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WO1995001380A1 - Procede de preparation de polymeres olefiniques chlores et chlorosulfones - Google Patents

Procede de preparation de polymeres olefiniques chlores et chlorosulfones Download PDF

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Publication number
WO1995001380A1
WO1995001380A1 PCT/US1994/007075 US9407075W WO9501380A1 WO 1995001380 A1 WO1995001380 A1 WO 1995001380A1 US 9407075 W US9407075 W US 9407075W WO 9501380 A1 WO9501380 A1 WO 9501380A1
Authority
WO
WIPO (PCT)
Prior art keywords
monofluorobenzene
chlorinated
olefin polymer
chlorine
extruder
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.)
Ceased
Application number
PCT/US1994/007075
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English (en)
Inventor
Christopher John Bish
Edward Gus Brugel
Royce Elton Ennis
Jerry Wayne Soape
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to EP94922001A priority Critical patent/EP0706534A1/fr
Priority to JP7503555A priority patent/JPH08512081A/ja
Publication of WO1995001380A1 publication Critical patent/WO1995001380A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • 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
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/38—Sulfohalogenation

Definitions

  • Chlorinated and chlorosulfonated olefin polymers are widely available materials which find use as general purpose elastomers, coating compositions, and adhesives.
  • the chlorinated polymers are prepared on a commercial scale by reaction of chlorine with olefin polymers either in solution or in aqueous suspension, while the chlorosulfonated analogues are prepared by reaction of olefin polymers with chlorine and either sulfuryl chloride or sulfur dioxide in solution.
  • carbon tetrachloride When solution processes are employed, carbon tetrachloride is the solvent of choice because it easily dissolves the polymeric reactants and chlorinated products, it is stable under chlorination and chlorosulfonation reaction conditions, and it is essentially inert to chlorination. In addition, it has always been readily available. However, because carbon tetrachloride is a suspected carcinogen and, further, because it is postulated that carbon tetrachloride can take part in reactions which deplete stratospheric ozone, its use has been subject to increasingly stringent emission controls. Consequently, the use of carbon tetrachloride on a large scale is undesirable for both safety and environmental reasons as well as for economic reasons.
  • halogenated solvents have been suggested, but none of these is a completely acceptable replacement for ⁇ carbon tetrachloride.
  • the halogenated aliphatic solvents methylene chloride, dichloroethane, trichloroethane, 1,2,3- trichloropropane, 1,1,2,2-tetrachloroethane and chloroform are subject to substantial chlorination under the conditions used for manufacture of chlorinated and chlorosulfonated olefin polymers.
  • the chlorinated solvents themselves or their by-products are toxic. In the case of chloroform, further chlorination leads to production of carbon tetrachloride.
  • Chlorofluorocarbons such as dichlorodifluoromethane or trichlorofluoromethane, are unacceptable because they too are suspected stratospheric ozone depleters.
  • Hydrochlorofluorocarbons such as trichlorotetrafluoropropane (HCFC-224) and dichloropentafluoropropane, (HCFC-225) undergo chlorination as the chlorine content of the olefin polymer base resin is increased towards 60-70 weight percent, resulting in formation of chlorofluorocarbons.
  • Monofluorobenzene has been suggested as a reaction solvent for chlorination and chlorosulfonation reactions, for example in Japanese Patent Application Kokai 60-149604 and U.S. Patent 4,663,396, but it has not been utilized in such processes on a commercial scale because, in addition to the above-described disadvantages of aromatic solvents, the use of monofluorobenzene is hazardous, due to formation of highly flammable vapors when the solvent is heated in the presence of air.
  • the present invention provides a safe process for preparation and isolation of chlorinated and chlorosulfonated olefin polymers containing low levels of solvent and by-products, wherein monofluorobenzene is utilized as a reaction solvent. Non-discolored chlorinated and chlorosulfonated olefin polymers are thereby produced, and, in addition, chlorination of the reaction solvent is substantially reduced.
  • the present invention is directed to a process for preparation of chlorinated olefin polymers having low residual solvent content which comprises
  • the chlorinating agent is also a chlorosulfonating agent, for example sulfuryl chloride, a mixture of sulfuryl chloride and chlorine, a mixture of sulfur dioxide and chlorine, or a mixture of chlorine, sulfuryl chloride and sulfur dioxide.
  • a chlorosulfonating agent for example sulfuryl chloride, a mixture of sulfuryl chloride and chlorine, a mixture of sulfur dioxide and chlorine, or a mixture of chlorine, sulfuryl chloride and sulfur dioxide.
  • sulfuryl chloride is also a chlorosulfonating agent
  • olefin polymers are chlorinated or chlorosulfonated in solution or suspension in monofluorobenzene and are isolated substantially in the absence of oxygen by means of a series of extruders to produce chlorinated or chlorosulfonated products having low levels of residual solvent and solvent by-products, in particular less than 0.5 weight percent.
  • olefin polymers is meant homopolymers and copolymers of C2-C8 alpha-monoolefins, including graft copolymers.
  • the copolyme r s may be dipolymers or higher order copolymers, such as terpolymers or tetrapolymers.
  • Particularly useful examples include homopolymers of C2-C3 alpha monoolefins, copolymers of ethylene and carbon monoxide, and copolymers of ethylene and at least one ethylenically unsaturated monomer selected from the group consisting of C3-C10 alpha monoolefins, C1-C12 alkyl esters of unsaturated C3-C20 monocarboxylic acids, unsaturated C3-C20 mono-or dicarboxylic acids, anhydrides of unsaturated C4-C8 dicarboxylic acids, and vinyl esters of saturated C2-Cjg carboxylic acids.
  • polymers include polyethylene, polypropylene, ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ethylene methyl acrylate copolymers, ethylene methyl methacrylate copolymers, ethylene n- butyl methacrylate copolymers, ethylene glycidyl methacrylate copolymers, graft copolymers of ethylene and maleic anhydride, graft copolymers of propylene and maleic anhydride, and copolymers of ethylene with propylene, butene, 3-methyl-l-pentene, hexene, or octene.
  • Preferred olefin polymers are polyethylene, ethylene propylene copolymers, ethylene butene copolymers, ethylene octene copolymers, copolymers of ethylene and acrylic acid, copolymers of ethylene and methacrylic acid, and copolymers of ethylene and vinyl acetate.
  • the olefin polymers have number average molecular weights within the range of 1,000 to 300,000.
  • the first step of the process of the present invention is carried out by dissolving or suspending an olefin polymer in monofluorobenzene having a water content of less than 50 ppm in a reactor in the presence of a free radical catalyst.
  • the reactor is glass-lined.
  • Monofluorobenzene of low water content is not readily available on a commercial scale.
  • it may be produced by pre-treatment of the monofluorobenzene prior to introduction to the reactor or it " may be generated in situ in the reactor.
  • a variety of pre-treatment methods may be employed.
  • Preferably the water is removed by distillation using a multiplate column.
  • Alternative methods include contact with molecular sieves or passage through a silica gel column.
  • One effective in situ method for removing water from the monofluorobenzene is the following.
  • the monofluorobenzene is heated to vaporize monofluorobenzene/water azeotrope, boiling point approximately 72-78°C at atmospheric pressure, after which the azeotrope may be removed from the reactor as a forecut. After its formation, the azeotrope may also be introduced to a separate reservoir wherein it is contained and prevented from contacting the solution or suspension of polyolefin in anhydrous monofluorobenzene during the chlorination reaction.
  • Other in situ methods include addition to the reactor of compounds which will react with water, for example thionyl chloride or phosgene. Combination of pre-treatment of the monofluorobenzene and in situ water removal are also contemplated by the present invention.
  • the suppression of the formation of monochloromonofluorobenzene is a very important factor in achieving the benefits of the present invention.
  • Reduced production of by-products, in particular monochloromonofluorobenzene may be 5 accomplished by adjusting several process parameters.
  • water in the reaction mixture should be reduced to a low level. Therefore, the monofluorobenzene used in the process contains less than 50 ppm water. It has been found that under such conditions, formation of chlorinated by-products, especially monochloromonofluorobenzene, is suppressed. In 0 addition, under such conditions, formation of sulfuric acid, which causes product degradation and discoloration, is substantially eliminated.
  • the second step of the process of the present invention involves chlorination of olefin polymer in the presence of a free radical catalyst.
  • Typical free radical catalysts include organic peroxides, organic 5 hydroperoxides, or aliphatic azo compounds. Specific examples include
  • Use of mixtures of free radical catalysts are also contemplated by the invention.
  • the amount of catalyst added will depend on the cycle time, which in turn 0 depends on rate of chlorine addition, final chlorine content of the polymer, and size of the reactor.
  • the initiator is introduced in amounts of 0.05-3% by weight of polymer present.
  • Auxiliary catalysts are often added to chlorosulfonation reactions of olefin polymers. These include amine compounds such as pyridine, quinoline, diazobicycloundecene, diazobicyclononane, and diazobicyclooctane.
  • the purpose of the auxiliary catalyst is to facilitate , incorporation of sulfonyl chloride groups onto the polymer backbone.
  • a further advantage of the use of monofluorobenzene as a solvent is that, surprisingly, such additional catalysts are not necessary.
  • Chlorination of the olefin polymer is accomplished by passing elemental chlorine into the reaction solvent at temperatures of about 50-150°C, preferably 80-110°C. In addition, the reaction is preferably run at pressures of 0J 0-0.35 MPa.
  • the chlorinating agent is added either simultaneously with the addition of free radical catalyst or following the addition of free radical catalyst to the reactor. It is important that a sufficient amount of free radical catalyst be present during the entire reaction to suppress chlorination of the monofluorobenzene solvent. This can be accomplished by continuous addition of free radical catalyst simultaneously with the addition of the chlorinating agent.
  • a sufficient level of free radical catalyst having a half-life such that active catalyst species are present throughout the duration of the chlorination reaction can be provided prior to introduction of the chlorinating agent . It is generally preferable to add the free radical catalyst continuously.
  • Half- lives for the free radical catalyst preferably range from 1 minute to 1 hour at temperatures of 80-110°C.
  • Sufficient chlorinating agent is introduced to provide a polymer chlorine level as high as desired, up to the theoretical limit. In the case of polyethylene, this is approximately 70 weight percent chlorine.
  • chlorine levels of at least 20 weight percent are desirable to provide products having good chemical resistance.
  • chlorosulfonyl cure sites may be introduced concurrently with polymer backbone chlorination by employing either sulfuryl chloride, a mixture of chlorine and sulfur dioxide, a mixture of chlorine and sulfuryl chloride, or a mixture of all three reagents as the. chlorinating agent.
  • sulfuryl chloride a mixture of chlorine and sulfur dioxide
  • chlorine and sulfuryl chloride a mixture of chlorine and sulfuryl chloride
  • chlorosulfonation it is possible to incorporate up to 6 weight percent sulfur in the polyolefin.
  • polymers having sulfur contents of 1-3 weight percent are produced.
  • Chlorinated and chlorosulfonated products having chlorine levels of about 20 to about 45 weight percent chlorine find use as elastomers, adhesives and flexible coatings, while products having chlorine contents as high as 50-70 weight percent are useful as additives to coating and adhesive compositions to promote adhesion to wet surfaces and to promote chemical resistance. Products having chlorine levels below 20 weight percent are useful as flow modifiers and surface modifiers.
  • chlorination of the monofluorobenzene reaction medium is reduced substantially.
  • levels of less than about 0.5 weight percent are produced in the reaction medium and a product generally containing less than 0J weight percent chlorinated monochloromonofluorobenzene is isolatable by extrusion.
  • Acid scavengers for example epoxy-containing compounds, may be added to the polymer solution prior to isolation in order to further stabilize the chlorinated resin during the isolation process.
  • Suitable epoxy compounds include condensation products of diglycidylether and bisphenol A, condensation products of epichlorohydrin with diphenols, glycols, or glycerine, epoxidized monounsaturated alkanes, and epoxidized soybean oil.
  • the epoxy stabilizer contains a phenoxy group.
  • an epoxidized alkane or soybean oil it is preferable that it also contains a sterically hindered compound. 5
  • the third step of the process of the present invention involves the isolation of the chlorinated or chlorosulfonated polymer product from the monofluorobenzene solvent.
  • two extruders are used in series, one of which acts as a preconcentrator and which is generally vertically mounted.
  • the polymer solution is introduced to the first extruder, substantially in the absence of o oxygen.
  • the extruder may be a single or double screw vented extruder which causes devolatilization of the product in a closed loop system.
  • the screws may be intermeshing or non-intermeshing. Non-intermeshing screws are preferable for increasing throughput without thermally degrading the polymer.
  • a faster screw speed is employed in this first extruder to give high free volume, which results in efficient vapor liquid separation without polymer entrainment. Generally, enough solvent is removed to produce a composition containing greater than 30 weight percent solids.
  • the mixture is then introduced to a second extruder wherein the screw speed is lower than that of the first extruder.
  • Extruder isolation also permits injection of carrier fluids, preferably water, carbon dioxide, or nitrogen to aid in removal of solvent.
  • carrier fluids preferably water, carbon dioxide, or nitrogen
  • addition of 2-5 weight percent water or nitrogen near the discharge end of the second of a series of two extruders results in lowering of residual solvent in the polymer.
  • the use of a closed loop system provides inherent process safety because contact of the polymer solvent mixture with oxygen is eliminated. In addition, the process is economically attractive because recovered solvent can be recycled.
  • the extruder be constructed of an alloy of nickel and chrome.
  • Chlorinated or chlorosulfonated olefin polymers prepared and isolated according to the provisions of the present invention contain less than 0.5 weight percent, generally less than 0.3 weight percent, combined residual monofluorobenzene and chlorinated by-products of monofluorobenzene, in particular monochloromonofluorobenzene.
  • the polymers are not discolored and vulcanizates of the polymers do not exhibit significant losses of tensile strength compared to corresponding polymers prepared in carbon tetrachloride or aromatic solvents such as chlorobenzene.
  • the tensile strengths of vulcanized polymers prepared according to the process of the present invention are substantially the same as those of corresponding compositions prepared in carbon tetrachloride. Substantially the same means, in this case, that the tensile strengths are within about 10% of the values of compositions prepared in carbon tetrachloride.
  • the invention is further illustrated by the following examples wherein all parts and percentages are by weight
  • Example 1 5 A 113 liter, glass-lined autoclave equipped with a stirrer and a hastalloy overhead condenser is charged with 86kg of monofluorobenzene containing less than 50 ppm water as a contaminant. Fifteen kilograms of polyethylene homopolymer having a density of 0.960g/cc and a melt index of 5.2g/10 minutes is added to the autoclave 0 and it is pressurized to 26 psig (0.28MPa) and then heated to 115°C to dissolve the polyethylene.
  • a free radical catalyst consisting of 2-methyl- 2,2'-azobispropanenitrile, at a concentration of lOg/1 in monofluorobenzene, is added at a rate of 5ml/minute for 10 minutes prior to chlorine addition. Addition of the catalyst is continued at that rate 5 throughout the reaction cycle. Chlorine gas is introduced at a rate of 2kg/hour. Reaction temperature is maintained at 106-109°C for 15 minutes. During this period the shut-off valve in the condensate return line to the autoclave is closed to prevent the monofluorobenzene/water azeotrope which forms from contacting the autoclave contents.
  • the loop- o seal is drained twice during this period to check for the presence of azeotrope which is evidenced by cloudy solvent.
  • a clear liquid indicates that the water/monofluorobenzene azeotrope has been removed from the reactor contents and the reaction mass is dry.
  • the shut-off valve is opened and the temperature is reduced to 99- 102°C. Sulfuryl chloride is then 5 introduced at a rate of 12kg/hour while chlorine gas flow was maintained at
  • the final stabilized product contains approximately 35 wt.% combined chlorine and 1.0 wt.% combined sulfur.
  • the polymer solution is removed from the , reactor to a hold tank from which it is pumped with a gear pump through a leaf type solution filter.
  • the filter and transfer lines are insulated in order to maintain the solution at a temperature above 50°C.
  • the solution is passed through a flow meter and automatic valve to maintain a constant flow rate and through a preheater which raises the temperature of the solution to greater than 90°C and approximately 30 psig pressure (0.31MPa).
  • the solution is then introduced to a vertically mounted 70 mm counter rotating non-intermeshing twin screw preconcentrating extruder having L/D of 16:1 at a feed port located approximately at the midpoint of the barrel section.
  • the extruder is equipped with a vent port operated at approximately 5 psig (0J4MPa) which is located above the feed point and through which at least half the solvent present in the feed solution is removed in vapor form.
  • the extruder is operated at 200 rpm and the barrel is maintained at 130°C.
  • the preconcentrating extruder is mounted atop and perpendicular to a devolatilizing extruder.
  • the drive of the preconcentrating extruder is fitted with a nitrogen chamber where a slight continuous flow of nitrogen is forced through the drive shaft seals.
  • the devolatilizing extruder is a counter rotating, non-intermeshing twin screw extruder with an L/D ratio of greater than 40.
  • the feed point is at least 12 diameters downstream of the drive end, which is also fitted with a nitrogen chamber.
  • Approximately 50% of the remaining solvent in the product stream entering the extruder is removed in vapor form via a rear vent port, operated at atmospheric pressure, located between the feed point and the drive end.
  • the remaining solvent is removed in stages of progressively lower pressure through three downstream vent ports with absolute pressure equal to one-half or less of the absolute pressure in the previous vent.
  • the barrel is heated to a temperature of 150°C in the first half of the devolatilizing extruder and the temperature of the second half is adjusted to maintain the discharge temperature of the polymer at less than 180°C.
  • the devolatilizer screw is operated at 100 rpm, approximately one-half that of the speed of the preconcentrating extruder.
  • the extruded product is non- degraded and has a color equal to that of the feed solution and contains less than 0.5% residual monofluorobenzene and chlorinated by-products of monofluorobenzene.
  • Example 1 The procedure of Example 1 is repeated with the following modifications. No sulfuryl chloride is used and the rate of addition of chlorine gas is increased to achieve a 35% chlorine level in the polymer.
  • the temperature of dissolution of the polyethylene is 110°C
  • the concentration of free radical catalyst in monofluorobenzene is 1%
  • the catalyst solution is added continuously at a rate of 5cc/minute.
  • Reaction temperature is maintained at 106-110°C and chlorine gas is added at a rate of 4kg/hour until a total of 18kg has been added.
  • 15 kg of linear polyethylene, having a melt index of 5.2g/10 minutes is chlorinated to a level of 35%.
  • the chlorinated polyethylene product is isolated from solution using the series of extruders described in Example 1 to yield a product having less than 0.5% monofluorobenzene solvent and chlorinated by-products of monofluorobenzene.

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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)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Procédé de préparation de polymères oléfiniques chlorés et chlorosulfonés contenant de faibles taux de solvant résiduel selon lequel on utilise comme milieu de réaction du monofluorobenzène et on isole le polymère à l'aide d'une série d'extrudeuses ventilées à boucle fermée. Ce procédé permet également de supprimer la formation d'un sous-produit tel que le monochloromonofluorobenzène.
PCT/US1994/007075 1993-06-30 1994-06-29 Procede de preparation de polymeres olefiniques chlores et chlorosulfones Ceased WO1995001380A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94922001A EP0706534A1 (fr) 1993-06-30 1994-06-29 Procede de preparation de polymeres olefiniques chlores et chlorosulfones
JP7503555A JPH08512081A (ja) 1993-06-30 1994-06-29 塩素化およびクロロスルホン化オレフィン重合体の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US8552793A 1993-06-30 1993-06-30
US08/260,123 USH1582H (en) 1993-06-30 1994-06-15 Process for preparation of chlorinated and chlorosulfonated olefin polymers having low levels of residual monofluorobenzene reaction solvent and its chlorinated by-products
US08/260,123 1994-06-15
US08/085,527 1994-06-15

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WO1995001380A1 true WO1995001380A1 (fr) 1995-01-12

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EP (1) EP0706534A1 (fr)
JP (1) JPH08512081A (fr)
WO (1) WO1995001380A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008011477A3 (fr) * 2006-07-20 2008-10-23 Albemarle Corp Technologie de traitement pour la récupération de polymères styréniques bromés à partir de mélanges réactifs dans lesquels ils sont formés et/ou conversion de ces mélanges en granules ou en pastilles
WO2012058002A1 (fr) * 2010-10-29 2012-05-03 Dow Global Technologies Llc Procédé d'extrusion à dégazage de matériau fondu
US9464175B2 (en) 2011-09-27 2016-10-11 Dow Global Technologies Llc Melt devolatilization extrusion processs
CN115386027A (zh) * 2022-09-14 2022-11-25 杭州新元化工技术开发有限公司 一种制备氯化聚氯乙烯的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080249254A1 (en) * 2007-04-03 2008-10-09 Royce Elton Ennis Process for chlorosulfonating polyolefins
US20090247719A1 (en) * 2008-03-31 2009-10-01 Dupont Performance Elastomers L.L.C. Process for chlorosulfonating polyolefins
JP2012067258A (ja) * 2010-09-27 2012-04-05 Tosoh Corp クロロスルホン化ポリオレフィンの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2097799A (en) * 1981-04-30 1982-11-10 Toyo Soda Mfg Co Ltd Chlorosulfonation of polyethylene
US5214107A (en) * 1992-08-03 1993-05-25 E. I. Du Pont De Nemours And Company Chlorination of olefin polymers in chlorofluorobenzene

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6017401B2 (ja) * 1980-09-04 1985-05-02 東ソー株式会社 クロロスルホン化ポリオレフィンの分離，乾燥法
JPS57123201A (en) * 1981-01-23 1982-07-31 Denki Kagaku Kogyo Kk Production of chlorosulfonated polyethylene polymer
JPS5933303A (ja) * 1982-08-18 1984-02-23 Toyo Soda Mfg Co Ltd クロロスルホン化ポリエチレン製造方法
JPS601206A (ja) * 1983-06-20 1985-01-07 Toyo Soda Mfg Co Ltd クロロスルホン化共重合体の製造方法
JPH0618815B2 (ja) * 1984-01-17 1994-03-16 東ソー株式会社 クロロスルホン化ポリエチレンの製造法
JPS60192730A (ja) * 1984-03-14 1985-10-01 Toyo Soda Mfg Co Ltd クロロスルホン化ポリオレフインマスタ−バツチの製法
JPS61120809A (ja) * 1984-11-16 1986-06-07 Denki Kagaku Kogyo Kk クロルスルホン化ポリオレフインの回収方法
JPS61123604A (ja) * 1984-11-19 1986-06-11 Denki Kagaku Kogyo Kk クロロスルホン化重合体溶液から溶剤を脱揮する方法
JPS61130307A (ja) * 1984-11-30 1986-06-18 Denki Kagaku Kogyo Kk クロルスルホン化ポリオレフインの回収方法
JPH05140219A (ja) * 1991-11-21 1993-06-08 Tosoh Corp クロロスルホン化ポリオレフインの製造法
JPH05140215A (ja) * 1991-11-22 1993-06-08 Tosoh Corp 塩素化ポリオレフインの製造法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2097799A (en) * 1981-04-30 1982-11-10 Toyo Soda Mfg Co Ltd Chlorosulfonation of polyethylene
US4544709A (en) * 1981-04-30 1985-10-01 Toyo Soda Manufacturing Co., Ltd. Process for producing chlorosulfonated polyethylene using a mixed solvent
US5214107A (en) * 1992-08-03 1993-05-25 E. I. Du Pont De Nemours And Company Chlorination of olefin polymers in chlorofluorobenzene

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 12, September 1982, Columbus, Ohio, US; abstract no. 93580e, "DRYING OF CHLOROSULFONATED POLYOLEFINS" page 62; column 1; *
CHEMICAL ABSTRACTS, vol. 97, no. 26, December 1982, Columbus, Ohio, US; abstract no. 217741e, "CHLOROSULFONATED POLYETHYLENE" page 79; column 1; *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008011477A3 (fr) * 2006-07-20 2008-10-23 Albemarle Corp Technologie de traitement pour la récupération de polymères styréniques bromés à partir de mélanges réactifs dans lesquels ils sont formés et/ou conversion de ces mélanges en granules ou en pastilles
US8273831B2 (en) 2006-07-20 2012-09-25 Albemarle Corporation Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles
US8450429B2 (en) 2006-07-20 2013-05-28 Ablemarle Corporation Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles
WO2012058002A1 (fr) * 2010-10-29 2012-05-03 Dow Global Technologies Llc Procédé d'extrusion à dégazage de matériau fondu
US9238723B2 (en) 2010-10-29 2016-01-19 Dow Global Technologies Llc Melt devolatilization extrusion process
US9464175B2 (en) 2011-09-27 2016-10-11 Dow Global Technologies Llc Melt devolatilization extrusion processs
CN115386027A (zh) * 2022-09-14 2022-11-25 杭州新元化工技术开发有限公司 一种制备氯化聚氯乙烯的方法
CN115386027B (zh) * 2022-09-14 2024-05-24 杭州新元化工技术开发有限公司 一种制备氯化聚氯乙烯的方法

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Publication number Publication date
JPH08512081A (ja) 1996-12-17
USH1582H (en) 1996-08-06
EP0706534A1 (fr) 1996-04-17

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