EP0754198A1 - Procede de polymerisation anionique de monomeres acryliques - Google Patents

Procede de polymerisation anionique de monomeres acryliques

Info

Publication number
EP0754198A1
EP0754198A1 EP96905350A EP96905350A EP0754198A1 EP 0754198 A1 EP0754198 A1 EP 0754198A1 EP 96905350 A EP96905350 A EP 96905350A EP 96905350 A EP96905350 A EP 96905350A EP 0754198 A1 EP0754198 A1 EP 0754198A1
Authority
EP
European Patent Office
Prior art keywords
process according
acrylic
methacrylate
acrylate
methacrylic
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Withdrawn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
EP96905350A
Other languages
German (de)
English (en)
Inventor
Munmaya Kumar Mishra
Shailaja Madhusudhan Shirodkar
Alfred Karl Jung
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.)
Texaco Development Corp
Original Assignee
Texaco Development Corp
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
Application filed by Texaco Development Corp filed Critical Texaco Development Corp
Publication of EP0754198A1 publication Critical patent/EP0754198A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent

Definitions

  • the invention relates to the polymerization of acrylic monomers, optionally using vinyl comonomers in the presence of an anionic initiator to form polymers or copolymers having a narrow molecular weight distribution.
  • R - M in which denotes an alkali metal or an alkaline earth metal and R denotes a straight-chain or branched alkyl containing 2 to 6 carbon atoms or an aryl have been employed.
  • initiators include sec- butyllithium, naphthalenesodium, 1,4-disodio-l,1,4,4- tetraphenyl butane, diphenylmethyl potassium, diphenylmethyl sodium, 1 ' -methylstyryllithium, 1,1- diphenyl-3-methylpentyllithium and others such as tertiary alcoholates of lithium and compounds containing trimethylsilyl groups.
  • the present invention relates to an improved process for the anionic polymerization or copolymerizatio of acrylates and methacrylates wherein the monomers and comonomers are added to the anionic polymerization reaction medium either at once or in very fast continuous manner. More specifically, the instant process comprises the steps of preparing an anionic polymerization initiation system and adding the monomers to be polymerized or copolymerized to the initiation system either at once or in a rapid continuous manner.
  • the present invention relates to the anionic polymerization of acrylate and methacrylate monomers optionally with vinyl comonomers.
  • Acrylic and methacrylic monomers which are polymerized in the present invention include acrylic acid, acrylic acid esters, acrylonitriles, acrylamides, methacrylic acid, methacrylic acid esters, methacrylonitriles, and methacrylamide.
  • the preferred acrylic and methacrylic monomers are alkyl acrylates or alkyl methacrylates wherein the alkyl group contains from 1 to 18 carbon atoms.
  • the alkyl radical can be either unsubstituted or substituted.
  • acrylates and methacrylates include methylacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, propyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hexyl acrylate, hexyl methacrylate, isopropyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate and stearyl methacrylate.
  • Vinyl comonomers include, for example, butadiene, isoprene, styrene, alpha methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, vinylnaphthalene, 2-vinylpyridine, 4-vinylpyridine and the like.
  • Initiators useful in the present invention include initiators of the formula:
  • R - M in which M is an alkali metal or an alkaline earth metal and R is a straight-chain or branched alkyl or cyclo-alkyl preferably having from 1 to 6 carbon atoms or an aryl.
  • initiators include, for example, hydrocarbyllithium initiators such as alkyllithium compounds, preferably methyl lithium, n-butyllithium, sec- butyllithium, cycloalkyllithium compounds, preferably, cyclohexyllithium and aryllithium compounds, preferably, phenyllithium, 1-methylstyryllithium, p-tolyllithium, naphyllithium and 1,l-diphenyl-3- methylpentyllithium.
  • Also useful initiators include, naphthalene sodium, 1,4-disodio-l,1.4,4-tetraphenylbutane diphenylmethyl-potassium and diphenylmethylsodium.
  • Tertiary alcoholates of lithium and compounds containing trimethylsilyl groups may also be employed.
  • the instant process is preferably carried out i the absence of moisture and oxygen and in the presence of at least one inert solvent.
  • the polymerization is conducted in the absence of any impurit which is detrimental to an anionic catalyst systems.
  • the inert solvent is preferably a hydrocarbon, an aromatic solvent or an ether.
  • Suitable solvents include isobutane, pentane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, diglyme, tetraglyme, orthoterphenyl, biphenyl, decalin or tetralin.
  • the polymerization or copolymerization temperature useful in the present process varies between about 30°C and about -78°C, preferably between about 0°C and -78°C.
  • the present process preferably employs 1,1- diphenylethylene in the initiator system for the anionic polymerization.
  • 1,1-diphenylethylene has relatively high electro-affinity and does not homopolymerize.
  • the instant process enables the preparation of a whole range of homopolymers and copolymers including block copolymers wherein the number average molecular weight range of about 500 to about 1,000,000 preferably from about 1,000 to about 500,000, most preferably from about 1,000 to about 200,000 (number average m.w.) and a polydispersity index of about 1.0 to about 2.0, preferably from about 1.0 to about 1.5.
  • the polymers and copolymers prepared in the present process have various known uses including, for example as lubricant additives.
  • the polymerization is generally carried out in an inert atmosphere, for example under a nitrogen, argon, etc. atmosphere.
  • Equipment used in the polymerization reaction should be carefully dried such as by drying at about 150°C for several hours. Solvents and reagents are also carefully dried.
  • THF tetrahydrofuran
  • the THF can be freshly distilled over sodium-benzophenone (from a characteristic purple color) .
  • Acrylic or methacrylic or other monomers or comonomers can be purified by passing the monomer or comonomer through neutral alumina.
  • Diphenyl ethylene (DPE) can be dried over molecular sieve.
  • the metallic initiators are normally used as received.
  • the polymerization system was titrated wit sec. butyllithium to a red endpoint (process for cleaning the impurities) ;

Landscapes

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

Abstract

Un polymère ou un copolymère ayant une faible polydispersivité est formé par un procédé de polymérisation anionique. Le procédé comprend les étapes suivantes: formation d'un milieu initiateur de polymérisation; addition rapide d'un monomère acrylique ou méthacrylique au milieu initiateur de la polymérisation; et polymérisation du monomère acrylique ou méthacrylique afin de former le polymère ou le copolymère ayant une faible polydispersivité.
EP96905350A 1995-01-27 1996-01-22 Procede de polymerisation anionique de monomeres acryliques Withdrawn EP0754198A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37897895A 1995-01-27 1995-01-27
US378978 1995-01-27
PCT/US1996/001468 WO1996023008A2 (fr) 1995-01-27 1996-01-22 Procede de polymerisation anionique de monomeres acryliques

Publications (1)

Publication Number Publication Date
EP0754198A1 true EP0754198A1 (fr) 1997-01-22

Family

ID=23495327

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96905350A Withdrawn EP0754198A1 (fr) 1995-01-27 1996-01-22 Procede de polymerisation anionique de monomeres acryliques

Country Status (4)

Country Link
EP (1) EP0754198A1 (fr)
JP (1) JPH09511785A (fr)
AU (1) AU4913796A (fr)
WO (1) WO1996023008A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5834408A (en) * 1997-10-24 1998-11-10 Ethyl Corporation Pour point depressants via anionic polymerization of (meth)acrylic monomers
US6013735A (en) * 1998-02-13 2000-01-11 Ethyl Corporation Process for the preparation of acrylate and methacrylate polymers
WO2019013600A1 (fr) * 2017-07-14 2019-01-17 주식회사 엘지화학 Procédé de préparation d'un polymère

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB836736A (en) * 1957-03-20 1960-06-09 Ici Ltd Polymerisation process
JP2926607B2 (ja) * 1989-06-05 1999-07-28 エルク アトケム ソシエテ アノニム アクリルモノマーのイオン重合方法および重合開始系

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9623008A2 *

Also Published As

Publication number Publication date
WO1996023008A2 (fr) 1996-08-01
JPH09511785A (ja) 1997-11-25
WO1996023008A3 (fr) 1997-02-13
AU4913796A (en) 1996-08-14

Similar Documents

Publication Publication Date Title
US5552491A (en) Star-branched acrylate and methacrylate polymers
JP2604344B2 (ja) （メタ）アクリルモノマーのアニオン重合開始系
Aoshima et al. Living cationic polymerization of vinyl monomers by organoaluminium halides: 1. EtAlCl2/ester initiating systems for living polymerization of vinyl ethers
CA2023555A1 (fr) Polymeres bloques a distribution etroite de poids moleculaires
US4767824A (en) Process for polymerizing acrylic monomers and possibly non-acrylic co-monomers
US5668231A (en) Heat-resistant maleimido polymers/block copolymers
JP2926607B2 (ja) アクリルモノマーのイオン重合方法および重合開始系
US4927703A (en) Process for the anionic polymerization of acrylic monomers and optionally of vinyl comonomers
CA1275519C (fr) Copolymere de styrene
EP0095086B1 (fr) Polymère optiquement actif polymérisable et procédé de préparation d'un polymère polymérisable
Wang et al. Anionic polymerization of acrylic monomers. 15. Living anionic copolymerization of mixtures of methyl methacrylate and tert-butyl acrylate as promoted by dibenzo-18-crown-6
EP0279463B1 (fr) Polymérisation par greffage de polymère de styrène substitué ayant des groupes vinylidènes pendants
US5723559A (en) Initiating process and system for the anionic polymerisation of acrylic monomers
US5670592A (en) System for priming the anionic polymerization of alkyl methacrylate
US4442261A (en) Cationically polymerizable macromolecular monomers and graft copolymers therefrom
Ito et al. Synthesis of well-defined block copolymers containing poly (N-isopropylacrylamide) segment by anionic block copolymerization of N-methoxymethyl-N-isopropylacrylamide
WO1996023008A2 (fr) Procede de polymerisation anionique de monomeres acryliques
Hirao et al. Anionic living polymerization of 4-vinyl (N, N-diisopropylbenzamide)
Sannigrahi et al. Copolymerization of methyl methacrylate with lauryl methacrylate using group transfer polymerization
JPH07110884B2 (ja) （メタ）アクリレートのアニオン重合開始剤組成物および重合方法
EP0633901A1 (fr) Agent d'amor age de polymerisation de norbornene, et polymeres prepares avec ces agents d'amor age
US20010003726A1 (en) Initiation system comprising an amino alcoholate ligand for anionic copolymerization of (meth)acrylic monomers and process using same
US3553170A (en) Copolymers of vinylboron compounds
JPH07242712A (ja) リビングランダム（メタ）アクリルコポリマーおよびそれから得られるコポリマーと、それらのアニオン共重合方法
Kitayama et al. Stereospecific living polymerization of methacrylate with binary initiator systems

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19961017

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB

17Q First examination report despatched

Effective date: 19970326

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19980609