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EP1525235A1 - Regulateur de microstructures pour la polymerisation anionique - Google Patents

Regulateur de microstructures pour la polymerisation anionique

Info

Publication number
EP1525235A1
EP1525235A1 EP02787664A EP02787664A EP1525235A1 EP 1525235 A1 EP1525235 A1 EP 1525235A1 EP 02787664 A EP02787664 A EP 02787664A EP 02787664 A EP02787664 A EP 02787664A EP 1525235 A1 EP1525235 A1 EP 1525235A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
randomizer
general formula
compound
microstructure
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Withdrawn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
EP02787664A
Other languages
German (de)
English (en)
Inventor
Walter Hellermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10243618A external-priority patent/DE10243618A1/de
Application filed by Individual filed Critical Individual
Publication of EP1525235A1 publication Critical patent/EP1525235A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • 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
    • 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 or optionally coupled, non - blocking copolymers based on conjugated dienes and vinylaromatic compounds by anionic polymerization, in particular at high temperatures, and the process products or Polymers and their use, in particular for the manufacture 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 vinylaromatic 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 - generally 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 - generally styrene - at the same time; ie a good randomizer effect is also achieved at the same time.
  • 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 frequently 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 structural governor for the anionic polymerization of dienes. However, no statement is made regarding the polymerization rate achieved with this.
  • alkyl tetrahydrofur- fururyl ethers are essentially suitable Modifiers for the anionic polymerization of dienes described. These regulators are said to be able to achieve much higher polymerization rates in the case of isoprene polymerization than in the case of TMEDA. However, these compounds are still too slow and at the same time are noticeable in the rubber due to an unpleasant smell.
  • microstructure control effect which occurs with increasing temperature should be small in order to enable a high polymerization temperature.
  • the effect of a microstructure regulator basically 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.
  • the subject of the present invention - according to a first aspect of the present invention - is thus a method according to claim 1. Further advantageous configurations are the subject of the subclaims (claims 2 to 10).
  • 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.
  • the present invention shows that the compounds of the general formulas (I a) to (I n), as defined in the claims, can be used as microstructure regulators and randomizers for anionic polymerization.
  • the compounds of the general formulas (I a) to (I n) 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 n) - generally ethers such as alkyl or alkylamino ethers or cyclic oxolane or morpholine alkyl ethers or cyclic oxolane or morpholine alkyl amino ethers - the particular advantage of still having a pronounced microstructure control effect even at a relatively high polymerization temperature (and consequently short reaction times).
  • the compounds of the general formulas (I a) to (I n) used according to the invention can be prepared by the processes known per se and described in the literature.
  • So z. B. the alkylamino ethers used according to the invention can be prepared from a sodium alcoholate and the corresponding alkyl halide by the Williamson ether synthesis (DE 41 19 576 AI). Some of the compounds are also commercially available; so z. B. the 2,2'-Dimorpholinodiethylether manufactured by BASF AG.
  • the four-tooth Lewis bases of the general formulas (I c), (I f) and (I k) are, for. B.
  • 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 are particularly suitable.
  • Aromatic solvents such as. B. benzene, toluene and. a. Mixtures of the compounds described above can of course also 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 inexpensive 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.
  • 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. Likewise, the structure regulators according to the invention can be used individually or in any quantity ratio with one another.
  • a potassium or sodium alcoholate in addition to the initiator in order to further improve the statistical distribution of the styrene units in the copolymers.
  • alkali or alkaline earth metal salts especially potassium or sodium salt ze, mono- or polyhydric alcohols and phenols and mono- or polyhydric carboxylic acids into consideration.
  • the potassium compounds are preferred.
  • Examples include the sodium or potassium salts of dimethyl ins, 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 called. 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 the 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 in a mixture with one another.
  • a variant of the process according to the invention consists in adding the polymerization units obtained after largely complete conversion of the monomers with a coupling agent to give star-shaped polymers couple.
  • 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 nm 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 of 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 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.
  • customary auxiliaries such as zinc oxide, stearic acid, resin acids, anti-aging agents and ozone protection waxes.
  • 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 the retreading of 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 to produce 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.
  • DEEE 2- (2-dimethylaminoethoxy) -l-ethoxyethane
  • DEM 4- (2- (dimethylamino) ethyl) molin
  • BTFM bis-tetrahydrofurfurylmethane
  • 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 ⁇ -HMR analysis:
  • TBEE (1-ethoxy-2-tert-butoxyethane) serves here as a comparator according to EP-A-0 304 589.

Landscapes

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

Abstract

L'invention concerne un procédé de production de polymères non séquencés éventuellement couplés à base de diènes conjugués ou de copolymères non séquencés éventuellement couplés à base de diènes conjugués et de composés aromatiques vinyliques par polymérisation anionique dans un solvant organique inerte en présence d'un composé organolithium utilisé en tant qu'initiateur et d'un régulateur et/ou répartiteur aléatoire de microstructures, des composés d'éther spécifiques étant utilisés en tant que régulateur et/ou répartiteur aléatoire de microstructures. Les polymères ainsi produits conviennent en particulier pour la production de matériaux amortisseurs, de pneus, d'éléments de pneu (par exemple de bandes de roulement et de flancs de pneu) et d'articles techniques en caoutchouc.
EP02787664A 2002-07-25 2002-11-13 Regulateur de microstructures pour la polymerisation anionique Withdrawn EP1525235A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10233988 2002-07-25
DE10233988 2002-07-25
DE10243618 2002-09-19
DE10243618A DE10243618A1 (de) 2001-11-23 2002-09-19 Mikrostrukturregler zur Herstellung von Homo- und Copolymeren von Dienen und Vinylaromaten durch anionische Polymerisation
PCT/EP2002/012689 WO2004014966A1 (fr) 2002-07-25 2002-11-13 Regulateur de microstructures pour la polymerisation anionique

Publications (1)

Publication Number Publication Date
EP1525235A1 true EP1525235A1 (fr) 2005-04-27

Family

ID=31716587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02787664A Withdrawn EP1525235A1 (fr) 2002-07-25 2002-11-13 Regulateur de microstructures pour la polymerisation anionique

Country Status (3)

Country Link
EP (1) EP1525235A1 (fr)
AU (1) AU2002351991A1 (fr)
WO (1) WO2004014966A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3822219A (en) * 1970-07-23 1974-07-02 Gulf Resources & Chem Corp Catalyst composition
CN1118496C (zh) * 2000-04-20 2003-08-20 江苏圣杰实业有限公司 共轭二烯和/或单乙烯基芳烃聚合物的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004014966A1 *

Also Published As

Publication number Publication date
AU2002351991A1 (en) 2004-02-25
WO2004014966A1 (fr) 2004-02-19

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