EP1345971A1 - Method for shortstopping polymerization processes in the manufacture of synthetic rubbers - Google Patents

Method for shortstopping polymerization processes in the manufacture of synthetic rubbers

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Withdrawn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)
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/en
Withdrawn legal-status Critical Current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
    • 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

This invention is related to a new shortstopping combination for use in stopping free radical and redox intiated polymerization is the combination of hydroxylamine (free base) (HA) and i-propylhydroxylamine (IPAH). It is more effective as related N-alcylated-hydroxylamines with regard to mooney stability. The combination is not corrosive to metals used in commercial equipment fr emulsion polymerization and prevents the rust formation and the formation of nitrosamins, coagulate and precipitate.

Description

METHOD FOR SHORTSTOPPING POLYMERIZATION PROCESSES IN THE MANUFACTURE OF SYNTHETIC RUBBERS
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.
The main application of free radical or redox polymerization is the emulsion polymerizations used in making elastomers such as styrene-butadiene rubber (SBR), butadiene rubber (BR) and acrylonitrile-butadiene rubber (NBR). Much study has been made toward finding good short-stops and numerous compounds have been found quite useful. However, the compounds used heretofore have certain disadvantages and are not generally satisfactory with all types of polymerization systems. Well known as conventional shortstopping agents are carbamates, hydoquinone, hydracine, polysulfide, nitrocompounds, N- alcylated hydroxylamines and/or other more (US 5.348.372 US 3.296.177;.EP 656 371 ; EP-AO 437 293; DE-A-15 95 177).
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. 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 secundary amines using N,N-dialcylated hydroxylamines and/or carbamates.
The problem has been excellently resolved by using a shortstopping agent as mixture of hydroxylamine (free base) und i-propylhydroylamine. In this way latex free of coagulate and precipitate and rubbers without nitrosamines and their precursors are produced. Never was found a drifting of the mooneyviscosity in latex or rubber.
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). According to the invention there is disclosed a process for preparing a synthetic latex and rubber by free radical and redox initiated emulsion polymerization of a conjugated diene and a monoolefine in an aqueous medium and terminating the polymerization by the addition of a shortstopping agent combination consisting of hydroxylamin (free base) (HA) and i-propylhydroxylamin (IPAH).
The process being characterized in that a mixture consist of hydroxylamin (free base) (HA) and i-propylhydroxylamin (IPAH) is used as shortstopping agent comprising:
a) from 0.001 to 0.499 parts by weight of HA per 100 parts of monomers initially charged,
b) from 0.499 to 0.001 parts by weight of IPHA per 100 parts of monomers initially charged.
Preferably, 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 manner by which the shortstopping agent is added is occured with convential techniques used in rubber polymerization processes. Preferably, the original solutions (HA 50 percent, IPHA 15 percent) and or 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 practice of this invention is further illustrated by references to the following examples which are intended to be representative rather than restrictive of the scope of this invention. The term "parts" as employed in the following examples refers to parts by weight of shortstopping agent per 100 parts of monomer charged. EXAMPLES
For free radical or redox initiated emulsion polymerization we carried out using a could soap styrene butadien polymerization is listed in table 1 :
Table 1
All polymerizations were carried out at 5°C to about 60 percent conversion of monomer to polymer.
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).
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
22 percent solution. The results are given in table 2.
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.
The addition of shortstop agent will be made after the desired degree of polymerization directly in the latex.
The presence of nitrosamines was determined by gaschromatographiy using a thermal energy analyzer, called BGA-method. Table 2
* detection: N-nitrosodimethylamine, N-nitrosodietylamine, N-nitrosodipropylamine, N- nitrosodibutylamine, N-nitrosopiperidine, N-nitosopyrrolidine, N-nitosomorpholine *1)Summary of N-nitrosodimethylamine and N-nitrosodiethylamine in rubber. *2) coagulate/precipitate was detected after monomer recovery *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.
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).
Surprisingly, use of hydroxylamine(HA) and i-propylhydroxylamine(IPAH) resulted in no nitrosamines and coagulate being detected. In the same way resulted a very mooney stable latex without drifting (Examples 2-8). The advantage of the invention is a better shortstopp effect and a better prevention of popcorn formation in the gasphase and also in the liquid-(latex) phase. Besides the quantities of the two components of the mixture forming the shortstopping agent are lower that those required by the use of each single component, thus justifying the existence of a synergetic effect of the two components with respect to the shortstopping reaction.

Claims

CLAIMS:
1. A method of stopping free radical or redox polymerization comprising a mixture of hydroxylamine (HA) and i-propylhydroxylamine (IPAH) to a polymerizing mixture when a predetermined conversion has been reached.
2. The method of claim 1 wherein the mixture in an amount from 0.005 to 0.2 parts by weight each 100 parts by weight of initial monomer (phm) is added.
3. The method of claim 1 wherein the mixture consist of 0.001 to 0.499 parts by weight hydroxylamine(HA) and 0.499 to 0.001 parts by weight i-propylhydroxylamine (IPAH) by weight of initial monomer (phm), preferably 0.01 to 0.2 parts by weight hydroxylamine(HA) and 0.2 to 0.01 parts by weight i-propylhydroxylamine (IPAH) by weight of initial monomer (phm).
The method of claim 1 wherein the shortstopping agents are used in the original concentrations of the both components, IPAH 15 percent in water and HA 50 percent in water.
EP01993625A 2000-11-07 2001-10-23 Method for shortstopping polymerization processes in the manufacture of synthetic rubbers Withdrawn EP1345971A1 (en)

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 (en) 2003-09-24

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Country Status (4)

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EP (1) EP1345971A1 (en)
AU (1) AU2002225840A1 (en)
TW (1) TW588057B (en)
WO (1) WO2002038617A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102282184B (en) 2009-01-14 2014-06-18 斯泰隆欧洲有限责任公司 Increased monomer conversion in emulsion polymerization
WO2013188632A1 (en) 2012-06-14 2013-12-19 Dow Global Technologies Llc Alkyl hyroxylamine compounds and their use for shortstopping free radical polymerizations
DE112013004793T5 (en) 2012-09-28 2015-07-16 Angus Chemical Company Alkylhydroxylamine compounds and their use for stopping free radical polymerizations

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
NL268619A (en) * 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 (en) * 1993-12-03 1996-10-31 Enichem Elastomers PROCEDURE FOR THE TERMINATION OF EMULSION CURING THAT DOES NOT GENERATE NITROSAMINES
US5384372A (en) * 1994-03-30 1995-01-24 The Goodyear Tire & Rubber Company Shortstopping of free radical polymerizations
AU7281998A (en) * 1997-05-16 1998-12-08 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 *

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

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