WO2015090447A1 - Sulfur-containing polymers - Google Patents

Sulfur-containing polymers Download PDF

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Publication number
WO2015090447A1
WO2015090447A1 PCT/EP2013/077700 EP2013077700W WO2015090447A1 WO 2015090447 A1 WO2015090447 A1 WO 2015090447A1 EP 2013077700 W EP2013077700 W EP 2013077700W WO 2015090447 A1 WO2015090447 A1 WO 2015090447A1
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Prior art keywords
sulfur
polymer
elastomeric
containing polymer
styrene
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PCT/EP2013/077700
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English (en)
French (fr)
Inventor
Christian DÖRING
Sven Thiele
Joachim Kiesekamp
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Trinseo Europe Gmbh
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Application filed by Trinseo Europe Gmbh filed Critical Trinseo Europe Gmbh
Priority to EP13821106.5A priority Critical patent/EP3083270A1/en
Priority to PCT/EP2013/077700 priority patent/WO2015090447A1/en
Priority to TW103137027A priority patent/TW201525006A/zh
Publication of WO2015090447A1 publication Critical patent/WO2015090447A1/en

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    • 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
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • 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
    • C08F236/10—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 with vinyl-aromatic monomers
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/04—Homopolymers and 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
    • C08F36/06—Butadiene

Definitions

  • the present invention is directed to novel sulfur-containing polymers, specifically elastomeric polymers containing one or more polysulfide (i.e. di-, tri-, tetra- or higher sulfide) bridges within the linear polymer chain.
  • the invention is also directed to a method of making the sulfur-containing polymer.
  • the invention further relates to an uncured, i.e. non-crosslinked, polymer composition comprising the sulfur-containing polymer of the invention.
  • the invention relates to the use of the sulfur-containing polymer or uncured polymer composition in selected applications, i.e. for preparing selected cured (crosslinked or vulcanized) elastomeric polymer compositions or rubber goods.
  • composition of a cured rubber compound as being part of automobile tires, especially of tire threads, very much influences the running characteristics of such tires.
  • various additives may be added and/or special elastomeric polymers can be used. Additives include, for example, processing aids, fillers (such as carbon black), plasticizers, antioxidants, vulcanizing agents, accelerators and activators,
  • Crosslinking of the polymer chains by means of a vulcanization system produces a three- dimensional, wide-meshed chemical network, thus rendering the resulting rubber more rigid and tear-resistant, in. particular resistant to tear propagation, depending on the crosslinking density.
  • the crosslinking process forms crosslinks between the polymer chains, usually by means of bridges such as sulfur bridges upon sulfur-vulcanized diene rubbers.
  • the length of the sulfur bridges will depend on the ratio of sulfur to accelerator, distinguishing between conventional networks (ratio of sulfur/accelerator of 10: 1 to 2: 1 ), semi-efficient networks (2: 1 to 1 :2), and efficient networks (1 :2 to 1 : 10).
  • EP 0 316 857 describes an anionic polymerization process using an initiator mixture comprising a di-iithium compound and an organic diamine or triamine.
  • the resultmg polymer preferably triblock styrene-isoprene-styrene polymers, are said to exhibit a narrow molecular weight distribution, resulting in increased tensile rupture strength properties of adhesive formulations.
  • an elastomeric polymer having, when used in vulcanized rubber composition, improved abrasion resistance and/or rolling resistance, while maintaining or even improving other relevant rubber properties;, including wet grip.
  • the invention provides an elastomeric sulfur-containing polymer represented by the following Formula 1 :
  • S is a sulfur atom
  • P is an elastomeric polymer chain obtained by anionic polymerization of at least one conjugated diene and optionally a vinylaromatic compound in the presence of a diinitiator
  • Y is the dicarbanion group derived from the diinitiator
  • x is, independently for each group S x , an integer selected from 1 and higher, with the proviso that x is selected from 2, 3 and 4 for at least one group S x ,
  • z is an integer selected from 1 to 160, and
  • F is independently a terminal group selected from H, -SH, -SOH, -SCI, -SSCi, -S0 2 H and -SO . 3H,
  • the invention provides a method of making the e!astomcric sulfur- containing polymer of Formula 1 comprising the steps of:
  • step (ii) reacting the anionic living polymer chains of step (i) with sulfur monochloride (S2CI 2 ).
  • the invention provides a non-cured polymer composition
  • a non-cured polymer composition comprising the elastomeric sulfur-containing polymer of Formula 1 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for preparation of the anionic living polymer chains and (ii) components which remain after solvent removal from the polymerization process.
  • the invention provides for the use of the elastomeric sulfur-containing polymer of Formula 1 according to the first aspect of the invention or of the polymer composition according to the third aspect of the invention in (i) footwear, (ii) golf balls, (iii) membranes that do not contain reinforcements (such as but not limited to fibers or fabrics), (iv) adhesives, (v) modified plastics, including polybutadiene-modified acrylonitrile-styrene copolymers (ABS) and high impact polystyrene (polybutadiene-modified polystyrene, HIPS), and (vi) films that are not for automotive interiors or aircraft interiors.
  • footwear elastomeric sulfur-containing polymer of Formula 1 according to the first aspect of the invention or of the polymer composition according to the third aspect of the invention
  • reinforcements such as but not limited to fibers or fabrics
  • adhesives such as but not limited to fibers or fabrics
  • modified plastics including polybutadiene-modified acrylonitrile
  • the elastomeric sulfur-containing polymer and compositions thereof have beneficial properties especially when used in the manufacture of tires. Specifically, it was surprisingly found that cured polymer compositions ("cured rubber compounds") produced from the elastomeric sulfur-containing polymer of Formula 1 exhibit improved abrasion resistance and roiling resistance, while maintaining or even improving other rubber properties, including wet grip and tensile properties.
  • the beneficial properties were in particular found when using and curing ( vulcanizing) a polymer composition of the invention containing both the elastomeric sulfur-containing polymer and additionally one or more inorganic fillers.
  • vulcanization using a sulfur-containing vulcanizing agent can be carried out at a reduced level of the vulcanizing agent.
  • the elastomeric sulfur-containing polymer of the present invention is generally represented by Formula 1 as defined above.
  • the elastomeric polymer chains P contained in the polymer of the invention are obtained by carrying out an anionic polymerization of at least one conjugated die e and optionally a vinylaromatic compound in the presence of a diinitiator.
  • the living anionic polymer chains P are subsequently reacted with sulfur monochloride (S2CI2) and, thus, form the elastomeric sulfur-containing polymer of the invention.
  • Exemplary conjugated dienes useful in preparing the living anionic polymer chains include 1 ,3 -butadiene, 2-(Ci-Cj alkyl)- 1,3 -butadiene such as isoprene (2- methyl- 1,3 -butadiene), 2,3- dimethyl- 1 ,3 -butadiene, 1 ,3-pentadiene, 2,4-hexadiene, 1 ,3-hexadiene, 1 ,3-heptadiene, 1 ,3- octadiene, 2-methyl-2,4-pentadiene f cyclopentadiene, 2,4-hexadiene and 1 ,3-cyc!ooctadiene.
  • 2-(Ci-Cj alkyl)- 1,3 -butadiene such as isoprene (2- methyl- 1,3 -butadiene), 2,3- dimethyl- 1 ,3 -butadiene, 1 ,3-
  • conjugated dienes include 1 ,3 -butadiene and isoprene. In one embodiment, the conjugated diene is 1,3- butadiene.
  • the vinylaromatic compound includes monoviiiylaromatic compounds, i.e. compounds having only one vinyl group attached to an aromatic group, and di- or higher vinylaromatic compounds which have two or more vinyl groups attached to an aromatic group.
  • exemplary vinylaromatic compounds optionally used together with the at least one conjugated diene include styrene, C j.4 alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4- methylstyrene, 2,4-dimethylstyreiie, 2,4,6-trimethylstyrene, a-methylstyrene, 2,4- diisopropylstyrene and 4-tert-butyIstyrene, stilbene, vinyl benzyl dimethylamine, (4- vinylbenzyl)dimethy] aminoefhyJ ether, ⁇ , ⁇ -dimethylaminoethyl styrene,
  • vinylpyridine and di vinylaromatic compounds such as 1,2-divinylbenzene, 1,3- divinylbenzene and 1,4-divinylbenzene.
  • a mixture of two or more vinylaromatic compounds may be used.
  • a preferred vinylaromatic compound is a monovinylaromatic compound, more preferably styrene.
  • the monovinylaromatic compound(s) may be used in total amounts of up to 70 wt,%, preferably up to 60 wt.% and more preferably up to 50 wt.%, based on the total weight of monomers used in the polymerization reaction for preparing the living anionic polymer ehains.
  • the di- or higher vinylaromatic compounds such as divinylbenzene, including 1,2-divinylbenzene, 1 ,3 -divinylbenzene and 1 ,4-divinylben.zene, may be used in total amount of 1 wt.% or less (based on the total molar weight of the monomers used to make the polymer).
  • the living anionic polymer chains are obtained from a random copoiymerization of 1,3 -butadiene as the conjugated diene and styrene as the vinylaromatic compound, preferably using styrene in an amount of from 5 to 70 wt.%.
  • the diinitiator used in the preparation of the living anionic polymer chains can be any initiator compound known in the art and effecting initiation of the polymerization reaction by providing at least two carbanions in a single initiator molecule. Two or more different diinitiators may be used in combination. Organolithium di initiators are preferred for use in the present invention. Diinitiators useful in the present invention are those disclosed in EP 0 316 857, EP 0 413 294, US 4,182,818, US 4,196,153, US 5,561 ,210, US 5,521 ,255 and WO 2011/047220, each being incorporated herein by reference in its entirety.
  • the amount of diinitiator used (total amount) will be selected on the basis of the monomers to be polymerized and the target molecular weight of the living anionic polymer chains. However, the amount is typically 0.05 to 20 mmol, preferably 0.1 to 10 mmol per 100 grams of monomer (total amount of polymerizable monomer).
  • the diinitiator may be used in combination with one or more further initiator compounds not falling within, the characterization of a diinitiator.
  • Such further initiator compounds include organometal compounds, especially organolithium compounds, such as ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexyllithium, 1 ,4-dilithio-n-butane, i ,3-di(2-lithio-2-hexyl)benzene and l,3-di(2-lithio-2- propyl)benzene.
  • organolithium compounds such as ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexyllithium, 1 ,4-dilithio-n-
  • n-butyllithium and sec-butyllithium are preferred. If a combination of diinitiator and further initiator compound is used, the amount of the diinitiator is at least 25 mol% 5 based on the total amount of initiator compounds (including diinitiator).
  • Polar coordinator compounds as known in the art may optionally be added to the monomer mixture or polymerization reaction, in order to adjust the microstructiire (i.e. the content of vinyl bonds) of the conjugated diene part of the living anionic polymer chains, or to adjust the composition distribution of any viny!aromatic compound in the living anionic polymer chains (thus acting as a randomizer compound), A combination of two or more polar coordinator compounds may be used.
  • Polar coordinator compounds useful in the invention are generally exemplified by Lewis base compounds.
  • Suitable Lewis bases for use in the present invention are, for example, ether compounds such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, (Cj-Cg alkyl)tetrahydrofurylethers (including methyltetrahydrofurylether.
  • ether compounds such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, (Cj-Cg alkyl)tetrahydrofurylethers (including methyltetrahydrofurylether
  • ethyltetrahydrofiirylether propyltetrahydrofurylether, butyltetrahydrofurylether, hexyltetrahydrofurylether and octyltetrahydrofurylether
  • tetrahydrofuran 2,2-(bistetrahydrofurfuryl)propane
  • bistetrahydrofurfurylformal methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, a- methoxytetrahydrofuran, dimethoxybenzene and dimethoxyethane
  • tertiary amines such as triethylamine, pyridine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl ethylenediamine, dipiperidinoethane, methyl ether of ⁇ , ⁇ -die
  • the polar coordinator compound will typically be added at a molar ratio of polar coordinator compound to initiator compound of from 0.012:1 to 10: 1 , preferably from 0.1 : 1 to 8: 1 and more preferably from 0.25: 1 to about 6:1.
  • the polymerization process used for preparing the living anionic polymer chains is preferably conducted as a solution polymerization, wherein the formed polymer is substantially soluble in the reaction mixture, or as a suspension slurry polymerization, wherein, the formed polymer is substantially insoluble in the reaction medium. More preferably, the living anionic polymer chains are obtained in a solution polymerization.
  • the solution polymerization normally is carried out at a pressure of not more than 10 MPa (absolute pressure), preferably in a temperature range of from 0 to 120°C.
  • the polymerization can be conducted under batch, continuous or semi-continuous polymerization conditions.
  • the living anionic polymer chains are reacted with sulfur monochloride (S2CI2) to provide the sulfur-containing elastomeric polymer of Formula 1.
  • sulfur monochloride acts as a coupling agent to link two living anionic polymer molecules end-to-end and to produce a linear polymer (as opposed to the S- crosslinked network obtain in a conventional vulcanization reaction using elemental sulfur).
  • Sulfur monochloride may be added intermittently (at regular or irregular intervals) or continuously during the polymerization reaction. When asymmetrical coupling is desired, it is preferable to add sulfur monochloride continuously during the polymerization reaction. Such continuous addition is normally effected in a reaction zone separate from the zone where the bulk of the polymerization is taking place. Sulfur monochloride is preferably added to the polymerization reaction at a time when a high degree of conversion of monomer has already been achieved. For example, the coupling agent will normally be added when at least 80% of the monomer has been polymerized. In a preferred embodiment, sulfur chloride is not added until at least 90% of the monomer has been polymerized.
  • a substantial amount of the chain ends of the polymer produced in the polymerization process is not terminated when sulfur monochloride is added. That is, living polymer chain ends are present and capable of reacting with the sulfur monochloride in a polymer chain, coupling reaction.
  • the coupling reaction may be carried out in a temperature range of from 0°C to 150°C, preferably from 15°C to 120°C and even more preferably from 40°C to 1 (X)°C. There is no limitation for the duration of the coupling reaction. However, with respect to an economical polymerization, process, for example in the case of a batch polymerization process, the coupling reaction is usually stopped at about 1 to 60 minutes after the addition of the sulfur monochloride.
  • Sulfur monochloride can be added to the polymerization reaction in the form of a solution in a hydrocarbon solvent, for example in cyclohexane, with suitable mixing for distribution and reaction.
  • sulfur monochloride is used in an amount of from 0.01 to 10 mol, preferably from 0.05 to 8 mol and more preferably from 0,2 to 5 mol for every 10 moles of living anionic polymer chain, ends.
  • reaction mixture typically involves removal of polymerization and/or reaction, solvent by steam stripping or vacuum evaporation techniques and will determine the type of the terminal groups F of the elastomeric sulfur-containing polymer of Formula 1.
  • an anionic chain end may not have reacted with sulfur monochloride and is protonated during work-up, resulting in F being hydrogen, or is may have reacted with sulfur monochloride, without further linkage to another anionic living polymer chain, so that sulfur monochloride or a derivative thereof acts as an end-capping agent.
  • the elastomeric sulfur-containing polymer of the invention is represented by Formula 1 as defined herein.
  • z is an integer selected from 1 to 80, more preferably from 1 to 40, In one embodiment, z is at least 2.
  • x is an integer selected from 1 to 8, more preferably from 1 to 6, even more preferably from 1 to 4, with the proviso that x is an integer selected from 2, 3 and 4 for at least one group S x .
  • z is an integer selected from 1 to 40 and x is an integer selected from 1 to 4, with the proviso as above.
  • the elastomeric sulfur-containing polymer of the invention is a styrene-butadtene copolymer represented by the following Formula 2:
  • SBR is an elastomeric polymer chain obtained by anionic polymerization of 1,3-butadiene and styrene in the presence of a diinitiator
  • styrene typically constitutes from 5 to 70 % by weight, preferably from 5 to 60% by weight and more preferably from 5 to 50 % by weight, based on the total weight of the polymer.
  • An amount of less than 5 % by weight of styrene may result in a deteriorated balance of rolling resistance, wet skid and abrasion resistance, and in reduced tensile strength, whereas an amount of more than 70 % by weight may lead to increased hysteresis loss.
  • the elastomeric sulfur containing polymer of Formula 2 may be a block or random copolymer. Preferably 40 % by weight or more of the styrene repeating units are linked singly, and 10 % by weight or less are "blocks" of eight or more styrene monomers linked successively. A polymer falling outside these limits may exhibit increased hysteresis loss.
  • the length of successively linked vinyl aromatic units, including styrene repeating units, can be determined by an ozonolysis-gel permeation chromatography method developed by Tanaka et al. (Polymer, Vol. 22, Pages 1721 -1723 (1981)).
  • the elastomeric sulfur-containing polymer of Formula 1 of the present invention usually contains sulfur in a total amount of from 0.10 to 30 g/kg of polymer, preferably from 0.1 to 10 g/kg and more preferably from 0.5 to 3 g/kg.
  • sulfur in a total amount of from 0.10 to 30 g/kg of polymer, preferably from 0.1 to 10 g/kg and more preferably from 0.5 to 3 g/kg.
  • the content of 1 ,2-bonds (vinyl bond content") in the butadiene part of the polymer, it is preferably from 2 to 90 % by weight, particularly preferably from 5 to 75 % by weight for most applications, based on the total weight of the polymer.
  • a vulcanized rubber compound obtained from the polymer may have an inferior balance of wet skid resistance, roiling resistance and abrasion resistance.
  • a vulcanized rubber compound obtained from the polymer may exhibit inferior tensile strength and abrasion resistance and a relatively high hysteresis loss.
  • the elastomeric sulfur- containing polymer of the present invention preferably has a Mooney viscosity of up to 150 MU, preferably up to 120 MU and more preferably from 20 to 120 MU (ML 1+4, 100°C; determined in accordance with ASTM D 1646 (2004) using a Monsanto MV2000 instrument). If the Mooney viscosity of the elastomeric sulfur-containing polymer is more than.
  • the processability as reflected by filler incorporation and heat build-up in the internal mixer, banding on the roll mill, extrusion rate, extrudate die swell and smoothness, is likely to be negatively affected because the compounding machinery used by the tire manufacturers are not designed to handle such high Mooney rubber grades, and the time and costs of processing increases.
  • a Mooney viscosity of less than 20 may not be preferred due to increased tack and cold flow of the uncross! inked elastomeric polymer, resulting in difficult handling, poor green strength and poor dimensional stability during storage.
  • a Mooney viscosity of less than 20 may be preferred.
  • the number average molecular weight of the elastomeric sulfor-containing polymer of the invention is usually in the range of 5 to 2000 kg/mol, preferably from. 10 to 1500 kg/mol and more preferably from 15 to 1.000 kg mol.
  • the elastomeric sulfur-containing polymer of Formula 1 is prepared in a method comprising the steps of:
  • step (ii) reacting the anionic living polymer chains of step (i) with sulfur monochloride (S 2 G 2 ).
  • the method provides an elastomeric sulfur-containing polymer of Formula 2, as defined herein, and comprises the steps of;
  • step (ii) reacting the anionic living styrene-butadiene copolymer chains of step (i) with sulfur monochloride (S2CI.2).
  • the non-cured polymer composition of the present invention comprises the elastomeric sulfur-containing polymer of Formula 1 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for preparation of the anionic living polymer chains and (ii) components which remain after solvent removal from, the polymerization process.
  • the elastomeric sulfur- containing polymer contained in the polymer composition is represented by Formula 2 as defined herein.
  • the non-cured (non-crosslinked or unvulcanized) polymer composition is typically obtained by conventional work-up of the reaction mixture obtained after reaction of the anionic living polymer chains with sulfur monochloride. Work-up means the removal of the solvent using steam stripping or vacuum evaporation techniques.
  • Components which are added to or formed as a result of the polymerization process include, in particular, oils (extender oils), stabilizers, fillers and further polymers.
  • oils can be added to the polymer prior to or after the termination of the polymerization process.
  • oils see WO 2009/148932 and US 2005/0159513, each of which is incorporated herein by reference in its entirety.
  • One or more stabilizers can optionally be added to the polymer prior to or after the termination of the polymerization process to prevent the degradation of the elastomeric polymer by molecular oxygen.
  • Antioxidants based on sterically hindered phenols such as 2,6-di-tert-bntyl-4-methylphenoI 5 6 > 6'-methyIenebis(2-tert-butyI-4-methylphenol) > Iso- octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexamethylenebis[3-(3 s 5 ⁇ di ⁇ tert- butyl-4-hydroxyphenyl)propionate] , octadecyl-3 -(3 ,5-di-tert-butyl-4-hydroxyphenyl) propionate, isotridecyi-3-(3,5-di-tert-buty -hydroxypheny])
  • One or more fillers can be added to the polymer prior to or after the termination of the polymerization process.
  • suitable fillers include carbon black (including electroconductive carbon black),, carbon nanotubes (CNT) (including discrete CNT, hollow carbon fibers (HCF) and modified CNT carrying one or more functional groups, such as hydroxy!, car boxy I and earbonyl groups), graphite, graphene (including discrete graphene platelets), silica, carbon-silica dual-phase filler, clays (layered silicates, including exfoliated nanoclay and organoclay), calcium carbonate, magnesium carbonate, lignin, amorphous fillers, such as glass particle-based fillers, starch-based fillers, and combinations thereof. Further examples of suitable fillers are described in WO 2009/148932 which is fully incorporated herein by reference.
  • polymers as part of the polymer composition of the invention are, in particular, polymers which are formed in the polymerization process but which are not in accordance with Formula 1 of the present invention.
  • the elastomcric sulfur-containing polymer of Formula 1 of the invention, including the polymer of Formula 2, and the respective polymer composition comprising such polymer are beneficially used in and for preparing (i) footwear, (ii) golf balls, (iii) membranes that do not contain reinforcements (such as but not limited to fibers or fabrics), (iv) adhesives, (v) modified plastics, including polybutadiene-modified acrylonitrile-styrene copolymers (ABS) and high impact polystyrene (polybutadiene-modified polystyrene, HIPS), and (vi) films that are not for automotive interiors or aircraft interiors.
  • ABS polybutadiene-modified acrylonitrile-styrene copolymers
  • HIPS high impact polystyren
  • Root temperature refers to a temperature of about 20-25°C, or to 20°C when the measurement of a specific parameter is concerned,
  • the vinyl bond content in the butadiene part of the (co)polymer was determined by IR absorption spectrometry (Morello method, I S 66 FT-IR spectrometer, Bruker Analytic GmbH).
  • the IR samples were prepared using CS 2 as a swelling agent.
  • Bonded styrene content A calibration curve was prepared by IR absorption spectrometry (IFS 66 FT-IR spectrometer). The IR samples were prepared using CS 2 as a swelling agent. For the IR determination of bonded styrene in styrene-butadiene copolymers, four bands were assessed: a) for trans- 1 ,4-pol butadiene units at 966 cm "1 , b) for cis- 1 ,4-polybutadiene units at 730 cm “1 , c) for 1 ,2-polybutadiene units at 910 cm 4 , and d) for bonded styrene (styrene aromatic bond) at 700 cm "5 .
  • the band heights are normalized according to the appropriate extinction coefficients and added to a total of 100%.
  • the normalization is done via ⁇ - and ,3 C-NMR.
  • Sulfur content was determined by X-ray fluorescence spectrometry (XRF) on an Axios spectrometer (PANalyticai). Data analysis were done with the software PCFPW from Fundex. Samples were prepared in a hot press and measured immediately,
  • GPC-Method SEC calibrated with narrow distributed polystyrene standard.
  • each GPC device 3 columns of 300 mm length each were used in a connected mode (Column Type 7991 1 GP- MXB, Pigel 10 pm MIXED-B GPC/SEC Columns, Agilent Technologies)
  • GPC Standards EasiCai PS-1 Polystyrene Standards, Spatula A F B
  • Mw/Mn PolydispersitY
  • the Mpl -Mp4 values correspond to the molecular weight measured at the first, second, third or fourth peaks of the GPC curve [the first peak M l (lowest molecular weight) is located on the right side of the curve, and the last peak (highest molecular weight) is located on the left side of the curve], respectively.
  • Tg glass transition
  • Polymerizations and the synthesis of the initiator II were performed in a nitrogen atmosphere under exclusion of moisture and oxygen.
  • S 2 CI 2 Sulfur monochloride
  • the copolymerizations were performed in a double wall, 10 liter steel reactor, which was first purged with nitrogen, before adding of organic solvent, monomers, polar coordinator compound, initiator compound and other components. The following components were then added, in this order: cyclohexane solvent (4600 grams); butadiene monomer, styrene monomer, tetramethylethylene diamine (TMEDA) and the mixture was heated to 40°C, followed by titration with n-butyl lithium to remove traces of moisture or other impurities, The polymerization initiator compound (II or n-BuLi) was added into the polymerization reactor to initiate the polymerization reaction.
  • cyclohexane solvent 4600 grams
  • butadiene monomer styrene monomer
  • TMEDA tetramethylethylene diamine
  • the polymerization was performed for 80 minutes, not allowing the polymerization temperature to exceed 60°C. Next, 2.3% (Examples 1-3, 5, 6) or 0.5% (Example 4) of the total butadiene monomer amount was added, followed by the addition of the coupling agent, unless stated otherwise. After 5 minutes (Examples 2, 3) or 10 minutes (Examples 1 , 4-6), the polymerization was terminated by the addition of methanol (one equivalent based on initiator). 0.25 wt% IRGANOX 1520 based on the total monomer weight was added as a stabilizer to the polymer solution. This mixture was stirred for 10 minutes.
  • vinyl content is that of the 1 ,2-polybutadiene unit content of the final copolymer, and is determined by IR Spectroscopy
  • Polymer compositions were prepared from the polymers of Examples 2 and 4.
  • the polymer of Example 2 is an. e!astomeric sulfur-containing polymer according to the invention, whereas the polymer of Example 4 is a comparative polymer not in accordance with the invention. All indications of amounts are based on weight, relative to 100 parts by weight of total rubber (phr), or relative to 100 parts by weight of silica (phf).
  • compositions were prepared in the conventional manner in two stages in a lab tangential blender.
  • Rubber compound El contains 100 phr of the polymer of Example 2.
  • Rubber compound VI uses the polymer of Example 4 instead, which has a similar molecular weight and contains SBR polymer segments, yet linked via silicon atoms instead of the di-, tri or tetrasulfide units according to the present invention. As a result, the polymer segments of Example 4 do not contain sulfur- ulcanizable groups.
  • a similar hardness (Shore A at room temperature) was established by adjusting the amounts of sulfur and accelerator.
  • Test pieces were prepared from each composition by vulcanization, and tested for typical physical properties in the rubber industry, using the following test methods:
  • Tg Glass transition temperature (Tg) derived from loss factor tan ⁇ obtained from dynamic- mechanical measurement according to DIN 53 513 (temperature sweep)
  • rubber compound El made with a polymer of the invention has, at almost identical Tg. a substantially higher impact resilience at 70 °C than the comparative rubber compound VI, indicating a much improved (reduced) rolling resistance of El versus VI .
  • rubber compound El exhibits improved abrasion resistance (reduced abrasion) and increased tensile strength over rubber compound VI , At the same, the remaining physical properties can be maintained at almost the same level.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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PCT/EP2013/077700 2013-12-20 2013-12-20 Sulfur-containing polymers WO2015090447A1 (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US20160297948A1 (en) * 2013-12-20 2016-10-13 Continental Reifen Deutschland Gmbh Rubber mixture and vehicle tire
FR3068357A1 (fr) * 2017-06-30 2019-01-04 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc ayant une bonne tenue au fluage
WO2019115470A1 (fr) * 2017-12-11 2019-06-20 Compagnie Generale Des Etablissements Michelin Procédé de synthèse d'un polymère fonctionnel ou non à structure particulière
CN111978447A (zh) * 2019-05-21 2020-11-24 中国石油化工股份有限公司 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
DE1260794B (de) * 1963-08-06 1968-02-08 Bayer Ag Verfahren zur Herstellung kautschukelastischer Dienpolymerer mit verbesserten Eigenschaften
US5567784A (en) * 1994-10-10 1996-10-22 Bayer Ag Process for producing diene rubbers polymerized by means of Nd catalysts and exhibiting reduced cold flow and low intrinsic odor
WO2013127448A1 (en) * 2012-02-29 2013-09-06 Styron Europe Gmbh Process for producing diene polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1260794B (de) * 1963-08-06 1968-02-08 Bayer Ag Verfahren zur Herstellung kautschukelastischer Dienpolymerer mit verbesserten Eigenschaften
US5567784A (en) * 1994-10-10 1996-10-22 Bayer Ag Process for producing diene rubbers polymerized by means of Nd catalysts and exhibiting reduced cold flow and low intrinsic odor
WO2013127448A1 (en) * 2012-02-29 2013-09-06 Styron Europe Gmbh Process for producing diene polymers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160297948A1 (en) * 2013-12-20 2016-10-13 Continental Reifen Deutschland Gmbh Rubber mixture and vehicle tire
US9701809B2 (en) * 2013-12-20 2017-07-11 Continental Reifen Deutschland Gmbh Rubber mixture and vehicle tire
FR3068357A1 (fr) * 2017-06-30 2019-01-04 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc ayant une bonne tenue au fluage
WO2019115470A1 (fr) * 2017-12-11 2019-06-20 Compagnie Generale Des Etablissements Michelin Procédé de synthèse d'un polymère fonctionnel ou non à structure particulière
CN111978447A (zh) * 2019-05-21 2020-11-24 中国石油化工股份有限公司 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法
CN111978447B (zh) * 2019-05-21 2023-04-11 中国石油化工股份有限公司 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法

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