neodymium compounds which are soluble in hydrocarbons.
• the neodymium compound used particularly preferably comprises neodymium carboxylates or neodymium alcoholates, in particular neodymium neodecanoate, neodymium octanoate, neodymium naphthenate, neodymium 2,2-diethyihexanoate and/or neodymium 2,2-diethylheptanoate
• polydispersity is generally determined by gel permeation chromatography (GPC); it is the quotient obtained by dividing weight-average molar mass Mw by number-average molar mass Mn, and therefore represents the breadth of molar-mass distribution.
• the PDI index does not provide an adequate description of the actual properties of the polymer.
• no information is provided about the marginal regions of the molar-mass distribution, since the PDI merely provides a quotient calculated from the weight-average and number-average molar masses.
• MDI molar-mass-distribution index
• the polybutadiene according to the invention therefore has the desired excellent properties in tyre mixtures.
• the 1,4-cis content of the polybutadiene according to the invention is >95%, preferably >96%, and its 1,2-vinyl content is ⁇ 1%, preferably ⁇ 0.8%, particularly preferably ⁇ 0.7%.
• the solution viscosity (RT, 5.43%, toluene) of the polybutadiene according to the invention is preferably from 350 to 630 mPas, with preference from 400 to 580 mPas.
• the branching index (BI) of the polybutadiene according to the invention is from 5 to 7.
• the BI is the quotient obtained by dividing solution viscosity by Mooney viscosity. It is known that, for polymers of identical structure, solution viscosity increases proportionally as Mooney viscosity increases. If the increase is subproportional, i.e. if BI is smaller than 5, solution viscosity is reduced by polymer branching, and this reduces the linearity of the polymer and increases the undesired number of free chain ends. Any superproportional increase, i.e. BI greater than 7, is mostly brought about by an increased number of very high-molecular-weight polymer chains, and makes production of the polymer more difficult.
• the Mooney relaxation of the polybutadiene according to the invention is moreover preferably smaller than 6% after 30 sec. Mooney relaxation is brought about by slippage of the polymer chains after dynamic stressing of the polymer after the end of the Mooney measurement process, and indicates the linearity of the polymer.
• the molar-mass distribution of the polybutadiene according to the invention is Mw 90% ⁇ 1 000 000 g/mol and Mw 10%>100 000 g/mol. This molar-mass distribution is ideal for the polybutadiene according to the invention, since, as described above, it provides easy production and at the same time guarantees the desired good final properties of the polymer.
• the polybutadiene according to the invention not only has improved rolling resistance and increased rebound resilience, but also is easier to produce, because it is associated with less deposition on the walls of the reactor, and less gelling, and therefore longer operating time of the reactor. Maintenance of the reactors is thus minimized, and this saves time and expense.
• the polybutadiene according to the invention has other advantages during the production process, during transport, and during storage and processing, and also has the characteristics required for use in golf balls or ih tyre production.
• a further invention is a process for producing the polybutadiene according to the invention, by carrying out the following steps:
• the process according to the invention it was possible to form a catalyst system which is based on neodymium and which has ideal activity, and which leads to the desired abovementioned properties of the polymer.
• the final properties of the polymer and the cost-effectiveness of the production process are functions of the amount and mode of action of the catalyst constituents. If, for example, the amount of catalyst used is too small, although the molar mass rises, and the Mooney viscosity of the polymer therefore rises, there is a corresponding slowing of the reaction of the monomer, and this is undesirable for economic reasons.
• component D is a monomer identical with that used for producing high-molecular-weight neodymium-catalysed polybutadienes.
• the presence of the diene during catalyst production is particularly important, since it permits formation of a stable catalyst complex.
• the solvent used can comprise hexane, cyclohexane, toluene, or a solvent mixture of the C6 fraction. It is equally possible to use other solvents.
• the solvent can be added in pure form or in the form of solvents of the individual catalyst components.
• the amount of solvent depends on component A, where the concentration of component A with respect to the solvent is from 0.05 to 0.3 mol/L, preferably from 0.08 to 0.2 mol/L.
• the molar ratio of component A to component B is from 1:1 to 1:100, preferably from 1:3 to 1:80 and particularly preferably from 1:3 to 1:50
• the molar ratio of component A to component C is from 1:0.4 to 1:15, preferably from 1:0.5 to 1:8
• the molar ratio of component A to component D is from 1:1 to 1:200, preferably from 1:2 to 1:100 and particularly preferably from 1:3 to 1:50
• the molar ratio of component A to component E is from 1:0.5 to 1:20, preferably from 1:0.7 to 1:10 and particularly preferably from 1:0.8 to 1:8.
• the cooling temperature in step 1 of the modified catalyst production process is preferably ⁇ 10° C. or ⁇ 20° C., preferably ⁇ 30° C., particularly preferably ⁇ 60° C. It is surprising that the said step has led to a catalyst system with which the polybutadiene according to the invention can be produced.
• the invention further provides rubber mixtures comprising a polybutadiene according to the invention.
• organic solvents These solvents must be inert in relation to the catalyst system used.
• aromatic, aliphatic and cycloaliphatic hydrocarbons are suitable, examples being benzene, toluene, pentane, n-hexane, isohexane, heptane and cyclohexane.
• the polymerization reaction can be carried out either continuously or batchwise.
• the polymerization reaction is carried out at a temperature of from ⁇ 20 to 150° C., preferably from 0 to 120° C.
• the catalyst composed of components A, B, C, D and E is added to a mixture of 100 parts by weight of solvent with from 5 to 50 parts by weight, preferably from 8 to 30 parts by weight, of Monomer.
• the catalyst is deactivated via addition of small amounts of, for example, water, carboxylic acids or alcohols.
• stabilizers can be added to the polymer solution, prior to work-up.
• stabilizers used are sterically hindered phenols or aromatic amines or phosphites, e.g. 2,6-di-tert-butyl-4,5-methylphenol.
• the polymers are isolated via evaporation to concentrate the polymer solution, via precipitation by a non-solvent, such as methanol, ethanol, or acetone, or preferably via steam-distillation of the solvent.
• a non-solvent such as methanol, ethanol, or acetone
• water is removed by using suitable sieving assemblies or suitable assemblies comprising screws, examples being expeller screws and expander screws, or by using a fluidized-bed dryer.
• the usual processes are used for drying, for example in a drying cabinet or in a screw-conveyer dryer.
• the polybutadienes according to the invention can be used alone, in a blend with aromatic or aliphatic oils, or in a mixture with other rubbers.
• Suitable additional rubbers for producing rubber vulcanizates are not only natural rubber but also synthetic rubbers. Examples of preferred synthetic rubbers are described, in W. Hofmann, Kautschuktechnologie [Rubber Technology], Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They encompass inter alia
• Materials of interest for the production of motor vehicle tyres are in particular natural rubber, emulsion SBR, and also solution SBR rubbers with glass transition temperature above —50° C., which may, if appropriate, have modification by silyl ethers or by other functional groups, as described in EP-A-0 447 066, polybutadiene rubber having high 1,4-cis content (>90%), produced by using catalysts based on Ni, Co, Ti or Nd, and also polybutadiene rubber having vinyl content of from 0 to 75%, and also mixtures of these.
• the invention further provides the rubber mixtures, which generally comprise from 5 to 300 parts by weight of an active or inert filler, e.g.
• the fillers mentioned can be used alone or in a mixture.
• the rubber mixtures comprise, as fillers, a mixture of pale-coloured fillers, e.g. fine-particle silicas, and of carbon blacks, where the ratio of pale-coloured fillers to carbon blacks in the mixture is from 0.05 to 20, preferably from 0.1 to 10.
• the form in which the fillers are added to the solution of the polybutadienes according to the invention is preferably that of solids or of slurry in water or in a solvent.
• the rubber solution can be produced in advance, but it is preferable that the solution deriving from the polymerization reaction is used directly.
• the solvent is then removed thermally or preferably with the aid of steam. The conditions for the said stripping process can easily be determined through preliminary experimentation.
• the rubber mixtures according to the invention also comprise crosslinking agents, if appropriate.
• Crosslinking agents used can comprise sulphur or peroxides, and sulphur is particularly preferred here.
• the rubber mixtures according to the invention can comprise further rubber auxiliaries, such as reaction accelerators, antioxidants, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarding agents, metal oxides, and also activators, e.g. triethanolamine, polyethylene glycol, hexanetriol, etc., these being known to the rubber industry.
• Preferred filler activators are sulphur-containing silyl ethers, in particular bis(trialkoxysilylalkyl)polysulphides, as described in DE-A-2,141,159 and DE-A-2,255,577, oligomeric and/or polymeric sulphur-containing silyl ethers of DE-A-4,435,311 and EP-A-0 670 347, and metcaptoalkyltrialkoxysilanes, in particular mercaptopropyltriethoxysilane and thiocyanatoalkyl silyl ether, e.g. as described in DE-A-195 44 469.
• the amounts used of the rubber auxiliaries are usual amounts, and depend inter alia on the intended use. Examples of usual amounts are amounts of from 0.1 to 50% by weight, based on rubber.
• the rubber mixtures according to the invention can be vulcanized at usual temperatures of from 100 to 200° C., preferably from 130 to 180° C. (if appropriate under pressure of from 10 to 200 bar).
• the rubber mixtures according to the invention have excellent suitability for producing mouldings of any type.
• Non-limiting examples of the said mouldings are O-rings, profiles, gaskets, membranes, tyres, tyre treads, damping elements and hoses.
• the rubber mixtures according to the invention are moreover suitable for impact modifying thermoplastics, in particular for polystyrene and styrene/acrylonitrile copolymers.
• the rubber mixtures are particularly suitably used for golf balls, in particular golf-ball cores.
• Solution viscosity (5.43% in toluene, at room temperature): 518 mPas; BI: 6.4
• Example 3 ML 1 + 4/100 MU 80 52 Shore A hardness @ 61 61 60° C.
• Inventive Example 1 exhibits improved dynamic properties in comparison with Comparative Example 3, discernible in greater tensile strength (F median) and greater tensile strain (D median).
• Inventive Example 1 exhibits markedly improved rebound resilience when compared with Comparative Example 3.
• Inventive Example 1 exhibits a smaller maximum value than Comparative Example 3 for the tangent delta (tan d) loss factor, this being a sign of reduced energy absorption by the polymer, and it is therefore possible to conclude that rolling resistance is markedly lower in Inventive Example 1 than in Comparative Example 3.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Health & Medical Sciences (AREA)
• Physical Education & Sports Medicine (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymerization Catalysts (AREA)

Applications Claiming Priority (3)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=41651376

Family Applications (3)

Family Applications After (2)

Country Status (14)

Cited By (7)

Families Citing this family (16)

Citations (2)

Family Cites Families (30)

• 2009
  • 2009-10-16 EP EP09173297A patent/EP2311889A1/de not_active Withdrawn
• 2010
  • 2010-10-14 MX MX2012004362A patent/MX2012004362A/es active IP Right Grant
  • 2010-10-14 BR BR112012008782-7A patent/BR112012008782B1/pt not_active IP Right Cessation
  • 2010-10-14 RU RU2012119827/04A patent/RU2554351C9/ru active
  • 2010-10-14 US US13/500,440 patent/US20120208964A1/en not_active Abandoned
  • 2010-10-14 JP JP2012533639A patent/JP5577406B2/ja active Active
  • 2010-10-14 EP EP10763728.2A patent/EP2488561B1/de active Active
  • 2010-10-14 PL PL10763728T patent/PL2488561T3/pl unknown
  • 2010-10-14 KR KR1020127012473A patent/KR101393830B1/ko active IP Right Grant
  • 2010-10-14 ES ES10763728.2T patent/ES2661064T3/es active Active
  • 2010-10-14 CN CN201080046732.4A patent/CN102574955B/zh active Active
  • 2010-10-14 WO PCT/EP2010/065461 patent/WO2011045393A1/de active Application Filing
  • 2010-10-14 HU HUE10763728A patent/HUE036937T2/hu unknown
  • 2010-10-15 TW TW099135151A patent/TWI488867B/zh not_active IP Right Cessation
• 2012
  • 2012-04-13 ZA ZA2012/02719A patent/ZA201202719B/en unknown
• 2013
  • 2013-04-11 US US13/860,892 patent/US8846837B2/en active Active
• 2014
  • 2014-08-27 US US14/470,287 patent/US9279025B2/en active Active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events