EP1345971A1 - Verfahren zum stoppen von polymerisationsverfahren bei der herstellung von synthesekautschuk - Google Patents

Verfahren zum stoppen von polymerisationsverfahren bei der herstellung von synthesekautschuk

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Withdrawn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
English (en)
French (fr)
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/de
Withdrawn legal-status Critical Current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)
EP01993625A 2000-11-07 2001-10-23 Verfahren zum stoppen von polymerisationsverfahren bei der herstellung von synthesekautschuk Withdrawn EP1345971A1 (de)

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 (en) 2000-11-07 2001-10-23 Method for shortstopping polymerization processes in the manufacture of synthetic rubbers

Publications (1)

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

Family

ID=22930439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01993625A Withdrawn EP1345971A1 (de) 2000-11-07 2001-10-23 Verfahren zum stoppen von polymerisationsverfahren bei der herstellung von synthesekautschuk

Country Status (4)

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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG172024A1 (en) * 2009-01-14 2011-07-28 Styron Europe Gmbh Increased monomer conversion in emulsion polymerization
BR112014030662B1 (pt) 2012-06-14 2021-07-06 Dow Global Technologies Llc método para finalizar uma reação de polimerização de emulsão iniciada por radical livre e método para produzir um elastômero
WO2014052212A1 (en) 2012-09-28 2014-04-03 Dow Global Technologies Llc 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 (de) * 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 (en) * 1992-10-21 1994-04-22 Betzdearborn Inc. Compositions and methods for inhibiting styrene polymerization
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 (en) * 1997-05-16 1998-11-19 Angus Chemical Company N-ethylhydroxylamine as a shortstopping agent for free radical polymerization
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
TW588057B (en) 2004-05-21
WO2002038617A1 (en) 2002-05-16
AU2002225840A1 (en) 2002-05-21

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