EP1345971A1 - Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques - Google Patents

Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques

Info

Publication number
EP1345971A1
EP1345971A1 EP01993625A EP01993625A EP1345971A1 EP 1345971 A1 EP1345971 A1 EP 1345971A1 EP 01993625 A EP01993625 A EP 01993625A EP 01993625 A EP01993625 A EP 01993625A EP 1345971 A1 EP1345971 A1 EP 1345971A1
Authority
EP
European Patent Office
Prior art keywords
weight
shortstopping
parts
ipah
mixture
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Withdrawn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
EP01993625A
Other languages
German (de)
English (en)
Inventor
Hartmut K. Stiller
Hans A R. Edel
Doris R. Marx
Heinz-Jurgen Bogen
Ilona Guth
Klaus Hohne
Wolfgang Krebes
Friedhelm Mathies
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP1345971A1 publication Critical patent/EP1345971A1/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Withdrawn legal-status Critical Current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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent

Definitions

  • This invention relates to an improved method for shortstopping polymerization processes for making synthetic rubber, such as butadiene-styrene copolymers.
  • Free radical or redox initiated emulsion polymerizations are generally terminated by mixing the latex with shortstopping agents, which are used to prevent a free radical or redox polymerzation reaction from proceeding to completion. The polymerization must be stopped to get a product of the desired characteristics. The properties of the polymers produced vary with the percentage of the monomers conversion.
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • N- monoalkylhydroxylamines have been suggested as shortstopping agents, particularly isopropylhydroxylamin (IPHA) in US 5.384.372; WO 98/51714). In this case the final rubber was free of nitrosamines and their precursors.
  • IPHA isopropylhydroxylamin
  • the disadvantage of the described solutions is an not exactly stopping process by drifting the mooneyviscosity and the formation of coagulate and precipitate in the recovery vessels.
  • Another problem is the formation of depoty amines using N,N-dialcylated hydroxylamines and/or carbamates.
  • the present invention relates to a method for terminating a free radical initiated emulsion polymerization comprising adding to the emulsion a shortstopping agent consisting of a mixture of i-Propylhydroxylamin (IPAH) and Hydroxylamin (HA) (free base).
  • a shortstopping agent consisting of a mixture of i-Propylhydroxylamin (IPAH) and Hydroxylamin (HA) (free base).
  • HA hydroxylamin (free base)
  • IPAH i-propylhydroxylamin
  • a mixture of 0,01 to 0,2 parts by weight HA and 0,2 to 0,01 parts by weight IPAH is added.
  • the mixture of shortstopping agent is added in an amount from 0.005 to 0.2 parts by weight each 100 parts by weight of initial monomer (phm), preferably 0J to 0.4 parts by weight of initial monomer (phm).
  • the shortstopping agent is added is occured with convential techniques used in rubber polymerization processes.
  • the original solutions HA 50 percent, IPHA 15 percent
  • an aqueous solution of the shortstopping mixture will be added to the polymerization reaction mass when the desired conversion is obtained
  • the preferable used polymerization system is a styrene butadiene polymerization.
  • the shortstopping agent was then added.
  • Example 1 was shortstopped with a dilute aqueous solution of a 90/10 ratio by weight mixture of sodium dimethyldithiocarbamate (DTC) and N,N-diethylhydroxylamine (DEHA).
  • DTC sodium dimethyldithiocarbamate
  • DEHA N,N-diethylhydroxylamine
  • Example 2 3, 4, 5, 6 7, and 8 was shortstopped with a dilute aqueous solution of hydroxylamine (HA) 50 percent and i-propylhydroxylamin (IPAH) 15 percent in water as a
  • the mixture of both components was formed as batch or in linedosing, with or without deionized water from the original components.
  • the preferential concentration could vary from 1 percent to 25 percent on the active components in water.
  • shortstop agent will be made after the desired degree of polymerization directly in the latex.
  • * 3) not detected The shortstopp mixture was realized by mixing original solutions of of hydroxylamine (free base)(HA) 50 percent and i-propylhydroxylamin (IPAH) 15 percent in water.
  • sample 1 Use of conventional shortstopping agents in sample 1 resulted in relatively high levels of nitrosamines being detected in the rubber. Also was found a high amount of coagulate using dimethyldithiocarbamate (DTC) and N,N-diethylhydroxylamine (DEHA) (examplel).
  • DTC dimethyldithiocarbamate
  • DEHA N,N-diethylhydroxylamine

Landscapes

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

Abstract

L'invention concerne une nouvelle combinaison d'interruption à utiliser pour interrompre la polymérisation radicalaire et initiée par oxydoréduction. Cette combinaison comporte de l'hydroxylamine (base libre) (HA) et de l'i-propylhydroxylamine (IPAH). Cette combinaison est plus efficace pour ce qui est des hydroxylamines N-alcylées par rapport à la stabilité mooney. Ladite combinaison n'est pas corrosive pour les métaux utilisés dans les équipements commerciaux pour la polymérisation par émulsion et prévient la formation de rouille et la formation de nitrosamines, de coagulat et de précipité.
EP01993625A 2000-11-07 2001-10-23 Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques Withdrawn EP1345971A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US24638500P 2000-11-07 2000-11-07
US246385P 2000-11-07
PCT/US2001/045609 WO2002038617A1 (fr) 2000-11-07 2001-10-23 Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques

Publications (1)

Publication Number Publication Date
EP1345971A1 true EP1345971A1 (fr) 2003-09-24

Family

ID=22930439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01993625A Withdrawn EP1345971A1 (fr) 2000-11-07 2001-10-23 Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques

Country Status (4)

Country Link
EP (1) EP1345971A1 (fr)
AU (1) AU2002225840A1 (fr)
TW (1) TW588057B (fr)
WO (1) WO2002038617A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2376551T3 (pl) 2009-01-14 2013-02-28 Trinseo Europe Gmbh Zwiększona konwersja monomeru w polimeryzacji emulsyjnej
WO2013188632A1 (fr) 2012-06-14 2013-12-19 Dow Global Technologies Llc Composés alkyl hydroxylamines et leur utilisation pour arrêter des polymérisations par radicaux libres
US9309331B2 (en) 2012-09-28 2016-04-12 Angus Chemical Company Alkyl hydroxylamine compounds and their use for shortstopping free radical polymerizations

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL131752C (fr) * 1960-09-08
US3296177A (en) * 1964-11-13 1967-01-03 Pennsalt Chemicals Corp Stopping agents for synthetic rubber polymerization
US4912239A (en) * 1987-11-13 1990-03-27 Dow Corning Corporation Method for stabilizing unsaturated organosilicone compositions
CA2099168A1 (fr) * 1992-10-21 1994-04-22 Betzdearborn Inc. Compositions et methodes pour l'inhibition de la polymerisation du styrene
IT1265250B1 (it) * 1993-12-03 1996-10-31 Enichem Elastomers Procedimento per la terminazione di polimerizzazione in emulsione che non genera nitrosammine
US5384372A (en) * 1994-03-30 1995-01-24 The Goodyear Tire & Rubber Company Shortstopping of free radical polymerizations
WO1998051714A1 (fr) * 1997-05-16 1998-11-19 Angus Chemical Company N-ethylhydroxylamine en tant qu'agent inhibiteur de la polymerisation des radicaux libres
US6495065B1 (en) * 1999-09-09 2002-12-17 Atofina Chemicals, Inc. Nitrosamine-inhibiting compositions for shortstopping of free radical emulsion polymerizations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0238617A1 *

Also Published As

Publication number Publication date
AU2002225840A1 (en) 2002-05-21
TW588057B (en) 2004-05-21
WO2002038617A1 (fr) 2002-05-16

Similar Documents

Publication Publication Date Title
Nicolas et al. Nitroxide-mediated controlled free-radical emulsion polymerization of styrene and n-butyl acrylate with a water-soluble alkoxyamine as initiator
US20070149709A1 (en) Surfactantless synthesis of amphiphilic cationic block copolymers
CA2136049C (fr) Procede permettant d'interrompre les polymerisations en emulsion ne produisant pas de nitrosamines
US20080090962A1 (en) Hydrogenation and epoxidation of polymers made by controlled polymerization
US4201848A (en) Process for preparing polymers having high molecular weight
US6723255B2 (en) Compositions for shortstopping free radical emulsion polymerizations and stabilizing latices made therefrom
US20110269930A1 (en) Increased monomer conversion in emulsion polymerization
JP4846897B2 (ja) 遊離基乳化重合のショートストップのためのニトロソアミン阻害性組成物
EP1345971A1 (fr) Procede d'interruption de processus de polymerisation dans la fabrication de caoutchoucs synthetiques
US3341487A (en) Process for stopping emulsion polymerizations by the addition of dithiocarbamate salts and alkyl hydroxyl amines
JP2951741B2 (ja) 乳化重合の停止方法
CA1229945A (fr) Preparation de polymeres antidegradables de masse moleculaire elevee
US20040019165A1 (en) Method for shortstopping polymerization processes in the manufacture of synthetic rubbers
EP1263799A1 (fr) Procede d'elimination de residu de catalyse d'hydrogenation provenant de polymeres hydrogenes
EP0998502A1 (fr) Procede ameliore permettant d'eliminer le catalyseur d'hydrogenation de copolymeres sequences par reduction de la viscosite du ciment-polymere et par accroissement de la teneur en vinyle des copolymeres sequences
JPS645046B2 (fr)
KR100610274B1 (ko) 중합체시멘트로부터금속잔기의추출방법
Burfield et al. Persulphate initiated graft copolymerization of methacrylamide in natural rubber latex—I. The influence of non-rubber components
GB1558835A (en) Process for preparing polymers having high molecular weight
USH2030H1 (en) Process for the preparation of random copolymers of conjugated dienes and vinyl aromatic compounds
EP2841470B1 (fr) Composés alkyl hydroxylamines et leur utilisation pour arrêter des polymérisations par radicaux libres
JP6219940B2 (ja) アルキルヒドロキシルアミン化合物およびフリーラジカル重合を重合停止させるためのそれらの用途
Lin et al. Polymerization of Dimethylaminoethylmethacrylate‐Methyl Chloride Initiated by a Sacrificial Anode

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: 20030610

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20040906

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: 20050117