US3706724A - Process for the dehydrochlorination of chlorinated polyolefins - Google Patents

Process for the dehydrochlorination of chlorinated polyolefins Download PDF

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Publication number
US3706724A
US3706724A US159427A US3706724DA US3706724A US 3706724 A US3706724 A US 3706724A US 159427 A US159427 A US 159427A US 3706724D A US3706724D A US 3706724DA US 3706724 A US3706724 A US 3706724A
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chlorinated
dehydrochlorination
chlorinated polyolefin
weight
fluidized bed
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US159427A
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Robert R Blanchard
James S Kennedy
Reginald F Roberts
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Dow Chemical Co
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Dow Chemical Co
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule

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  • the chlorinated polyolefins are normally reacted with an acceptor for hydrogen chloride such as the metal oxides, metal hydroxides, metal alcoholates, metal sulfides, metal hydrogen sulfides, metal mercaptides and metal salts of slightly dissociated organic acids, for example, carbonates of alkali metals or alkaline earth metals and the like.
  • an acceptor for hydrogen chloride such as the metal oxides, metal hydroxides, metal alcoholates, metal sulfides, metal hydrogen sulfides, metal mercaptides and metal salts of slightly dissociated organic acids, for example, carbonates of alkali metals or alkaline earth metals and the like.
  • dehydrochlorination has been accomplished by blending the chlorinated polyolefins and the acceptor for hydrogen chloride on heated mill rolls or in high speed mixers such as a Banbury mixer; however, such procedure produces a dehydrochlorinated product in the form of agglomerated particles of relative large mass or as a slabstock, which is diflicultly manageable where subsequent vulcanization or crosslinking is desired.
  • the chlorinated polyolefins which may be readily dehydrochlorinated to form particulate materials may be any comminnted chlorinated polyolefin obtained by chlorination in solution, in the molten state or in aqueous suspension.
  • materials prepared by the suspension chlorination in an inert medium of finely divided essentially linear polyethylene and interpolymers containing at least about 90 mole percent ethylene with the remainder being one or more ethylenically unsaturated comonomers e.g. the chlorinated polyolefins prepared in aqueous suspension as described in the United States Patent 3,454,544, issued July 8, 1969, and which contain from about 25 to 75 percent by weight chlorine and preferably from about 36 to 48 percent by weight chlorine.
  • Exemplary of the Lewis acid catalysts which may be used include zinc oxide (in HCl solution), aluminum chloride, magnesium chloride, ferric chloride, cuprous chloride, with zinc chloride being preferred.
  • Such catalysts are used in amounts of from about 0.25 to 0.5 phr. based on chlorinated polyethylene. It has further been discovered, which discovery froms a part of the present invention, that optimum rates of dehydrochlorination were obtained by addition of the Lewis acid to comminnted, wet, chlorinated polyethylene, i.e. wherein said chlorinated polyethylene contained at least about 10 percent by weight water in the polymer particles.
  • the catalyzed chlorinated polyolefin is then maintained in the form of a fluidized bed by placing such material, in any suitable reactor wherein a substantially inert gas, preferably oxygen, gaseous HCl or nitrogen, may be continuously passed therethrough.
  • a substantially inert gas preferably oxygen, gaseous HCl or nitrogen
  • magnesium silicate is particularly effective.
  • Exemplary of other useful inert materials are carbon black and titanium dioxide.
  • dehydrochlorinated product recovered as a particulate material which is especially adaptable for use in subsequent conventional vulcanization or crosslinking reactions.
  • the percent dehydrochlorination may be determined by dissolving the dehydrochlorinated product in a solvent such as ortho-dichlorobenzene to which is then added an excess of iodine monochloride in a carbon tetrachloride solution. Iodine is then liberated from unreacted ICl with excess alcoholic potassium iodide. The iodine is then backtitrated with 0.1 N thiosulfate and the percent unsaturation calculated. 7
  • EXAMPLE 1 (A) Preparation of the chlorinated polyolefin In each of a series of experiments, an aqueous slurry comprising from about 3200 to 3600 grams of water and 160 to 180 grams of a polyethylene having an essentially linear and unbranched molecular structure containing less than about 1 methyl group per 100 methylene units in its molecule; a density of about 0.96; an average molecular weight of about 67,000 and which had been prepared using a catalyst composed of triisobutyl aluminum and titanium tetrachloride; was charged to a 1 /2 gallon autoclave with from 6.4 to 7.2 grams of calcium chloride; from to 8 g. of a platy magnesium silicate; about 0.5 cc.
  • each charge was further individually chlorinated in a second suspension chlorination step, at a temperature of 128 C. until a total chlorine content of between about 36 and 48 percent was obtained.
  • FIG. 1 Fluidization apparatus
  • the designated chlorinated polethylene was formed into a fluid bed utilizing the apparatus set forth in FIG. 1.
  • Such apparatus consists of a 4-foot section of 4-inch I.D. glass pipe wherein air or nitrogen gas was used as the fluidizing medium. Heat was provided by passing the fluidizing gas through electric heaters. Rotameters were installed so that a constant flow of gas could be maintained.
  • (C) Resin preparation In the preferred process of the present invention, the Lewis acid catalyst was added generally in aqueous solution to particulate chlorinated polyethylene containing at least about 10 percent by weight water. Thereafter the catalyzed chlorinated polyethylene was dried under mild conditions, i.e., at a temperature of about 40f C. under normal pressure.
  • FIG. 2 illustrates the increase in dehydrochlorination rate achieved by utilization of this-procedure as contrasted to blending the Lewis acid catalyst with dried chlorinated polyethylene. Additionally, it has been found that addition of the Lewis acid catalyst during the chlorination. of the polyolefin did not provide dehydrochlorination as the catalyst is substantially completely removed while washing the chlorinated polyolefin subsequent to the chlorination reaction.
  • FIG. 3 illustrates the comparative eflectiveness of a series of Lewis acids when added to wet chlorinated polyethylene containing 36 percent by weight chlorine at a concentration of 0.5 part by weight. It is apparent that zinc chloride is noticeably the more effective.
  • FIG. 4 illustrates the effect of zinc chloride concentration on dehydrochlorination rate'when added to wet chlorinated polyethylene and fluidized by the procedure of the present invention.
  • FIG. 6 illustrates the effect of fluidization temperature when a zinc chloride catalyzed chlorinated polyethylene, containing 0.5 phr. of an oxylated diphenylamine antioxidant, is dehydrochlorinated by the process of this invention.
  • FIG. 5 A comparison of the data of FIG. 5 and FIG. 6 illustrates the increase in dehydrochlorination rate achieved using the oxylated diphenylamine antioxidant.
  • FIGS. 7 and 8 illustrates the eflect of antioxidant concentration upon the rate of dehydrochlorination.
  • a process for preparing particulate dehydrochlorinated chlorinated polyolefins comprising (1) preparing a catalyzed chlorinated polyolefin by substantially uniformly admixing from about 0.25 to 0.5 part by weight of a Lewis acid per 100 parts of a comminuted chlorinated polyolefin,
  • chlorinated polyolefin is chlorinated polyethylene containing from about 36 to 48 percent by weight chlorine.
  • a process for preparing particulate dehydrochlorinated chlorinated polyethylene comprising (1) preparing a catalyzed chlorinated polyolefin by substantially uniformly admixing from about 0.25 to 0.5 part by weight of zinc chloride in the form of an aqueous solution per 100 parts of a comminuted chlorinated polyethylene having a chlorine content of between about 36 and 48 percent by weight and containing at least about 10 percent by weight water,

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  • Chemical & Material Sciences (AREA)
  • General 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)
US159427A 1971-07-02 1971-07-02 Process for the dehydrochlorination of chlorinated polyolefins Expired - Lifetime US3706724A (en)

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US15942771A 1971-07-02 1971-07-02
NL7214020A NL7214020A (fr) 1971-07-02 1972-10-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855347A (en) * 1972-09-15 1974-12-17 Badger Co Process for hydrogenating halogenated hydrocarbons
US3909486A (en) * 1973-06-28 1975-09-30 Gen Electric Method of halogenating thermoplastic polyolefins
US4764297A (en) * 1987-03-20 1988-08-10 The Lubrizol Corporation Protic solvent in a dehydrohalogenation process, the product obtained therefrom and lubricant compositions containing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855347A (en) * 1972-09-15 1974-12-17 Badger Co Process for hydrogenating halogenated hydrocarbons
US3909486A (en) * 1973-06-28 1975-09-30 Gen Electric Method of halogenating thermoplastic polyolefins
US4764297A (en) * 1987-03-20 1988-08-10 The Lubrizol Corporation Protic solvent in a dehydrohalogenation process, the product obtained therefrom and lubricant compositions containing same

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Publication number Publication date
NL7214020A (fr) 1974-04-19
BE817310Q (fr) 1975-01-06

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