Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
  • B29D30/0654—Flexible cores therefor, e.g. bladders, bags, membranes, diaphragms
• • 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
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers 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
  • C08F236/04—Copolymers 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
  • C08F236/08—Isoprene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
  • C08L15/02—Rubber derivatives containing halogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
  • B29D30/0654—Flexible cores therefor, e.g. bladders, bags, membranes, diaphragms
  • B29D2030/0655—Constructional or chemical features of the flexible cores

Definitions

• the present invention relates to rubber compositions equipped with polyorganosiloxanes as plasticizers.
• the present invention relates to the use of (meth) acrylate-modified polyorganosiloxanes as plasticizers in rubber compositions which are used as heating bladders in tire manufacture.
• the present invention also relates to rubber compositions which are particularly suitable for the manufacture of and use in bladders for the production of tires.
• Rubber compositions which are vulcanized by means of a resin crosslinking are known and are used in various branches of industry. Rubber articles on this basis are used, for example, for the production of heating bellows, which are used in the production of all types of tires.
• the non-crosslinked green tire is vulcanized in the tire production itself.
• the process of vulcanization describes the crosslinking of rubber compositions under pressure and elevated temperature. Covalent bonds are made between the polymers and an elastomer network is built up.
• vulcanization of rubber compounds can take place via different mechanisms.
• the most commonly used type of vulcanization is sulfur vulcanization.
• Rubber mi- compounds can also be crosslinked or vulcanized with peroxides, amines or resins.
• the green tire is placed in a tire press for molding and vulcanized.
• the task of heating bladders is to press the green tire under pressure and at high temperatures against the inner wall of the tire press during vulcanization in order to give the tire its profile.
• the bladder absorbs a pressure medium such as hot water or steam.
• the required bladders can be made from rubber compositions.
• Rubber compositions for heating bellows usually consist of a polymer system, a filler, zinc oxide, a plasticizer oil and a crosslinking resin.
• other customary processing additives are components of the rubber composition.
• the polymer is often butyl rubber, optionally with an addition of chloroprene rubber, if the crosslinking resin is not halogenated.
• Carbon black is often used as a filler.
• Zinc oxide acts as a catalyst for resin crosslinking and improves thermal conductivity.
• Castor oil is used as plasticizer oil in known heating bellows, as described in more detail below.
• halogenated formaldehyde-alkylphenol resin with methylol groups is usually used as a crosslinking resin.
• additional additives such as homogenizers can be added to the corresponding compositions.
• Heating bellows are also described which contain both butyl rubber and rubber with units derived from ⁇ -methylstyrene as a polymer system.
• a bladder goes through a cycle consisting of an inflation process and inflation Pressure medium, and subsequent relief, the discharge of the pressure medium, consists. This puts a mechanical load on the bladder. In addition to this mechanical load, the corresponding physical conditions also change to a considerable extent during the passage through the cycle. The significant pressure and temperature changes are particularly relevant here.
• the material used in the bladder must take this particular form of stress into account, particularly against the background of being able to produce the largest possible number of tires with one bladder. Depending on various factors such as tire size or vulcanization conditions, the bladder runs through a different number of cycles.
• Castor oil is considered to be a particularly suitable plasticizer and has proven itself over the past decades, as it has a relatively low volatility even at high temperatures and is generally suitable for reducing the tendency of resin-crosslinked mixtures to develop a so-called marching modulus during crosslinking demonstrate.
• rubber compositions containing castor oil are described in WO 2013/052206 A1 with a low modulus and good resistance to steam aging, with resistance being attempted here in addition to castor oil by adding hydrocarbon resins (hydrocarbon polymer modifiers (HPM)) to further increase the heating bellows to be produced.
• HPM hydrocarbon polymer modifiers
• EP 2 354 154 A1 and EP 2 151 479 A1 relate to rubber compositions which are vulcanized by peroxide and contain polyorganosiloxanes which are intended to improve the viscosity of the rubber during processing without the relevant mechanical properties of the vulcanizate obtained deteriorating (for example the module sinks).
• These polyorganosiloxanes have at least one organic component R which has at least one carbon-carbon multiple bond and optionally a further hydrocarbon component R2 with a chain length of 5 to 50 carbon atoms.
• R organic component
• R2 with a chain length of 5 to 50 carbon atoms.
• US 2011/0262573 A1 describes a manufacturing method for a bladder for tire manufacture, in which the surface of the bladder is modified by applying a layer that takes on the function of a release agent, but firmly on the surface Castor oil is used as a plasticizer for the bladder rubber compositions known from US 2011/0262573 A1.
• a polyorganosiloxane used in US 2011/0262573 A1 for surface coating on release agent replacement has a high molecular weight of up to 12,000 (average molecular weight, number average).
• US Pat. No. 4,710,541 describes a method for molding and vulcanizing rubber products such as tires in which an improved bladder is used.
• the bladder described in US 4,710,541 is modified to improve its separation properties from the tire material, for. B. via a suitable surface modification.
• the invention described in US 4,710,541 thus seeks to replace her conventional release agents.
• the polyorganosiloxane described in US Pat. No. 4,710,541 is in particular a high molecular weight polyorganosiloxane with a degree of polymerization of> 1,000, such as 7,000 dimethylsiloxy units, for example. It will be in great Quantities of, for example, 30 parts by weight to 70 parts by weight of rubber are used.
• the present invention relates to the use of one or more modified polyorganosiloxanes as plasticizers in rubber compositions, the rubber being vulcanized by means of one or more crosslinking resins, the polyorganosiloxane having 3 or more siloxane units and one or more organic components R 1 ent holds which has one or more carbon-carbon multiple bonds and at least 4 carbon atoms.
• the present invention relates to a method for producing a bladder for tire manufacture, in which a rubber composition which contains one or more modified polyorganosiloxanes, one or more crosslinking resins for crosslinking and optionally other conventional additives is vulcanized using the crosslinking resin wherein the modified polyorganosiloxane and rubber composition are as defined herein.
• a rubber composition comprises, which rubber composition comprises modified polyorganosiloxane and has been vulcanized by means of the crosslinking resin, the modified polyorganosiloxane and the rubber composition being as defined herein.
• Modified means the presence of an organic portion R 1 in the polyorganosiloxane according to the invention.
• Preferred embodiments of the invention can consist of the features disclosed below, without further components being present.
• FIG. 1 shows the results of the De Mattia kink test for vulcanized rubber compositions 1 to
• FIG. 2 shows the results of the De Mattia kink test for vulcanized rubber compositions 1 to 4 after their steam aging (48 hours at 190 ° C.).
• the inventors have surprisingly found that the use of certain polyorganosiloxanes that carry functional groups ("modified polyorganosiloxanes”) as plasticizers in rubber compositions that are used in heating bellows for friction fen production can be used to achieve the object of the invention.
• modified polyorganosiloxanes polyorganosiloxanes that carry functional groups
• the castor oil usually used in the rubber compositions on which they are based is partially or completely replaced by the polyorganosiloxanes according to the invention, heating linings for tire manufacture can be produced which have a longer service life compared to the heating linings known above.
• the plasticizer according to the invention thus acts in the volume of the rubber composition which contains it.
• a material present only on the surface of a rubber composition, e.g. a layer temporarily or permanently attached to it is not suitable as a plasticizer according to the invention.
• Polyorganosiloxanes per se are known substances. These are (macro) molecules that are built up according to the scheme (R2SiO) x , where R are usually hydrocarbon radicals (mostly methyl, more rarely ethyl, propyl, phenyl, etc.), see e.g. Römpp Chemie Lexikon 9th edition 1992 Volume 5, p. 4168).
• the polyorganosiloxanes used according to the invention are characterized in that they possess 3 or more siloxane units and have one or more organic components R 1 , in particular two or more organic components R 1 , and preferably one or more hydrocarbon components R 2 .
• proportions R 1 and R 2 present can each be the same or different.
• Polyorganosiloxanes used according to the invention have one or more organic components R 1 , where R 1 has one or more contains rere carbon-carbon multiple bonds and has at least 4 carbon atoms.
• the carbon-carbon multiple bond in R 1 is a carbon-carbon double bond, for example in a carbon chain or a ring of carbon atoms.
• the organic fraction R 1 is a monovalent radical.
• polyorganosiloxanes whose R 1 have at least five carbon atoms, such as at least six, in particular at least seven, carbon atoms, are particularly preferred.
• the polyorganosiloxane according to the invention has at least two carbon-carbon multiple bonds. This means that if the group R 1 has only a single carbon-carbon multiple bond, then at least two groups R 1 must be present. This embodiment is preferred. Alternatively, it is possible for a group R 1 to have at least two carbon-carbon multiple bonds. However, this embodiment is not preferred because the production of the corresponding polyorganosiloxanes is more complex.
• R 1 examples of suitable R 1 are cycloalkenyl, alkenyl, vinyl-containing, allyl-containing, norbornyl, (di) cyclopentenyl or groups derived from unsaturated acyloxy groups such as methacrylate or acrylate.
• Preferred monovalent radicals R 1 are derived from cyclohexene and (meth) acrylate, in particular (meth) acrylate-derived radicals R 1 , which are substituted by a hydrocarbon chain with one or more heteroatoms such as oxygen or sulfur and / or by one or more Heteroatoms such as oxygen and sulfur can be broken, are bound to the basic structure of the polyorganosiloxane.
• R 1 is a monovalent unsaturated acyloxy radical (ie a radical of the RCOO- type) with up to 15 C atoms (total number of C atoms including any substituents), the acyloxy radical being terminal (ie in the R unit) carries a substituted or unsubstituted double bond and is bonded to a silicon atom of the basic structure of the polyorganosiloxane via a hydrocarbon chain which preferably contains at least one oxygen atom in the chain and is preferably substituted with at least one hydroxyl group.
• R 1 is the following groups
• the carbon atom that is bound to the silicon atom is marked with an arrow.
• These functionalizations are accessible by reacting an SiH unit with a compound that has a double bond that is accessible for hydrosilylation, such as, for example:
• the number of carbon atoms between the silicon atom bearing the group R 1 and the carbon-carbon multiple bond is preferably 1 to 10, more preferably 2 to 7, such as 4.
• the shortest route becomes a double bond counted.
• R 1 is present as part of the structural unit I in the polyorganosiloxane according to the invention
• R is selected from methyl, Ethyl, propyl, butyl, pentyl or phenyl, where R is particularly preferably methyl.
• Polyorganosiloxanes preferred according to the invention have from 15 to 70, preferably 20 to 40 or 50 and in particular 20 to 30 structural units of type I D , which is a measure of the chain length of the polyorganosiloxane.
• Polyorganosiloxanes according to the invention optionally have one or more longer alkyl radicals R 2 , R 2 having a chain length of 5 to 50 carbon atoms.
• R 2 is according to one embodiment selected from branched or unbranched alkyl groups having 5 to 30 carbon atoms, in particular sondere unbranched alkyl groups having 5 to 30 carbon atoms, such as n-Cs to C3o-alkyl, preferably-CIO n to C 26 ⁇ Alkyl, preferably n-Ci 2 - to Cis-alkyl, such as n-Cis-alkyl.
• the alkyl radical R 2 is preferably contained in the polyorganosiloxane as part of unit II where y is 1, 2 or 3 and preferably 1, b is 0, 1 or 2, preferably 1 or 2 and in particular 1, and R 'is a monovalent organic radical as defined above for R in relation to structural unit (I) , but is chosen independently of R. It is preferred that R 'is selected from methyl, ethyl, propyl, butyl, pentyl or phenyl, with R' being particularly preferably methyl.
• polyorganosiloxanes according to the invention preferably also have the difunctional structural unit III D :
• radicals R ′′ are identical or different (and are preferably identical) and are selected from linear alkyl radicals, branched alkyl radicals, cycloalkyl radicals or aromatic radicals which have a Oxygen atom can be bonded to the polyorganosiloxane, and the radicals R ′′ are preferably methyl, ethyl, propyl and phenyl, in particular methyl.
• one (or two) monofunctional structural units III M is (are) also present in the polyorganosiloxane according to the invention:
• R '''3S1O 1/2] (IH M) where the radicals R''' are identical or different and be ⁇ are selected from hydroxy and linear alkyl groups, branched alkyl groups cycloalkyl or aromatic radicals attached through an oxygen atom can be, and the radicals R,,, are preferably hydroxy, methyl, ethyl, propyl and phenyl, in particular hydroxy and methyl. In a particularly be ⁇ vorzugten off are guiding form the R '''are the same and are methyl groups.
• a preferred structure of a polyorganosiloxane according to the invention is as follows:
• m and o are independently in the range from 0 to 40 and n and p can independently be 0, 1 or 2, with the proviso that the sum (m + n) is at least 1 and preferably the sum (o + p) is at least 1, with the further proviso that the sum (n + p) is at most 2, the sum (m + n + o + p) preferably being in the range up to 20, and (ii) q ranges from 0 to 100.
• the difunctional structural units I D , II D and III D in the polyorganosiloxane according to the invention are typically and preferably not arranged as a block, but are randomly distributed along the polysiloxane chain. It is also clear to the person skilled in the art that the parameters m, n, o, p and q are average values because the polyorganosiloxanes according to the invention are typically not obtained as uniform compounds during production.
• n is 1 or 2 and preferably 2, ie the functionalization R 1 is contained in the polyorganosiloxane (at least also) in monofunctional (terminal, terminal) structural units I M.
• n 2 and m is zero (0), that is to say that the functionalization R 1 is contained in the polyorganosiloxane exclusively in monofunctional (terminal, terminal) structural units I M.
• n 1 or 2
• the portion R 1 is bonded to a different silicon atom than the portion R 2 .
• the total number of siloxane units in the polyorganosiloxanes according to the invention is (m + o + q + 2) 10 to 100, more preferably 15 to 70, in particular 20 to 50, such as 20 to 30 or 40.
• the sum of the functionalized siloxane units in the polyorganosiloxanes according to the invention (m + n + o + p) is 2 to 15, preferably 2 to 6 or 10.
• Preferred ratios of the functionalizations with R 1 and R 2 in difunctional siloxane units I D and II D are (that is, m / o is) 10/90 to 99/1, more preferably 30/70 to 98/2, in particular 50/50 to 97 / 3, like 70/30 to 96/4 or 75/25 to 95/5.
• the number of unsubstituted difunctional siloxane units III D (q) in the polyorganosiloxanes according to the invention is preferably 5 to 60, more preferably 10 to 50, in particular 15 to 40, such as 20 to 30.
• Polyorganosiloxanes according to the invention can be present as compounds with a high viscosity which are liquid at room temperature (25 ° C.).
• the length of the siloxane chain ie sum of SiO units, sum (m + o + q + 2), from about 30
• the length of the hydrocarbon component R 2 possibly the length of the hydrocarbon component R 2 (from about 20 carbon atoms) and the possible number of
• the polyorgano siloxanes according to the invention can be solid at room temperature with hydrocarbons R 2 .
• the polyorganosiloxane according to the invention as a master batch which contains a) one or more rubbers and b) one or more polyorganosiloxanes according to the invention.
• the masterbatch preferably contains 0.5 to 30 parts by weight of polyorganosiloxane according to the invention, more preferably 0.5 to 20 parts by weight and in particular 0.5 to 10 parts by weight of polyorganosiloxane, based on 100 parts by weight of rubber (phr, parts per hundred parts rubber).
• the rubbers used in the masterbatch are typically rubbers which can be crosslinked by means of crosslinking resin, such as butyl rubber and chloroprene rubber.
• a masterbatch facilitates the incorporation of the polyorganosiloxane according to the invention into a rubber.
• polyorganosiloxane according to the invention in the form of a mixture comprising a) one or more solid carrier materials (preferably selected from inorganic fillers (such as silica) or wax-like materials (such as polyethylene waxes)) and b) or contains several polyorganosiloxanes according to the invention.
• solid carrier materials preferably selected from inorganic fillers (such as silica) or wax-like materials (such as polyethylene waxes)
• the weight ratio of a) carrier material to b) polyorganosiloxane according to the invention in the mixture is preferably 10/90 to 90/10, more preferably 20/80 to 80/20 and particularly preferably about 60/40.
• Preferred materials for mixtures are silicas or other inorganic fillers such as chalk or wax-like materials such as polyethylene waxes.
• a) a polyorganosiloxane which has two or more SiH groups is reacted with a compound which has at least one group R 1 to form a polyorganosiloxane with at least one group R 1 and optionally to obtain one or more remaining SiH groups, and b) optionally reacted the polyorganosiloxane obtained in step a) with at least one or more remaining SiH groups with an olefin in order to obtain a polyorganosiloxane according to the invention.
• a polyorganosiloxane which has two or more SiH groups is reacted with a compound which has at least one hydrosilylatable group and a further functional group R 3 which differs from it and which has under common hydrosilylation conditions is inert, such as an epoxide, in particular a glycidyl ether, in order to obtain a polyorganosiloxane having at least one group R 3
• the polyorganosiloxane obtained in step a) is reacted with a compound which has at least one group R 1 and ei ne has further functional group R 4 different therefrom, which is suitable to selectively form a bond with the group R 3 in order to obtain a polyorganosiloxane with at least one group R 1 and optionally one or more remaining unreacted R 3 groups
• a silane which has one or more hydrolyzable groups is functionalized with a group R 1
• b) optionally a silane which has one or more hydrolyzable groups is functionalized with a group R 2 functionalized
• the polyorganosiloxanes are used as plasticizers in rubber compositions.
• the polyorganosiloxanes according to the invention act in the volume of the rubber composition into which they are incorporated, in contrast to a pure modification of the surface of the rubber composition (if it is present as a molded part with a defined surface).
• the rubber composition is not modified on the surface with a coating.
• the rubber composition preferably contains 0.5 to 30 parts by weight of polyorganosiloxane according to the invention, more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, and in particular 2 to 8 parts by weight of polyorganosiloxane, based on 100 parts by weight of rubber (phr, parts per hundred parts rubber).
• the rubber composition preferably contains 1 to 10 phr polyorganosiloxane according to the invention.
• the rubber composition preferably contains 2 to 7 phr of the polyorganosiloxane according to the invention.
• the rubber composition preferably contains 2.5 to 6.5 phr of the polyorganosiloxane according to the invention.
• the rubber composition preferably contains 6 phr polyorganosiloxane according to the invention.
• the rubber is a rubber crosslinkable by means of a crosslinking resin.
• a crosslinking resin such rubbers which can be crosslinked with crosslinker resin cannot be vulcanized with peroxide crosslinkers, since these rubbers decompose under the corresponding reaction conditions.
• rubbers are used which are particularly suitable for the production of heating bellows which can be used in the production of tires.
• Preferred rubbers which can be used in the context of the use according to the invention are, for example, butyl rubber, brominated copolymers of isobutylene and p-methylstyrene and mixtures thereof.
• Suitable crosslinking resins for the use according to the invention are, in particular, those which are used in the vulcanization of rubber compositions in the context of the manufacture of heating bladders for tire production.
• Crosslinking resins that can form three-dimensional network structures are preferably used.
• Phenol-formaldehyde resins are particularly suitable here.
• the connectivity of this group of compounds is based on the reactivity Activity of the phenol methylol groups in the phenol-formaldehyde resins, which under the action of heat and elimination of water form an ⁇ , ß-unsaturated carbonyl compound containing exo-methylene groups, which in turn reacts with an isoprene-based rubber unit to form a chroman ring system.
• the phenol-formaldehyde resins used contain at least two phenolmethylol groups for the purpose of crosslinking.
• alkylphenol-formaldehyde resins in particular can be used for crosslinking, alkyl being preferably C4 to Cio-alkyl, such as, in particular, octyl.
• the crosslinking resin can optionally be halogenated, for example brominated, such as the brominated octylphenyl-formaldehyde resin SP-1055 available from Akrochem.
• a non-halogenated crosslinking resin such as the octylphenylformaldehyde resin SP-1045 available from Akrochem
• a suitable halogen-containing component such as chloroprene rubber is added.
• Acidic substances Lewis acids such as SnCl2 or FeCl 3 can also be used .
• the rubber composition preferably contains 0.5 to 30 parts by weight of crosslinking resin, more preferably 1 to 20 parts by weight, particularly preferably 2 to 15 parts by weight, and in particular 2 to 12 parts by weight of crosslinking resin, based on 100 parts by weight of rubber (phr, parts per hundred parts rubber).
• a rubber composition preferably also contains additives such as fillers (e.g. carbon black, silica, zinc oxide, calcium carbonate, barium sulfate, magnesium oxides, aluminum oxides, iron oxides, silicates) and substances required for crosslinking (zinc oxide, accelerators, magnesium oxide, sulfur), catalysts / activators for resin crosslinking (for example chloroprene rubber, zinc oxide, stearic acid or salts formed therefrom), anti-aging agents, homogenizers in the usual amounts.
• fillers e.g. carbon black, silica, zinc oxide, calcium carbonate, barium sulfate, magnesium oxides, aluminum oxides, iron oxides, silicates
• substances required for crosslinking zinc oxide, accelerators, magnesium oxide, sulfur
• catalysts / activators for resin crosslinking for example chloroprene rubber, zinc oxide, stearic acid or salts formed therefrom
• anti-aging agents for example chloroprene rubber, zinc oxide, stearic acid or salts formed there
• the invention also relates to a method for producing a bladder for tire manufacture, in which a rubber composition containing one or more inventive modified polyorganosiloxanes, one or more crosslinking resins for crosslinking and optionally other conventional additives is vulcanized by means of the crosslinking resin.
• the components are, as disclosed in detail in the following examples, thoroughly mixed conditions using suitable devices and conditions. Mixing processes and devices suitable for this per se are known to those skilled in the art.
• the invention further relates to a bladder for tire manufacture, which comprises a rubber composition vulcanizable with crosslinking resin, the rubber composition comprising a modified polyorganosiloxane according to the invention and having been vulcanized by means of the crosslinking resin.
• the inventors have surprisingly found that the use of the polyorganosiloxanes according to the invention as plasticizers in a rubber composition significantly extends the service life of a bladder made from this rubber composition for tire production, compared to a bladder for tire production, which is otherwise identical in composition and processing Vulkanisationsmi mixture with castor oil as a plasticizer (in the same concentration) is produced.
• the service life of a bladder is determined on the basis of a specimen in the fatigue buckling test according to De Mattia after steam aging (48 hours at 190 ° C.).
• the crack growth of the specimens of the different compounds is compared with one another. The lower the value for crack growth at a certain number of Load cycles, the longer the service life of the bladder.
• R 1 contains up to 15 carbon atoms, where R 1 is in particular a valued, unsaturated acyloxy radical (ie a radical of the RCOO- type) with up to 15 carbon atoms, the acyl radical being terminal dig carries a substituted or unsubstituted double bond and is bonded to a silicon atom of the basic structure of the polyorganosiloxane via a hydrocarbon chain which contains at least one oxygen atom in the chain and is preferably substituted with at least one hydroxyl group.
• R 1 is in particular a valued, unsaturated acyloxy radical (ie a radical of the RCOO- type) with up to 15 carbon atoms
• the acyl radical being terminal dig carries a substituted or unsubstituted double bond and is bonded to a silicon atom of the basic structure of the polyorganosiloxane via a hydrocarbon chain which contains at least one oxygen atom in the chain and is preferably substituted with at least one hydroxyl group.
• the rubber is vulcanized by means of one or more crosslinking resins, the rubber in particular comprises butyl rubber, brominated copolymers of isobutylene and p-methylstyrene or mixtures thereof, and chloroprene rubber as Crosslinking aid can be used.
• the further plasticizer other than polyorganosiloxane comprises castor oil and / or a hydrocarbon resin, preferably comprises castor oil, in particular is castor oil and / or a hydrocarbon resin, in particular is castor oil.
• the rubber composition contains further additives and constituents which are suitable for the manufacture of bladders for tire manufacture.
• the rubber composition after vulcanization, is suitable for use as a bladder in tire manufacture.
• the rubber composition contains, as further constituents, filler, catalyst for resin crosslinking and, if appropriate, further additives, in particular homogenizers.
• crosslinking resin is optionally halogenated formaldehyde-alkylphenol resin, the alkyl radical being in particular Ci- to Cio-alkyl.
• a method for producing a bladder for tire manufacture in which a rubber composition containing one or more modified polyorganosiloxanes, one or more crosslinking resins for crosslinking and optionally further conventional additives, is vulcanized by means of the crosslinking resin, the modified polyorganosiloxane and the Rubber composition as defined in any of the preceding paragraphs A to 0.
• Bladder for tire manufacture which comprises rubber composition vulcanizable with crosslinker resin, which rubber composition comprises modified polyorganosiloxane and has been vulcanized by means of the crosslinker resin, the modified polyorganosiloxane and the rubber composition as defined in one of the preceding paragraphs A to 0.
• POS is a short, di-terminal and poly-pendant, functionalized polyorganosiloxane.
• Mooney viscosity ISO 289-1 Unvulcanized rubber - Be determinations using a shear disc viscometer - Part 1: Determination of the Mooney viscosity.
• Shore A hardness DIN ISO 7619-1: 2012-02 Elastomers or thermoplastic elastomers - Determination of penetration hardness - Part 1: Durometer method (Shore hardness).
• Tensile strength / tension values / elongation at break DIN 53504 Testing of rubber and elastomers - determination of tensile strength, tensile strength, elongation at break and tension values in tensile tests.
• Tear propagation resistance DIN ISO 34-1 DIN elastomers or thermoplastic elastomers - Determination of the tear propagation resistance of the - Part 1: Strip, angular and arched test specimens.
• Rubber compositions 1 to 4 were prepared as described below.
• a mixture of 50 parts by weight of carbon black (Luvomaxx BC N-330), 5 parts by weight of zinc oxide (resin seal GR), 5 parts by weight of Struktol 40 MS Flakes, 6 parts by weight of POS and 100 parts by weight of butyl rubber (Butyl RB 301) and 5 parts by weight of chloroprene rubber (Neoprene WRT ) was placed in an upside-down mixing process in a laboratory internal mixer at 80 ° C start temperature and 70 revolutions / minute. After 30 seconds the stamp was lifted and swept and after 180 seconds the mixture was ejected.
• the vulcanized rubber compositions 1 to 4 were also examined in the De Mattia endurance buckling test (Table 5 and FIG. 1).
• the vulcanized rubber compositions 1 to 4 were subjected to steam aging for 48 hours at 190 ° C.
• the following properties of the vulcanized rubber compositions 1 to 4 were determined after steam aging.
• the changes in the corresponding properties caused by steam aging are also given below (Table 6).
• the vulcanized rubber compositions 1 to 4 were also examined after steam aging (48 h at 190 ° C.) in the De Mattia endurance test (Table 7 and FIG. 2).
• Rubber composition 1 illustrates the prior art and serves as a comparison (control).
• 3 phr POS in combination with 3 phr castor oil in rubber composition 2 or 6 phr POS in rubber composition 3
• the volcanic curve is reduced depending on the amount of POS used.
• 6 phr POS in combination with a 2 phr higher use of crosslinking resin SP 1045, the volcanic curve of rubber composition 4 reaches a level comparable to that of rubber composition 1.
• the vulcanized rubber composition 4 has a very balanced property profile. It is particularly worth mentioning that the vulcanized rubber composition 4 in the crack growth according to De Mattia now clearly separates itself from the control (rubber composition 1) and has a significantly improved crack resistance.
• rubber composition 1 shows inferior flexibility of the vulcanizate. This is illustrated by the strong increases in Shore hardness, tensile strength and modulus.
• the use of only 3 phr POS in combination with 3 phr ri zinus oil (rubber composition 2) also leads to good results in the endurance buckling test (De Mattia test).

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