EP1453869A2 - Regulateur de microstructure pour la polymerisation anionique - Google Patents

Regulateur de microstructure pour la polymerisation anionique

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Publication number
EP1453869A2
EP1453869A2 EP02792760A EP02792760A EP1453869A2 EP 1453869 A2 EP1453869 A2 EP 1453869A2 EP 02792760 A EP02792760 A EP 02792760A EP 02792760 A EP02792760 A EP 02792760A EP 1453869 A2 EP1453869 A2 EP 1453869A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
randomizer
radical
microstructure
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02792760A
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German (de)
English (en)
Inventor
Walter Hellermann
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Individual
Original Assignee
Individual
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Publication date
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Publication of EP1453869A2 publication Critical patent/EP1453869A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
    • C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • 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

Definitions

  • the present invention relates to a process for the preparation of optionally coupled, non-blocking polymers based on conjugated dienes and optionally monovinylaromatic compounds by anionic polymerization, in particular at high temperatures, and to the process products or polymers prepared in this way and their use, in particular for the preparation of Tires and tire components as well as damping elements.
  • microstructure regulators of the prior art have the disadvantage that their efficiency is significantly reduced at high polymerization temperatures. Furthermore, in most cases they have only a weak influence on the statistical incorporation of the vinyl aromatic component, ie there is a poor randomizer effect.
  • the term microstructure regulator includes, in particular, a multidentate Lewis base which, in addition to the microstructure, also specifically controls the statistical incorporation of vinylaromatic compounds - usually styrene - at the same time; ie a good randomizer effect is also achieved at the same time.
  • a multidentate Lewis base which, in addition to the microstructure, also specifically controls the statistical incorporation of vinylaromatic compounds - usually styrene - at the same time; ie a good randomizer effect is also achieved at the same time.
  • microstructure regulators DE-PS 27 07 761 and 31 15 878.
  • surface-active agents must also be used for the statistical incorporation of the monomers in the polymer molecule.
  • EP-A-0 304 589 describes certain ethylene glycol dialkyl ethers as suitable microstructure regulators.
  • these compounds show a significant drop in the microstructure control action at higher polymerization temperatures and, moreover, do not have an optimal randomizer action.
  • a major disadvantage of the microstructure regulators of the prior art is the often weakening regulating action when the polymerization temperature rises.
  • EP-A-507 222 and US-A-5 112 929 describe cyclic 1,3-dioxolane acetals such as e.g. B. 2- (2-oxolanyl) dioxolane as micro structure regulator for the anionic polymerization of dienes.
  • cyclic 1,3-dioxolane acetals such as e.g. B. 2- (2-oxolanyl) dioxolane as micro structure regulator for the anionic polymerization of dienes.
  • the reduction in the microstructure control effect which occurs with increasing temperature should be small in order to enable a high polymerization temperature.
  • the effect of a molecular structure regulator depends on the ratio of the molar amounts of regulator and initiator.
  • Molar ratio regulator / initiator is generally between 1: 1 to 10: 1. The effect to be achieved according to 1. should already be achievable with a molar ratio regulator / initiator of less than 5: 1.
  • An object of the present invention is to provide a method of the type described above which avoids the aforementioned disadvantages.
  • Another object of the invention is to produce non-blocking polymers (that is, in the case of diene copolymerization, the styrene units should be largely incorporated statically in the polymer chain so that the copolymers can be used, for example, to produce tires and damping materials).
  • the polymers or rubbers obtainable by this process should have a glass transition temperature in the range from -70 ° C. to +10 ° C., in particular -30 ° C. to 0 ° C.
  • Another object of the present invention - according to a second aspect of the present invention - are the products or polymers obtainable by the process according to the invention.
  • the process products or polymers according to the invention are distinguished in particular by a high proportion of 1,2-structural units of butadiene and 1,2- and 3,4-structural units of isoprene.
  • Another object of the present invention - according to a third aspect of the present invention - is the use of the products or polymers obtainable by the process according to the invention, as described in more detail in claims 12 to 16.
  • Another object of the present invention - according to a fourth aspect of the present invention - are products produced with the polymers produced according to the invention, in particular damping materials, tires and tire components (for example tire treads or sidewalls) and technical rubber articles.
  • a further object of the present invention - according to a fifth aspect of the present invention - are the compounds of the general formulas (I c) and (I d) defined in claims 1 to 3, in particular for anionic polymerization.
  • the present invention shows that the compounds of the general formulas (I a) to (I g), as defined in the claims, can be used as Mil ⁇ ostmktur controllers and randomizers for anionic polymerization.
  • the compounds of the general formulas (I a) to (I g) have both the properties of a good microstructure regulator and that of a good randomizer.
  • the compounds of the general formulas (I a) to (I g) - generally ethers such as alkyl or alkylamino ethers or cyclic dioxolane or dioxane alkyl ethers or cyclic dioxolane or dioxane alkylamino ethers - have particular advantage of having a pronounced Mil ⁇ O structure control effect even at a relatively high polymerization temperature (and consequently short reaction times).
  • the compounds of the general formula (I a) to (I g) used according to the invention can be prepared by the processes known per se and described in the literature.
  • So z. B the Akylaminoether used according to the invention for example by Williamson ether synthesis from a sodium alcoholate and the corresponding alkyl halide (DE 41 19 576 AI).
  • 2-Dimethylaminomethyl-1,3-dioxolane (DM AD) is produced, for example, according to US Pat. No. 2,439,969 and DE 825 416.
  • An inert organic solvent is generally used as the reaction medium for the process according to the invention.
  • Hydrocarbons with 5 to 12 carbon atoms, such as pentane, hexane, heptane and octane, and their cyclic analogs.
  • Aromatic solvents such as. B. benzene, toluene, etc. Of course, mixtures of the compounds described above can be used.
  • Alkyl lithium compounds which are easily accessible by reacting lithium with the corresponding alkyl halides are generally used as the catalyst for the process according to the invention.
  • the alkyl radicals generally have 1 to 10 carbon atoms. Individual hydrogen atoms can be substituted by phenyl radicals.
  • the following alkyl lithium compounds are particularly suitable: methyl lithium, ethyl lithium and pentyllithium. Sec. And n-butyl lithium is preferred.
  • bi-functional organic lithium compounds can also be used. However, these are less easily accessible and, in particular, less cheap than their monofunctional analogs if one wants to produce star-shaped solution rubbers.
  • the amount of catalyst used depends on the molecular weight to be adjusted. This is usually in the range of 50,000 to 1,500,000.
  • the microstructure regulator is preferably added at the start of the reaction. However, if it should be appropriate for any reason, it can also be added during the polymerization.
  • the Mil ⁇ o Modell controllers according to the invention can also be used individually or in any quantity ratio with one another.
  • the alkali metal or alkaline earth metal salts in particular potassium or sodium salts, mono- or polyhydric alcohols and phenols and mono- or polyvalent carboxylic acids come into consideration.
  • the potassium compounds are preferred.
  • Examples include the sodium or potassium salts of dimethylamine, di-n-butylamine, dibutylamine, lauric acid, palmitic acid, stearic acid, benzoic acid, phthalic acid, methyl alcohol, ethyl alcohol, Isopropyl alcohol, propyl alcohol, tert-butyl alcohol, tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol or phenol. Potassium tert-butoxide is particularly preferred.
  • Anionic surface-active compounds with a hydrophilic group such as. B. -S0 3 M or -OS0 3 M, where M is potassium or sodium or rubidium, are additionally added to the initiator.
  • Examples are salts of alkylarylsulfonic acids, such as. As potassium stearyl benzene sulfonate, potassium dodecyl benzene sulfonate, potassium nonyl benzene sulfonate and potassium decyl benzene sulfonate or salts of sulfuric acid esters of higher alcohols, such as. B. Potassium stearyl sulfate, potassium dodecyl sulfate, potassium decyl sulfate, potassium nonyl sulfate and potassium N-methyl taurate.
  • the following compounds are suitable as conjugated dienes: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene. 1,3-Butadiene and isoprene are particularly preferred.
  • the following vinyl aromatic compounds are suitable for copolymerization with the conjugated dienes: 3-methylstyrene, 4-methylstyrene, styrene, 1-vinylnaphthalene and 2-vinylnaphthalene, styrene being particularly preferred.
  • the vinyl aromatic compounds as well as the conjugated dienes can be used individually or as a mixture with one another.
  • a variant of the process according to the invention consists in coupling the polymerization units obtained after the monomers have been largely reacted with a coupling agent to form star-shaped polymers.
  • Coupling agents suitable for this purpose are in particular tetrahalides of the elements silicon, germanium, tin and lead and aromatics which carry at least two vinyl groups, such as, for example, B. 1,3,5-trivinylbenzene and 1,3- and 1,4-divinylbenzene.
  • the polymerization is generally carried out in the temperature range from 50 to 90 ° C.
  • the polymerization is preferably carried out at temperatures from 80 to 150.degree.
  • the coupling is generally carried out at 0 to 150 ° C, preferably at 40 to 100 ° C.
  • the process according to the invention can be operated batchwise or continuously.
  • the amorphous polymers obtained are to be processed into vulcanizates, they are generally mixed with active, reinforcing fillers, a vulcanizing agent and customary additives.
  • active and inactive fillers used in the rubber industry are used as fillers.
  • these are highly disperse silicas treated with silane coupling agents with specific surfaces of 5 to 1000 m 2 / g, preferably 20-400 m 2 / g, and with primary particle sizes of 10 to 400 ⁇ m and carbon blacks with BET surfaces of 20 up to 200 m 2 / g.
  • the fillers can be used alone or in a mixture.
  • Masses which are intended for the production of tire treads are generally formed into raw tread strips.
  • homogenization and shaping which can be carried out, for example, in an extruder, the conditions of temperature and time are chosen so that no vulcanization occurs.
  • the rubber component can in this case, for example, 10 to 70% by mass from a reaction product according to the invention and 90 to 30% by mass from a known, amorphous, highly unsaturated general-purpose rubber, such as. B. styrene / butadiene rubber, 1,4-cis-polybutadiene, 1,4-cis-polyisoprene or natural rubber.
  • a known, amorphous, highly unsaturated general-purpose rubber such as. B. styrene / butadiene rubber, 1,4-cis-polybutadiene, 1,4-cis-polyisoprene or natural rubber.
  • Usual vulcanizing agents contain e.g. B. sulfur in combination with accelerators.
  • the amount of the vulcanizing agent depends on the other components in the vulcanizable mass and can be determined by simple, orientation tests.
  • plasticizer oils customary in rubber technology preferably aromatic, aliphatic and naphthenic and paraffinic hydrocarbons, and customary auxiliaries such as zinc oxide, stearic acid, resin acids, anti-aging agents and ozone protection waxes.
  • Particularly preferred are the new, label-free naphthenic process oils of the type TDAE (Treated Distillate Aromatic Extracts), such as. B. BP Vivatec 500, or of the type MES (M Idly Refined Solvates), such as. B. BP Vivatec 200.
  • the polymers according to the invention are particularly suitable for the production of treads for car and truck tires, both for the production of new tires and for retreading old tires.
  • the tire treads obtained are characterized by an excellent braking effect both in ABS braking and in blocking braking on wet roads. Also to be emphasized is the extraordinarily high reversion stability during the vulcanization process and the extraordinarily high network stability of the tire treads under dynamic stress.
  • the polymers according to the invention can also be used for the production of damping elements (see, for example, DE-OS 24 59 357).
  • the polymers according to the invention are produced as follows:
  • Other components of this mixture were in particular pentane, heptane and octane and their isomers.
  • the solvent was dried over a molecular sieve with a pore size of 0.4 nm, so that the water content was reduced to below 10 ppm, and then stripped with Na.
  • the organic lithium compound was n-butyllithium (BuLi), which was used in the form of a 15 percent by weight solution in hexane. Before being used, isoprene was separated from the stabilizer by distillation. The glycol and amino ethers were dried over aluminum oxide and then titrated with n-butyllithium in the presence of o-phenanthroline.
  • the divinylbenzene (DVB) was used in the form of a solution dried over A1 2 0 3 and containing 44% m- and 20% p-divinylbenzene.
  • Coupling yield is the percentage of rubber which has a star-shaped structure after reaction with a coupling agent and which is distinguished from the uncoupled rubber by a considerably higher molecular weight.
  • the determination is carried out with the GPC analysis, using tetrahydrofuran as the solvent and polystyrene as the column material.
  • the polymers are characterized by a light scattering detector. For this purpose, samples are taken from the reactor before the coupling agent is added and at the end of the reaction.
  • the microstructure is determined by 'H-NMR or by means of IR spectrometry.
  • the glass transition temperature Tg was measured with a vibration elastometer (1 Hz at 1 ° C / min. Heating time).
  • the block styrene content was determined according to Houben-Weyl, Methods of Organic Chemistry Vol. 14/1 (1961), page 698. The following examples serve to further illustrate the present invention without, however, restricting its scope.
  • DMAD 2-dimethylaminomethyl-1,3-dioxolane
  • TBEE 1-ethoxy-2-tert-butoxy-ethane
  • hexane a monomer mixture of 40 parts of 1,3-butadiene, 40 parts of isoprene, 20 parts of styrene, 0.02 parts of DVB and 1.0 part of ethylene glycol tert-butyl ether (TBEE), and after drying over molecular sieves (0, 4 ⁇ m) titrated with butyllithium under thermoelectric control.
  • TEE ethylene glycol tert-butyl ether
  • the polymerization was started at 40 ° C. by adding 0.05 part of n-butyllithium. The temperature reached 108 ° C after 8 minutes with slight cooling. At this temperature, the mixture was allowed to react for 30 minutes.
  • the polymerization was stopped by adding a solution of 0.5 part of 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) in 2 parts of moist toluene.
  • the solvent was distilled off with steam and the polymer was dried in a forced-air drying cabinet at 70 ° C. for 24 hours.
  • star polymers were produced in the subsequent experiments.
  • hexane a monomer mixture of 75 parts of 1,3-butadiene and 25 parts of styrene and 0.7 part of l-ethoxy-2-n-butoxyethane are placed in a V2A autoclave flushed with dry nitrogen and, after drying over molecular sieves (0 , 4 nm) titrated with butyl lithium under thermoelectric control.
  • the polymerization was started at 35 ° C. by adding 0.080 parts of n-BuLi. The temperature reached 113 ° C after 10 minutes with slight cooling. At this temperature, the mixture could react for 30 minutes. Then 0.81 part of divinylbenzene was added at this temperature.
  • the polymerization was carried out by adding a solution of 0.5 part of 2,2'-methylene bis (4-methyl-6-tert-butylphenol) stopped in 2 parts of wet toluene.
  • the solvent was distilled off with steam and the polymer was dried in a forced-air drying cabinet at 70 ° C. for 24 hours.
  • the temperature dependence of the microstructure control effect was investigated using isoprene and butadiene polymerizations.
  • the microstructures of the polyisoprenes were determined by 'H-NMR analysis.
  • the reaction rate constants were calculated from the time conversion curves in accordance with a 1st order reaction.
  • the 3,4-polyisoprene was stabilized with 0.5% BKF and worked up by precipitation with isopropanol / methanol and subsequent drying at 50 ° C.
  • the microstructure of the polymer is determined by 'H-HMR analysis:
  • EDE is significantly faster than TBEE, although EDE also performs better in the microstructure control at 70 ° C.
  • the randomizer effects of the regulators were investigated using isothermal butadiene / styrene copolymerizations with 40% by weight styrene at 50 ° C. with a regulator / n-BuLi ratio of 5.
  • Copolymerization of butadiene and styrene to determine the randomizer effect 703 g of hexane, 50.6 g (0.94 mol) of butadiene, 33.7 g (0.32 mol) of styrene and 4.8 are placed in a 2-1 steel reactor under a nitrogen atmosphere mmol filled microstructure regulator. After the temperature has been raised to 50 ° C., the reactor contents are titrated with 0.33 mmol of n-butyllithium (14% solution in hexane) until the color changes, after addition of 1 ml of 1% benzene o-phenanthroline solution, and the polymerization started by adding 0.96 mmol of n-butyllithium.
  • the structure of the copolymer is determined by IR analysis.
  • the block polystyrene content is determined by KMn0 4 degradation.
  • Table 5 Randomizer effect when copolymerizing butadiene / styrene 60/40 at 50 ° C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de production de polymères sans bloc éventuellement couplés sur la base de diènes conjugués et de composés éventuellement monovinylaromatiques par polymérisation anionique dans un milieu de solution organique inerte en présence d'un composé organique de Lithium comme initiateur, ainsi qu'un régulateur et/ou transformateur de microstructure, des composés d'éther spécifiques étant introduits comme régulateur et/ou transformateur de microstructure. Les polymères résultants conviennent en particulier pour la production de matériaux amortisseurs, des pneus, ou des éléments de pneus (par exemple des chapes ou des épaulements de pneus) et des articles techniques en caoutchouc.
EP02792760A 2001-11-23 2002-11-13 Regulateur de microstructure pour la polymerisation anionique Withdrawn EP1453869A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10157637 2001-11-23
DE10157637 2001-11-23
DE10158609 2001-11-29
DE10158609 2001-11-29
PCT/EP2002/012687 WO2003044065A2 (fr) 2001-11-23 2002-11-13 Regulateur de microstructure pour la polymerisation anionique i

Publications (1)

Publication Number Publication Date
EP1453869A2 true EP1453869A2 (fr) 2004-09-08

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EP02792760A Withdrawn EP1453869A2 (fr) 2001-11-23 2002-11-13 Regulateur de microstructure pour la polymerisation anionique

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EP (1) EP1453869A2 (fr)
AU (1) AU2002358503A1 (fr)
WO (1) WO2003044065A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10234746B4 (de) * 2002-07-30 2004-04-29 Sasol Germany Gmbh Verfahren zur Herstellung von Polymerisaten unter Verwendung von konjugierten Dienen und vinylaromatischen Verbindungen, nach diesem Verfahren hergestellte Polymerisate und deren Verwendung
CA2576167C (fr) * 2004-08-06 2010-02-02 Jsr Corporation Procede de fabrication de caoutchouc de copolymere de diene conjugue
WO2016108713A1 (fr) * 2014-12-30 2016-07-07 Публичное акционерное общество "СИБУР Холдинг" Procédé de production de copolymère à blocs styrène-butadiène

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Publication number Priority date Publication date Assignee Title
US3822219A (en) * 1970-07-23 1974-07-02 Gulf Resources & Chem Corp Catalyst composition
GB8316052D0 (en) * 1983-06-13 1983-07-20 Shell Int Research Elastomeric copolymers
DE3724870A1 (de) * 1987-07-28 1989-02-09 Huels Chemische Werke Ag Verfahren zur herstellung von polymerisaten auf basis von konjugierten dienen und ggf. monovinylaromatischen verbindungen
DE10055497A1 (de) * 2000-11-09 2002-05-29 Bayer Ag Modifizierungsmittel für die anionische Polymerisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03044065A3 *

Also Published As

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WO2003044065A3 (fr) 2004-01-22
AU2002358503A1 (en) 2003-06-10
AU2002358503A8 (en) 2003-06-10
WO2003044065A2 (fr) 2003-05-30

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