EP0020521A1 - Verwendung eines elektrolyten im emulsions-polymerisationsverfahren für die herstellung von vinyl-dispersionsharzen - Google Patents

Verwendung eines elektrolyten im emulsions-polymerisationsverfahren für die herstellung von vinyl-dispersionsharzen

Info

Publication number
EP0020521A1
EP0020521A1 EP79901388A EP79901388A EP0020521A1 EP 0020521 A1 EP0020521 A1 EP 0020521A1 EP 79901388 A EP79901388 A EP 79901388A EP 79901388 A EP79901388 A EP 79901388A EP 0020521 A1 EP0020521 A1 EP 0020521A1
Authority
EP
European Patent Office
Prior art keywords
polymer
electrolyte
premix
vinyl
monomer
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Withdrawn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
EP79901388A
Other languages
English (en)
French (fr)
Other versions
EP0020521A4 (de
Inventor
Bela Kalman Mikofalvy
James Wilson Turner
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.)
Goodrich Corp
Original Assignee
BF Goodrich Corp
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 BF Goodrich Corp filed Critical BF Goodrich Corp
Publication of EP0020521A1 publication Critical patent/EP0020521A1/de
Publication of EP0020521A4 publication Critical patent/EP0020521A4/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Withdrawn legal-status Critical Current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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • vinyl resins may be plasticized or changed from the hard, horny and stiff state to a soft, plastic workable condition by the addition thereto, at elevated temperatures, of certain plasticizers, such as dioctyl phthalate, and the like.
  • plasticizers such as dioctyl phthalate, and the like.
  • These vinyl polymers or resins are referred to as dispersion resins or paste resins and are usually made employing an aqueous emulsion polymerization technique. In some cases, a suspension polymerization process has been used, but emulsion polymerization is preferred.
  • a plasticizer it is referred to as a "plastisol" .
  • the plastisols can be used in making molded products, films, coatings, and the like.
  • the vinyl dispersion resin must be capable of being mixed with the plasticizers easily and uniformly to form low viscosity plastisols which are stable, containing particles of uniform and proper size, and capable of producing films, and like products, of good clarity.
  • suitable latices have been difficult to obtain since the latices usually contain particles of varying size and are either too fine or too large.
  • Various proposals have heretofore been made to overcome these difficulties but not with the ultimate success desired.
  • the particles of polymer to be used in a plastisol should preferably be spherical in shape to present as small a particle surface as possible for minimum solvation. Also, a dispersion of spheres provides the lowest flow viscosity for charging molds, coating and like operations (See U.S. "Patent No. J,179,646, issued April 20, 1965).
  • the polymerization reaction of the vinyl monomer or monomers is conducted in an aqueous alkaline medium using a free radical yielding polymerization initiator, at a temperature below about 48°C, in the presence of the ammoniumsalt of a high fatty acid containing from 8 to 20 carbon atoms, and at least one long straight chain alcohol containing from 14 to 24 carbon atoms, wherein the ratio of alcohol to emulsifier is equal to or greater than 1.0, and wherein the reaction ingredients are thoroughly mixed, and preferably homogenized, prior to polymeriza tion.
  • the polymer buildup in the reactor is reduced and multiple polymerizations can be run in the reactor without opening the same thereby substantially reducing the amount of unreacted monomer in the surrounding atmosphere.
  • vinyl dispersion resin refers to polymers and copolymers of vinyl and vinylidene halides such as vinyl chloride, vinylidene chloride, and the like.
  • vinylidene monomers may be mentioned the ⁇ , ⁇ -olefinically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, ⁇ -cyanoacrylic acid, and the like; esters of acrylic acids, such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, and the like; esters of methacrylic acid, such as methyl methacrylate, butyl methacrylate, and the like; nitriles such as a ⁇ rylonitrile and methacrylonitrile; acrylamides, such as methyl acrylamide, N-methylol acrylamide, N-butoxyl methacrylamide, and the like; vinyl ethers, such as ethyl vinyl ether, chloroethyl vinyl ether, and the like; the vinyl ketones; styrene and styrene derivatives including ⁇
  • the present invention is particularly applicable to the manufacture of vinyl dispersion resins or pastes made by the polymerization of vinyl chloride or vinylidene chloride alone or in admixture with one or more vinylidene monomers copolymerizable therewith in amounts as great as about 80% by weight, based on the weight of the monomer mixture.
  • the most preferred vinyl dispersion resin is polyvinyl chloride (PVC) and the invention, for simplicity and convenience, will be described in connection therewith, it being understood that this is merely intended in an illustrative and not a limitative sense.
  • the electrolytes useful in the present invention are ammonium carbonate ((NH 4 ) 2 CO 3 ), calcium chloride (CaCl 2 ), calcium carbonate (CaCO 3 ) , ammonium phosphate, the bicarbonates, the sodium salts such as carbonates, bicarbonates and phosphates, and the like.
  • the amount of electrolyte suitable for use in the present invention will vary from about 0.05% to about 6.0% by weight, based on the weight of the monomer or monomers being polymerized. Preferably an amount in the range of 0.1% to 2.0% by weight is employed.
  • the friable aggregates resulting from the process of the instant invention represent a distinct advantage or improvement over prior known means for recovering vinyl dispersion or paste resins from the water for use in plastisols, for example, spray drying and subsequent grinding.
  • the friable aggregates of the present process can easily be handled in the post polymerization stages of polymer or resin recovery.
  • the friable aggregates are easily formed and the individual spherical particles of the vinyl dispersion resins, of a size required for paste resins are easily formed by crushing, simple grinding or rubbing of said aggregates.
  • the individual spherical particles of polymer will have a size or diameter in the range of 0.1 micron to about 10.0 microns.
  • Another surprising feature of the present, invention is that polymer buildup on the internal surfaces of the reactor is reduced. While it is not known precisely why such reduction in buildup occurs, it is believed to be due in part not only to the presence of the electrolyte in the recipe, but also to the speed of the reaction and the lower reaction temperatures, since it is known that the higher the temperature of reaction for prolonged periods of time increases the likelihood of excessive polymer buildup. In any event, the polymer buildup problem is greatly improved when using the present invention. Further, when employing the present process, the vinyl dispersion resin and the plastisol application properties, such as heat stability, water resistance, flow properties, and the like, are not adversely effected and in fact, if anything, they are improved.
  • emulsifiers When making vinyl dispersion resins by the emulsion polymerization procedure it is necessary to employ a proper emulsifier or emulsifier system.
  • various fatty acid derivatives and salts thereof may be employed, as well as the sulfate and sulfonate type soaps of from C 12 to C 20 alkyl or aryl hydrocarbons, or various combinations thereof.
  • the ammonium salt of a long chain saturated fatty acid is employed as the emulsifier.
  • the saturated fatty acids which are useful may be either natural or synthetic and should contain from 8 to 20 carbon atoms.
  • ammonium salt emulsifier is employed in an amount in the range of about 0.5% to about 4.0% by weight based on the weight of the monomer or monomers being polymerized.
  • the ammonium salts of the fatty acids can be made by mixing the fatty acid and ammonium hydroxide, separating the salt and then adding the same to the polymerization medium or polymerization premix in the usual fashion. However, it is preferred to form the ammonium salt in situ, that is, by adding the fatty acid and ammonium hydroxide separately to the polymerization mixture or medium wherein they react to form the salt. An excess of ammonium hydroxide, over that necessary to react with the fatty acid, should be employed in order to maintain the reaction medium on the alkaline side.
  • a long straight chain saturated alcohol in combination therewith, said alcohol being one containing from 14 to 24 carbon atoms.
  • examples of such alcohols are tetradecano1, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, tricosanol, and tetracosanol.
  • Mixtures of the alcohols can also be employed and in many cases an alcohol mixture is preferred, such as, for example, a mixture, of a 14 carbon alcohol and an 18 carbon alcohol.
  • the reaction medium should be maintained on the alkaline side, and preferably at a high pH.
  • the present process can be conducted at a pH in the range of about 7.0 to about 12.0. However, it is preferred to operate in a pH range of about 8.0 to about 10.5. If the pH is too high it takes too much NH 4 OH and if the pH is too low, for example, below 7.0, the polymer buildup in the reactor increases and the coagulum increases.
  • the amount of NH 4 OH needed to properly adjust the pH will depend in part on the particular emulsifier system being used in the reaction mixture. Of course, other alkaline agents may be employed to adjust the pH of the reaction mixture, such as NaOH, KOH, etc. The choice of a particular alkaline agent depends upon the ingredients in the reaction medium.
  • the process of the present invention wherein an electrolyte is employed in the reaction mixture and the product is tray dried, is conducted in the presence of a compound or compounds capable of initiating the polymerization reaction.
  • Free radical yielding initiators normally used for polymerizing olefinically unsaturated monomers, are satisfactory.
  • the useful initiators or catalysts include, for example, the various peroxygen compounds, such as lauryl peroxide, isoprppyl perdxydicarb ⁇ nate, benzoyl 'peroxide/ t-butyl hydroperoxide, t-butyl peroxypivalate, cumene hydro- peroxide, t-butyl diperphthalate, pelargonyl peroxide, 1-hydroxycyclohexyl hydroperoxide, and the like; azo compounds such as azodiisobutyronitrile, dimethylazo- diisobutyrate, and the like.
  • peroxygen compounds such as lauryl peroxide, isoprppyl perdxydicarb ⁇ nate, benzoyl 'peroxide/ t-butyl hydroperoxide, t-butyl peroxypivalate, cumene hydro- peroxide, t-butyl diperphthalate, pelargonyl peroxide, 1-hydroxy
  • premix is homogenized prior to introduction into the reactor.
  • the temperature is adjusted to that at which the reaction is to take place.
  • the temperature of reaction of the instant emulsion polymerization process is important since the intrinsic viscosity (IV) of the resultant vinyl dispersion resin is a direct function of the temperature of reaction. That is the higher the temperature the lower the IV. Accordingly, the end use for the vinyl dispersion resin to be produced will normally dictate the reaction temperature. For example, when producing vinyl dispersion resins to be used in coatings or in casting flexible films, a lower temperature will be employed in order to attain a higher IV which is desirable for many coating applications and film-forming operations. We have found that for the end uses to which the vinyl dispersion resins of this invention are particularly adapted, polymerization temperatures in the- range of about 30°C to about 70°C are satisfactory. However, it is preferred to employ a temperature in the range of about 30°C to about 55°C.
  • the polymer buildup in the reactor increases.
  • the polymer buildup is not of the hard crusty type and can be removed by rinsing or hosing down with water and without opening the reactor when appropriate spray nozzles are installed in the reactor.
  • this buildup is controlled and reduced by the presence of the electrolyte in the reaction medium. In combination with the electrolyte, the walls of the reactor are kept cool, during the polymerization reaction, especially during the early stages of the reaction when most of the buildup, if any, forms.
  • the vinyl dispersion resin is isolated in powder form, that is, in the form of discrete spherical polymer particles. This is accomplished by filtering the latex from the polymerization reactor in order to recover the friable aggregates of polymer, tray drying the filtered latex at a temperature in the range of about 23°C to about 100 °C. under atmospheric pressure during the course of which the electrolyte comes off .
  • the drying temperature can be lower or higher than the limits of said range of temperature depending upon whether or not the drying step takes place under a vacuum or under positive pressure.
  • the time of the tray drying step will depend upon the particular polymer being dried. However, the tray drying should continue until the water content of the polymer is about 0.1% by weight or lower.
  • Plastisols are made with the vinyl dispersion resins of the present invention by uniformly blending or intimately mixing, by conventional means using heat and agitation, with 100 parts by weight of the vinyl dispersion resin in the form of discrete spherical polymer particles, from about 30 to about 100 parts by weight of one or more plasticizers .
  • the useful plasticizers may be described as the alkyl and alkoxy alkyl esters of dicarboxylic acids or the esters of a polyhydric alcohol and a monobasic acid.
  • the preferred plasticizers are the liquid, diesters of aliphatic alcohols having from 4 to 20 carbon atoms and dibasic carboxylic acids having from 6 to 14 carbon atoms
  • the plastisols made from the vinyl dispersion resins of the present invention should have the desired yield and preferably with little or no dilatency. Yield is simply defined as resistance to flow and is normally determined numerically through viscosity measurements employing well known standard techniques . Normally such values are arrived at by calculation from viscosity measurements using a Brookfield Model RVF Viscometer according to ASTM method D1824-61T. Yield is determined from viscosity measurements of the plastisols at varying r.p.m.
  • a mpnomer premix tank or vessel was evacuated.
  • the premix tank was first charged with the water and then, under agitation, the electrolyte was added followed by the emulsifier and then the alcohol mixture.
  • the catalyst was added next, and lastly, the vinyl chloride.
  • the temperature in the premix tank was controlled at about 25°C, by means of a cooling jacket.
  • the mixture was agitated for about 15 minutes. Thereafter, the mixture, or monomer premix was passed through a Mantin Ganlin 2 stage homogenizer at a temperature of 25°C into the polymerization reactor which had previously been evacuated.
  • the pressure in the first stage of the homogenizer was 600 psig.
  • EXAMPLE II EXAMPLE II .
  • a series of runs were made to show the effect of varying the concentration of the electrolyte.
  • the same polymerization procedure as in Example I was employed with the exception that homogenization was not used.
  • the plastisols were also made as in Example I. The results are in the following table:

Landscapes

  • 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)
EP19790901388 1978-10-30 1980-05-20 Verwendung eines elektrolyten im emulsions-polymerisationsverfahren für die herstellung von vinyl-dispersionsharzen. Withdrawn EP0020521A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US95581778A 1978-10-30 1978-10-30
US955817 1978-10-30

Publications (2)

Publication Number Publication Date
EP0020521A1 true EP0020521A1 (de) 1981-01-07
EP0020521A4 EP0020521A4 (de) 1981-02-24

Family

ID=25497388

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19790901388 Withdrawn EP0020521A4 (de) 1978-10-30 1980-05-20 Verwendung eines elektrolyten im emulsions-polymerisationsverfahren für die herstellung von vinyl-dispersionsharzen.

Country Status (9)

Country Link
EP (1) EP0020521A4 (de)
JP (1) JPS55500869A (de)
KR (1) KR830000854B1 (de)
AU (1) AU528510B2 (de)
BE (1) BE879728A (de)
CA (1) CA1138150A (de)
IN (1) IN150093B (de)
NO (1) NO793472L (de)
WO (1) WO1980000967A1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179646A (en) * 1959-09-28 1965-04-20 Dow Chemical Co Polymerization to produce friable aggregates of individual spheres of polyvinyl chloride
US3226350A (en) * 1962-07-23 1965-12-28 Goodyear Tire & Rubber Preparation of high solids vinyl chloride polymer latex
US4098978A (en) * 1975-11-12 1978-07-04 The B. F. Goodrich Company Process for emulsion polymerization of vinylidene halides and product thereof
US4076920A (en) * 1976-11-02 1978-02-28 The B. F. Goodrich Company Process for producing homo- or copolymerization of vinyl or vinylidene halides having reduced polymer build-up in the reactor
US4071675A (en) * 1977-03-03 1978-01-31 Stauffer Chemical Company Emulsion polymerization of vinyl chloride using mixed emulsifier system in a single step in the absence of seed formation
US4150210A (en) * 1978-06-19 1979-04-17 Stauffer Chemical Company Emulsion polymerization of vinyl chloride polymers using mixed emulsifier system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8000967A1 *

Also Published As

Publication number Publication date
CA1138150A (en) 1982-12-21
WO1980000967A1 (en) 1980-05-15
NO793472L (no) 1980-05-02
IN150093B (de) 1982-07-17
JPS55500869A (de) 1980-10-30
AU528510B2 (en) 1983-05-05
AU5170879A (en) 1980-05-08
BE879728A (fr) 1980-02-15
KR830000854B1 (ko) 1983-04-21
EP0020521A4 (de) 1981-02-24

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Inventor name: TURNER, JAMES WILSON

Inventor name: MIKOFALVY, BELA KALMAN