EP0000430B1 - Procédé de polymérisation d'halogénures de vinyle - Google Patents

Procédé de polymérisation d'halogénures de vinyle Download PDF

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Publication number
EP0000430B1
EP0000430B1 EP78300113A EP78300113A EP0000430B1 EP 0000430 B1 EP0000430 B1 EP 0000430B1 EP 78300113 A EP78300113 A EP 78300113A EP 78300113 A EP78300113 A EP 78300113A EP 0000430 B1 EP0000430 B1 EP 0000430B1
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EP
European Patent Office
Prior art keywords
polymerization
chloride
vinyl
vinyl halide
build
Prior art date
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Expired
Application number
EP78300113A
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German (de)
English (en)
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EP0000430A1 (fr
Inventor
Boris Englin
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.)
Orica Ltd
Original Assignee
ICI Australia Ltd
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Publication date
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    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium

Definitions

  • the present invention relates to a process for the polymerization of vinyl halide monomers such as vinyl chloride in aqueous dispersion.
  • polymerization in aqueous dispersion polymerization in aqueous emulsion or aqueous suspension (including aqueous microsuspension), optionally in the presence of colloids such as polyvinyl alcohol and/or surfactants.
  • This deposit which varies in thickness, hardness and degree of adhesion to the metal is composed of polymer in several different physical forms.
  • the main type particularly from the standpoint of routine cleaning, is a hard film over the whole surface of the reactor. The thickness of this film varies from batch to batch but is normally a few thousandths of an inch thick.
  • the other types are hard or soft lumps which accumulate locally in the reactor or powder which is more generally distributed. The soft lumps are composed of material that has escaped the washing out process and are comparatively easy to remove.
  • the hard lumps are believed to originate as soft material that has been allowed to stay in the reactor for more than one batch or simply by polymerization of vinyl chloride in an area of very high or very low agitation, i.e.
  • a process for the polymerization of vinyl halide monomers in aqueous dispersion which process is characterized by the addition to the polymerization reaction medium of a composition comprising metal ions selected from chromium, copper, cobalt, nickel, manganese, tungsten and molybdenum, prior to the start of the polymerization reaction and by the addition to the polymerization reaction medium of an amount of a quinone or a hydroquinone that is less than 0.03% w/w of the vinyl halide monomer during the polymerization reaction.
  • composition can be added to the reaction medium without opening the reactor.
  • the reactors used for the polymerization do not need to be opened between each polymerization cycle, either to remove adhering build-up or to apply or remove anti-build-up coatings.
  • composition comprising these ions is not narrowly critical. We have found for example that good results may be obtained using an aqueous solution of the ion in the form of simple salts such as for example, nitrates, sulphates and acetates. Particularly good results are obtained using the chlorides.
  • the ion may also be in the form of complex ions such as amine complexes or complexes of the metallic ion with polyethers.
  • compositions comprising these metal ions are cuprous chloride, cupric sulphate, nickelous chloride cobaltous chloride, chromic chloride, manganese sulphate and ammonium molybdate.
  • Oxide compositions for example chromium trioxide and tungsten trioxide, may conveniently be dissolved in dilute acids such as hydrochloric and sulphuric acids.
  • the composition comprises copper, nickel, and cobalt ions, and most preferably the composition comprises chromium ions.
  • Compositions comprising two or more of the said metal ions may also be used.
  • the metal ion is added to the reaction mixture prior to the polymerization and during the polymerization a solution of a hydroquinone or a quinone, such as hydroquinone itself, benzoquinone or naphthoquinone, is injected into the reaction mixture.
  • a hydroquinone or a quinone such as hydroquinone itself, benzoquinone or naphthoquinone.
  • the concentration of hydroquinone or quinone is less than 0.03% w/w based on the monomer content, since above this level the polymerization reaction may be inhibited.
  • the operating conditions for polymerization according to the process of the present invention may be those customarily used.
  • the temperature is generally below 110°C and typically between 40 and 80°C and the pressure generally below 15 kg/cm 2 .
  • Compositions of metal ions of our invention comprising bromides are preferably used in polymerization processes carried out at temperatures below 60°C.
  • vinyl halide monomers those monomers polymerizable by free-radical polymerization which are olefinically unsaturated in the alpha position and substituted by at least one halogen atom. These monomers are preferably selected from substituted derivatives of ethylene and contain only two carbon atoms. Examples of such monomers include vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, chlorotrifluoroethylene and tetrafluoroethylene. The invention is preferably applied to the polymerization of fluorine- or chlorine-containing vinyl monomers, especially vinyl chloride.
  • polymerization is meant both the homopolymerization of the vinyl halide monomers and the copolymerization with each other or with other comonomers copolymerizable therewith.
  • vinyl esters such as vinyl acetate, acrylic esters such as methyl acrylate and butyl methacrylate, acrylic nitriles such as acrylonitrile and methacrylonitrile, unsaturated diesters such as diethyl maleate, allyl esters such as allyl acetate, a-olefines such a ethylene and propylene, vinyl ethers and styrene compounds.
  • the process according to the invention may be employed in any polymerization technique where the monomer(s) is dispersed in the form of droplets in a liquid aqueous phase.
  • the monomer(s) may be dispersed in the form of droplets in a liquid aqueous phase.
  • it may be used for polymerization in aqueous emulsion in which case any suitable emulsifying agent such as sodium lauryl sulphonate or sodium dodecyl benzene sulphonate and non-ionic emulsifying agents may be used.
  • the process of the invention is also most applicable to polymerization in aqueous suspension and microsuspension.
  • Any suitable dispersing agent may be used for polymerization in aqueous suspension, and particularly finely dispersed solids, gelatin, polyvinyl acetates of various degrees of hydrolysis, water-soluble cellulosic ethers and polyvinyl pyrrolidones. These dispersing agents can be used together with surface-active agents if desired.
  • the amount employed may vary widely and is generally between 0.05 and 1.5% by weight calculated on the amount of water used.
  • Any suitable free-radical polymerization initiator that is monomer-soluble may be used for polymerization in aqueous suspension.
  • these include peroxy compounds such as di-tertiary-butyl peroxide, lauroyl peroxide and acetyl cyclohexyl sulphonyl peroxide, t-butyl perpivalate, azo compounds such as azo-bis-isobutyronitrile and 2,2'-azo-bis - 2,4-dimethyl-valeronitrile, and boron alkyls.
  • Monomer-soluble free-radical polymerization initiators that are particularly suitable for use in the process according to the invention are the dialkyl peroxydicarbonates whose alkyl radicals contain up to 20 carbon atoms, such as diethyl peroxydicarbonate, diisopropyl peroxydicarbonate and di(tertiarybutyl-cyclohexyl)-peroxydicarbonate, and 2,2'-azo-bis-2,4-dimethylvaleronitrile and azo-bis-iso-butyronitrile. These initiators may be used in conventional quantities - generally speaking from 0.01 to 1% by weight calculated on monomer.
  • Polymerization in homogenised aqueous dispersion comprises mechanically homogenising an aqueous dispersion of the monomer or monomers in the presence of a surface-active agent (for example by subjecting it to a violent shearing action), and polymerizing the homogenised dispersion in the presence of an initiator that is monomer soluble.
  • emulsifying agents and monomer-soluble initiators can be used for polymerization in microsuspension such as for example an ionic emulsifying agent like sodium dodecylbenzenesulphonate, and peroxide initiators of the dialkanoyl peroxide type, e.g. lauroyl peroxide.
  • an ionic emulsifying agent like sodium dodecylbenzenesulphonate
  • peroxide initiators of the dialkanoyl peroxide type e.g. lauroyl peroxide.
  • the aqueous dispersions may contain one or more additives that are normally employed in conventional processes for polymerization in aqueous dispersion.
  • additives include particle size regulators, molecular weight regulators, stabilisers, plasticisers, colouring agents, reinforcing agents and processing aids.
  • the polymerization medium may also contain one or more substances which themselves inhibit polymerization build-up.
  • a stainless steel pressure vessel of 7 litres nominal capacity equipped with heating and cooling means was charged with 3500 ml of demineralized water, 2.4 g of a peroxydicarbonate catalyst and 1.75 g polyvinyl alcohol (partially hydrolyzed polyvinyl acetate). The contents of the vessel were stirred and the air above the liquid was removed by evacuation. Vinyl chloride monomer (3000 g) was added to the evacuated vessel and the contents were heated to 56°C. The temperature was maintained until pressure drop indicated the end of the reaction of polymerization.
  • the residual gas was vented off and the slurry of polyvinyl chloride in water was dropped down through the bottom valve.
  • the lid was opened and the remaining loose polymer was rinsed with water and the firm deposition of the polymer inside the autoclave was examined.
  • the total weight of the deposit constituted 0.6% w/w of the vinyl chloride monomer charged to the autoclave.
  • Example 1 The pressure vessel of Example 1 was thoroughly cleaned free from all deposit, washed and dried. The charging procedure of Example 1 was repeated and 5 minutes after vinyl chloride addition, a solution of 0.22 g of copper chloride dihydrate (0.003% w/w copper ion on vinyl chloride charge) in 35 mls water was injected into the polymerization mixture. The vessel contents were heated to the polymerization temperature of 56°C; after one hour at polymerization temperature 0.25 g of hydroquinone in 35 mls of water were injected and the reaction was finished as described in Example 1.
  • Example 1 The pressure vessel of Example 1 was thoroughly cleaned free from all deposit, washed and dried. The charging procedure of Example 1 was repeated and 5 min after vinyl chloride addition a solution of 0.22 g of copper chloride dihydrate (0.003% w/w copper ion based on vinyl chloride) in 10 ml of water and 0.5 ml concentrated hydrochloric acid was injected into the polymerization mixture.
  • the overall amount of the build-up deposit was only 0.2 g, or 0,007% w/w of the initial monomer charge.

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  • 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)
  • Polymerisation Methods In General (AREA)

Claims (5)

1. Procédé pour la polymérisation des halogénures de vinyle monomères en dispersion aqueuse, lequel procédé est caractérisé par l'addition, au milieu pour la réaction de polymérisation, d'une composition comprenant des ions de métaux choisis entre le chrome, le cuivre, le cobalt, le nickel, le manganèse, le tungstène et le molybdène avant le début de la réaction de polymérisation et par l'addition, au milieu pour la réaction de polymérisation, d'une quantité d'une quinone ou d'une hydroquinone qui est inférieure à 0,03% poids/poids de l'halogénure de vinyle monomère pendant la réaction de polymérisation.
2. Procédé suivant la revendication 1, dans lequel l'halogénure de vinyle monomère est le chlorure de vinyle.
3. Procédé suivant la revendication 1 ou la revendication 2 dans lequel l'ion de métal se présente sous forme d'un sel hydrosoluble choisi entre le nitrate, le sulfate, le chlorure et l'acétate.
4. Procédé suivant la revendication 3, dans lequel le sel hydrosoluble comprend du chlorure cuivrique.
5. Procédé suivant la revendication 3, dans lequel le sel hydrosoluble comprend du chlorure de chromyle.
EP78300113A 1977-07-15 1978-06-30 Procédé de polymérisation d'halogénures de vinyle Expired EP0000430B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPD087677 1977-07-15
AU876/77 1977-07-15

Publications (2)

Publication Number Publication Date
EP0000430A1 EP0000430A1 (fr) 1979-01-24
EP0000430B1 true EP0000430B1 (fr) 1981-08-12

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Family Applications (1)

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EP78300113A Expired EP0000430B1 (fr) 1977-07-15 1978-06-30 Procédé de polymérisation d'halogénures de vinyle

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EP (1) EP0000430B1 (fr)
DE (1) DE2860931D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3222002A1 (de) * 1982-06-11 1983-12-15 Röhm GmbH, 6100 Darmstadt Kontinuierliches emulsionspolymerisationsverfahren
DE3636756A1 (de) * 1986-10-29 1988-05-05 Basf Ag Verfahren zur herstellung von vinylchlorid-polymerisaten
US5414062A (en) * 1994-03-10 1995-05-09 Rohm And Haas Company Method for reduction of aqueous phase polymer formation in suspension polymerization
FR2990134B1 (fr) 2012-05-07 2014-11-21 Anaconda Pharma Composition pharmaceutique d'un inhibiteur du virus du papillome

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5345836B2 (fr) * 1974-04-26 1978-12-09
JPS5212291A (en) * 1975-07-18 1977-01-29 Shin Etsu Chem Co Ltd Process for polymerizing vinyl chloride
JPS5227491A (en) * 1975-08-28 1977-03-01 Chisso Corp Process for preparing a vinyl chloride polymer

Also Published As

Publication number Publication date
EP0000430A1 (fr) 1979-01-24
DE2860931D1 (en) 1981-11-12

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