EP0856011A2 - Polymerisation heterogene dans le co 2? - Google Patents

Polymerisation heterogene dans le co 2?

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Publication number
EP0856011A2
EP0856011A2 EP96940237A EP96940237A EP0856011A2 EP 0856011 A2 EP0856011 A2 EP 0856011A2 EP 96940237 A EP96940237 A EP 96940237A EP 96940237 A EP96940237 A EP 96940237A EP 0856011 A2 EP0856011 A2 EP 0856011A2
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EP
European Patent Office
Prior art keywords
polymer
polymerization
monomer
carbon dioxide
tert
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
EP96940237A
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German (de)
English (en)
Inventor
Joseph M. Desimone
Timothy Romack
Dorian A. Canelas
Katherine A. Shaffer
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University of North Carolina at Chapel Hill
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University of North Carolina at Chapel Hill
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Publication date
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Publication of EP0856011A2 publication Critical patent/EP0856011A2/fr
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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • 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
    • C08F2/04—Polymerisation in solution
    • 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
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes

Definitions

  • This invention relates generally to heterogeneous polymerizations carried out in a carbon dioxide continuous phase, and more specifically relates to heterogeneous polymerizations carried out in carbon dioxide in which a stabilizer reacts with the polymer formed during polymerization.
  • Emulsion polymerization is a heterogeneous process often used by industry to polymerize a wide variety of monomers using free radical mechanisms. It involves the polymerization of monomers in the form of emulsion polymerizations or latexes.
  • Polymers commonly formed by emulsions include acrylics, styrenics, polyvinylchloride (PVC) , styrene-butadiene rubber, ethylene-propylene terpolymers (EDPM) , polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS) , neoprene rubber, ethylene-vinyl acetate, styrene-maleic anhydride, tetrafluoroethylene, and vinyl fluoride.
  • PVC polyvinylchloride
  • EDPM ethylene-propylene terpolymers
  • ABS acrylonitrile-butadiene-styrene
  • the present invention provides a method of carrying out the polymerization of a monomer.
  • the method comprises (a) providing a reaction mixture comprising a monomer, a stabilizer precursor, and a polymerization initiator in a polymerization medium comprising carbon dioxide; and then (£>) polymerizing the monomer and the stabilizer precursor in the polymerization medium to form a heterogeneous reaction mixture comprising a polymer in the polymerization medium.
  • the stabilizer precursor is covalently bound to the polymer to provide an intrinsic surfactant in the polymer, which surfactant stabilizes the polymer in the heterogeneous reaction mixture.
  • the stabilizer precursor is capable of covalently bonding to and reacting with the monomer, the polymer, or the initiator during the polymerization step.
  • the present invention provides a polymer produced by the process outlined above.
  • the present invention is directed toward a method of carrying out the heterogeneous polymerization of a monomer and a stabilizer precursor which is capable of being polymerized in the polymer to provide an intrinsic surfactant in the polymer.
  • the intrinsic surfactant in turn stabilizes the forming polymer in the heterogeneous reaction mixture during the polymerization step.
  • the steps of the method comprise providing a reaction mixture comprising monomer, stabilizer precursor, and a polymerization initiator in a polymerization medium comprising carbon dioxide (C0 2 ) , and then polymerizing the monomer and stabilizer precursor in the reaction mixture to form a polymer.
  • polymer refers to homopolymers, oligomers, and copolymers, depending upon the number of monomers which are employed.
  • heterogeneous reaction mixture refers to a reaction mixture having at least two phases. One phase is termed the “continuous phase”, which comprises a fluid, and the other is termed the “dispersed phase", comprising the polymer or copolymer formed.
  • the polymerization reaction is initially homogeneous, wherein the monomer and stabilizer precursor are solubilized in the polymerization medium, and becomes heterogeneous as the polymerization proceeds and the polymer is formed.
  • the newly forming polymer forms the dispersed phase of the reaction.
  • the polymer is stabilized in the dispersed phase by the presence of the intrinsic surfactant which is formed by the polymerization of the stabilizer precursor and the monomer during the polymerization step.
  • the intrinsic surfactant which is formed reduces the surface tension between the phases .
  • heterogeneous reaction mixture or
  • heterogeneous polymerization is intended to encompass both dispersion polymerizations, in which the polymerization starts out homogeneous, and emulsion polymerizations, in which the polymerization starts out heterogeneous, and the polymerization initiator is preferentially solubilized in the continuous phase.
  • a compound is "preferentially solubilized” in one phase over another when it is more soluble in that phase.
  • the present invention is preferably carried out by dispersion polymerization. A dispersion polymerizaton starts as a one phase, homogeneous system where both the monomer and the initiator are soluble in the polymerization medium but the resulting polymer i ⁇ not.
  • Dispersion polymerizations are generally described in Barrett, K.E.J. Dispersion Polymerization in Organic Media; Wiley: London, 1975; and Napper, D.H. Polymeric Stabilization of Colloidal Dispersions; Academic Press: London, 1983, the disclosures of which are incorporated herein by reference in their entirety.
  • the polymerization is initiated homogeneously and the resulting polymer phase separates into primary particles. These primary particles become stabilized by stabilizers present in the system that prevent particle flocculation and aggregation.
  • Polymer colloids produced by dispersion polymerizations are usually stabilized by a "steric" mechanism as compared with an electrostatic mechanism that is common to collodial stabilizaton in aqueous environments. Steric stabilization of a collodial dispersion is usually imparted by amphiphilic macromolecules that become absorbed onto the surface of the dispersed phase.
  • amphiphilic macromolecules contain an anchoring segment, which attaches to the particle either by physical or chemical adsorption, and stabilizing moieties that are soluble in the continuous phase.
  • the stabilizing moieties project into the continuouse phase to prevent flocculation and thereby impart stability to the colloid.
  • Dispersion polymerizations are generally carried out in either an aqueous or an organic medium and lead to particles of collodial dimensions (i.e. 0.1 to 10 ⁇ m) .
  • Monomers which are useful in the present invention include any of a wide variety of monomers known to those skilled in the art.
  • Particularly suitable monomers can be selected from the group consisting of styrene monomers, acrylic monomers, vinyl chloride monomers, olefinic monomers, fluoroolefinic monomers, and maleic anhydride monomers.
  • the monomer is typically present in the amount of from 1 to 70 percent by weight based upon the entire weight of the homogeneous reaction mixture.
  • Two or more of the foregoing monomers may be employed in combination for the purpose of providing oligomers or copolymers. Any combination of monomers may be employed provided that the monomers selected are copolymerizable.
  • the stabilizer precursor is a compound which is capable of reacting with the monomer during the polymerization step to provide an intrinsic surfactant within the forming polymer.
  • the intrinsic surfactant is capable of reducing the interfacial energy between the dispersed polymer phase and the continuous carbon dioxide polymerization medium phase.
  • the presence of the formed intrinsic surfactant results in the formation of micron and submicron sized particles.
  • the unpolymerized stabilizer precursor is incapable of acting as a surfactant.
  • the stabilizer precursor may be referred to as a surfactant, or a reactive stabilizer.
  • the stabilizer precursors include any of a variety of compounds which are capable of reacting with any of the monomer, the polymer, or the initiator to provide the intrinsic surfactant.
  • Suitable stabilizer precursors may include macromonomers, macro-chain transfer agents, and macroinitiators.
  • the stabilizer precursor is a macromonomer which is capable of copolymerizing with the monomer.
  • the stabilizer precursor includes a segment which is soluble in carbon dioxide and a reactive segment which is capable of reacting with the monomer.
  • the carbon dioxide soluble segment of the stabilizer precursor may include any of a variety of segments that are soluble in carbon dioxide. Examples of suitable carbon dioxide soluble segments include fluorine-containing or siioxane-containing segments. Suitable fluorine-containing segments include amorphous or low melting fluoropolymers.
  • fluoropolymer has its conventional meaning in the art. See generally Fluoropolymers (L. Wall, Ed. 1972) (Wiley-Interscience Division of John Wiley & Sons) ; see also Fluorine- Containing Polymers, 7 Encyclopedia of Polymer Science and Engineering 256 (H. Mark et al . Eds., 2d Ed. 1985) .
  • fluoropolymers are those formed from: fluoroacrylate monomers such as 2-(N- ethylperfluorooctanesulfonamido) ethyl acrylate (“Et- FOSEA”) , 2- (N-ethylperfluorooctanesulfonamido) ethyl methacrylate (“EtFOSEMA” ) , 2- (N- methylperfluorooctanesulfonamido) ethyl acrylate (“MeFOSEA”) , 2- (N-methylperfluorooctanesulfonamido) - ethyl methacrylate (“MeFOSEMA”) , 1,1- dihydroperfluorooctyl acrylate (“FOA”), and 1,1- dihydroperfluorooctyl methacrylate (“FOMA”) ; fluoroolefin monomers such as tetrafluoroethylene
  • siioxane-containing compounds examples include siloxanes having C- L -Cg straight or branched chain alkyl, perfluoroalkyl, aryl, or alkylaryl groups, and alkoxy groups of the formula:
  • x is a number from 1-50.
  • the stabilizer precursor includes at least one reactive segment in addition to the carbon dioxide soluble segment.
  • the stabilizer precursor may include any suitable number of reactive segments.
  • the reactive segment of the stabilizer precursor may include any of a variety of suitable segments known to those skilled in the art, which are capable of polymerizing with the monomer to form the intrinsic surfactant.
  • at least one reactive segment is covalently attached to the carbon dioxide soluble segment .
  • suitable reactive segments include those described in U.S. Patent No. 4,981,727 to Brinduse et al., the disclosure of which is incorporated herein by reference in its entirety.
  • the reactive segments include a vinyl group or other group recognized by those skilled in the art as capable of polymerizing with the monomer by any of free radical, cationic, ring-opening metathesis, or step-growth polymerization mechanisms.
  • Preferred reactive segments include, for example, C 2 -C 12 alkenes; alkylidenes; phenyl substituted 1 or more times by unsaturated alkyl; alkoxyacryloyl; alkylthiol; alkylhalo; alkylcarboxy; halo; amino; H; hydroxy; alkylamino; or groups having the formula:
  • R x is C 1 -C 12 alkylene .
  • preferred stabilizer precursors include, but are not limited to, vinyl functional poly(dimethylsiloxane) , allyl functional poly(dimethylsiloxane) , 1-hexenyl functional poly(dimethylsiloxane) , vinylphenyl functional polydimethylsiloxane, vinyl benzyl terminated poly(dimethylsiloxane) , vinyl terminated poly(dimethylsiloxane) , methacryloxypropyl functional poly(dimethylsiloxane) , acryloxypropyl functional poly(dimethylsiloxane) , mercapto functional poly(dimethylsiloxane) , divinyl functional poly(dimethylsiloxane) , vinyl terminated diphenylsiloxane-dimethylsiloxane copolymer, vinylmethy1siloxane-dimethylsiloxane copolymer, ethacroloyl terminate
  • Particularly preferred stabilizer precursors include, but are not limited to, poly(dimethylsiloxane) - monomethacrylate, dimethylvinylsilyl poly(dimethylsiloxane) , mercaptopoly(dimethylsiloxane) , vinyl benzyl terminated poly(dimethylsiloxane) , vinyl terminated poly(dimethysiloxane) and methacryloyl terminated poly(1, 1-dihydroperfluorooctyl methacrylate) .
  • the stabilizer precursor is present in the reaction mixture at a concentration ranging from 0.05 to 10 percent by weight based upon the total weight of the homogeneous reaction mixture.
  • the reaction mixture preferably also includes a free radical initiator capable of initiating and/or accelerating the polymerization.
  • the initiator is included in the solution in a concentration ranging from 0.001 to 20 percent by weight of the homogeneous mixture.
  • Organic free radical initiators include, but are not limited to, the following: acetylcyclohexanesulfonyl peroxide; diacetyl peroxydicarbonate; dicyclohexyl peroxydicarbonate; di- 2-ethylhexyl peroxydicarbonate; tert-butyl perneodecanoate; 2,2'-azobis (4-methoxy-2, 4- dimethylvaleronitrile; tert-butyl perpivalate; dioctanoyl peroxide; dilauroyl peroxide; 2,2'-azobis (2, 4-dimethylvaleronitrile) ; tert-butylazo-2- cyanobutane; dibenzoyl peroxide; tert-butyl per-2- ethylhexanoate; tert-buty
  • Redox systems such as dimethylaniline-benzoyl peroxide, diethylaniline-benzoyl peroxide and diphenylamine-benzoyl peroxide can also be used to initiate the polymerization.
  • the preferred initiators are 2,2'- azobis (isobutyro-nitrile) ("AIBN") , and 2, 2' -azobis (4- methoxy-2,4-dimethylvaleronitrile) .
  • the polymerization medium of the present invention comprises carbon dioxide.
  • the carbon dioxide can be employed in a liquid, vapor, or supercritical phase. If liquid carbon dioxide is used, the temperature of the reaction should be below 31°C. Preferably, the carbon dioxide is in a liquid or
  • “supercritical” phase As used herein, “supercritical” means that a fluid medium is at a temperature that is sufficiently high that it cannot be liquified by pressure.
  • the thermodynamic properties of carbon dioxide are reported in Hyatt, J. Org. Chem. 49:5097- 5101 (1984) ; therein, it is stated that the critical temperature of carbon dioxide is about 31°C.
  • the reaction temperature should be chosen to provide sufficient heat energy to initiate and propagate the polymerization. Preferably, the reaction temperature will be between -50°C and 200°C, and more preferably will be between -20°C and 100°C.
  • the advantage of conducting the polymerization with supercritical carbon dioxide stems from the tendency of the solvent strength in a supercritical phase to be easily manipulated by varying the pressure of the fluid.
  • the pressure will preferably be between 15 to 45,000 psi, and more preferably between 200 and 10,000 psi.
  • the use of supercritical carbon dioxide permits one carrying out the polymerization to significantly influence the particle size, distribution, and other aspects of the final product without varying either the solvent temperature or composition (i.e., including a co- solvent) .
  • the polymerizing step of the present invention can be carried out by polymerization methods using apparatus and conditions known to those skilled in this art.
  • Similar apparatus and conditions may also be utilized during the step in which the reactive stabilizer reacts and becomes bonded to the polymer.
  • these steps may be carried out batchwise or continuously with thorough mixing of the reactants (i.e., initiator, monomer or monomers, and reactive stabilizer) in any appropriate high pressure vessel.
  • the reactants i.e., initiator, monomer or monomers, and reactive stabilizer
  • employing a continuous or semi-batch reactor may be useful to control polymer composition and composition distribution and may be useful in the copolymerization of two monomers with different reactivities.
  • the polymerization can be carried out by charging the reaction vessel with monomer, stabilizer precursor, initiator, and carbon dioxide, closing the reaction vessel, and bringing the reaction mixture to an appropriate temperature and pressure.
  • the reaction mixture may be introduced into the reaction vessel and heated to the polymerization temperature and brought to the polymerization pressure, with additional reaction mixture being added at a rate corresponding to the rate of polymerization.
  • the initiator, and some of each of the monomer and stabilizer precursor may be initially introduced into the reaction vessel and brought to temperature and pressure, with additional monomer and/or stabilizer precursor being added at the rate at which polymerization proceeds.
  • the mixture is allowed to polymerize for between about 2 and 24 hours, and preferably is stirred as the reaction proceeds.
  • the stabilizer precursor reacts with any of the monomer, the polymer, or the initiator to form an intrinsic surfactant.
  • the stabilizer precursor is copolymerized with the monomer to form the intrinsic surfactant in the polymer.
  • the polymer can be collected by methods such as venting of the polymerization medium or by fractionation.
  • a portion of the stabilizer precursor that is not copolymerized with the monomer may be recovered from the carbon dioxide and polymer mixture by fractionation, by reducing temperature and pressure, and thus is able to be reused.
  • the polymer can be collected by conventional means.
  • the polymers of the present invention may be retained in the carbon dioxide polymerization medium or re- dispersed in a carbon dioxide medium, and sprayed onto a surface. After the carbon dioxide evaporates, the polymer forms a coating on the surface.
  • the polymer formed by the present invention can also be used to form molded articles, such as valves and bottles, films, fibers, resins, and matrices for composite materials.
  • molded articles such as valves and bottles, films, fibers, resins, and matrices for composite materials.
  • the following examples are provided to illustrate the present invention, and should not be construed as limiting thereof.
  • M means molar concentration
  • NMR nuclear magnetic resonance
  • GPC means gel permeation chromatography
  • mg means milligrams
  • g means grams
  • mol means moles
  • g/mole means grams per mole
  • mL means milliliters
  • °C means degrees Celsius
  • psi means pounds per square inch
  • M n means number average molecular weight
  • MWD means molecular weight distribution
  • ppm means parts per million
  • ⁇ m means micrometers
  • AIBN means 2,2'- azobis (isobutyronitrile)
  • CoBF2»H20 means Cobaloximeborondifluoride»H 2
  • PDMS means poly(dimethylsiloxane)
  • poly(FOMA) means poly(1, 1' -dihydroperfluorooctyl methacrylate) .
  • 0.1518 g of PDMS macromonomer having a methacrylate terminus and a number average molecular weight of 11.3xl0 3 g/mole, and a stir bar are added to a 10 mL high pressure view cell. After purging the cell with argon for 15 minutes, 2.1 g of deoxygenated methyl methacrylate is added. The cell is pressurized with carbon dioxide to a pressure of ca. 1600 psi. The contents of the cell are stirred. The cell is heated to 65°C and additional carbon dioxide is added to achieve a cell pressure of 4930 psi at a temperature of 65°C.
  • the reaction is allowed to proceed for 4 hours, after which time the cell is immersed in a water bath and the carbon dioxide is quickly vented from the cell.
  • the cell is cooled to room temperature, and the resulting polymer, obtained in 87% yield, is a course white powder having a number average molecular weight of 3-OlxlO 5 g/mole and a molecular weight distribution of 2.4.
  • the polymer product is shown to be comprised of polymer particles having a diameter of ca. 2.5 ⁇ .
  • X H NMR spectroscopy indicates a polymer content of 7.3 weight percent PDMS.
  • Example 1 Polymer Wash The polymer prepared in Example 1 (0.050 g) is stirred in 20 mL hexanes at room temperature for 23 hours. The washed product is recovered by filtration and dried in vacuo. The morphology of the product is substantially unchanged by washing, while the number average molecular weight increases to 3.86xl0 5 g/mole and the molecular weight distribution decreases to 2.1. H NMR spectroscopy indicates a polymer content of 0.24 weight percent PDMS.
  • the polymer prepared according to Example 1 (0.0735 g) is extracted with carbon dioxide at room temperature and a pressure of 5000 psi at a flow rate of 1-2 mL/min for ca. 4 hours.
  • the morphology of the product is substantially unaffected by the extraction.
  • the material extracted from the product is identified as PDMS macromonomer by l NMR spectroscopy.
  • X H NMR spectroscopy indicates a polymer content of 0.26 weight percent PDMS.
  • the polymerization is carried out as in Example 1, with the exception that 0.399 g of PDMS macromonomer having a methafcrylate terminus is employed.
  • the polymerization produces 88% yield of polymer in the form of a coarse white powder having a number average molecular weight of 2.22x10 s g/mole and a molecular weight distribution of 3.8.
  • the product is comprised of polymer particles with an approximate diameter of 1.0 mm which are coated with excess PDMS macromonomer which is not covalently attached to the particles.
  • H NMR spectroscopy indicates a polymer content of 17 weight percent PDMS.
  • the polymer particles are extracted to remove excess PDMS macromonomer. Washing produces polymer particles having a diameter of ca. 1.0 ⁇ m which are no longer coated with excess PDMS macromonomer.
  • X H NMR spectroscopy indicates a polymer content of 0.68 weight percent PDMS.
  • the number average molecular weight of the polymer after extraction is 3.63xl0 5 g/mole and the molecular weight distribution is 2.3.
  • Example 5 Heterogeneous Polymerization with PDMS Macromonomer The polymerization is carried out as in
  • Example 1 with the exception that 0.001 g of PDMS macromonomer having a methacrylate terminus is employed. Polymer is obtained in 56% yield as a hard white solid with a number average molecular weight of 1.81x10 s g/mole.
  • the polymerization is carried out as in Example 1, except that PDMS macromonomer is omitted from the reaction mixture.
  • the resulting polymer is obtained in a 24% yield in the form of a clear, tacky polymer having a number average molecular weight of 6.5xl0 4 g/mole.
  • the polymerization is carried out as in Example 1, with the exception that 0.0401 g of AIBN, 0.0506 g of PDMS macromonomer and 2.0 g of styrene are employed and the reaction is carried out for 24 hours.
  • a white powdery polymer product containing a small amount of soft, tacky material is obtained in 71% yield.
  • the number average molecular weight of the resulting polymer is l. ⁇ xlO 4 g/mole and the molecular weight distribution is 3.1.
  • the polymerization is carried out as in Example 1, with the exception that 0.0200 g AIBN, 0.152 g PDMS macromonomer, 1.1 g butyl acrylate and 1.1 g methyl methacrylate are employed.
  • the resulting copolymer forms a stable latex in carbon dioxide which does not settle when stirring is discontinued.
  • the carbon dioxide is quickly vented onto a sheet of aluminum where the polymer forms a thin, opaque, non-tacky film.
  • the number average molecular weight of the resulting polymer is 2.0xl0 4 g/mole and the molecular weight distribution was 1.7.
  • the polymerization is carried out as in Example 1, with the exception that 0.054 g of PDMS macromonomer and 0.065 g 2, 2' -azobis (4-methoxy-2, 4- dimethylvaleronitrile) are employed, and the reaction is carried out at 30°C and 1000 psi for 21 hours.
  • the resulting polymer is obtained in 92% yield in the form of a fine white powder having an approximate average diameter of 6 ⁇ m, a number average molecular weight of 1.2xl0 5 g/mole and a molecular weight distribution of 2.3.
  • Example 11 Heterogeneous Polymerization with PDMS Macromonomer
  • the polymerization is carried out as in Example 1, with the exception that 0.200 g of a monovinyl terminated PDMS macromonomer with a number average molecular weight of 34.3xl0 3 g/mole, 0.040 g of AIBN, and 2.0 g vinyl acetate are employed.
  • a tacky white material is obtained in 53% yield.
  • the product is comprised of spherical particles which have an approximate average diameter of 10 ⁇ m, a number average molecular weight of 2.8xl0 3 g/mole, and a molecular weight distribution of 3.0.
  • Example 1 with the exception that 0.100 g of a monovinyl terminated PDMS macromonomer with a number average molecular weight of 34.3xl0 3 g/mole, 0.040 g of AIBN, and 2.0 g vinyl acetate are employed and the reaction is carried out for 18 hours. A coarse white powder is obtained in 92.1% yield.
  • the product is comprised of spherical particles which have an average diameter of about l ⁇ m, a number average molecular weight of 13.7xl0 3 g/mole, and a molecular weight distribution of 5.2.
  • the polymerization is carried out as in Example 1, with the exception that 0.100 g of a monovinyl terminated PDMS macromonomer with a number average molecular weight of 37.0xl0 3 g/mole, 0.040 g of AIBN, and 1.8 g vinyl acetate and 0.20 g ethylene are employed and the reaction is carried out for 18 hours.
  • the product a white solid, is obtained in 81.2% yield and has a number average molecular weight of 9.6xl0 3 g/mole and a molecular weight distribution of 3.3.
  • X H NMR spectroscopy indicates that the product is copolymer comprised of 26.2 mole percent ethylene and 73.8 mole percent vinyl acetate repeat units.
  • Fluoroalkyl methacrylate macromonomers are prepared in acetone through the polymerization of 1,1'- dihydroperfluorooctyl methacrylate in the presence of 4-lxlO "5 M CoBF 2 «H 2 0 using 2% by weight, based on FOMA, AIBN as the initiator. Reagents are mixed in air and subjected to 3 freeze-pump-thaw cycles before heating to 65°C for 8 hours. After the allotted reaction time, the mixture is poured slowly with stirring into a large excess of methanol to remove acetone, monomer, catalyst, and residual initiator. The methanol is decanted and the resulting product is re-dissolved in a , ot , a-trifluorotoluene, precipitated into methanol and dried overnight under vacuum at room temperature. ⁇ H
  • NMR indicates a methacryloyl terminated poly (FOMA) with a number average molecular weight of 4,900 g/mole.
  • the polymerization is carried out as in
  • Example 12 with the exception that 2.8xl0 "5 M CoBF 2 «H 2 0 is employed. X H NMR analysis of the resulting polymer indicates a methacryloyl terminated poly(FOMA) having a number average molecular weight of 6,400 g/mole.
  • Example 16
  • the polymerization is carried out as in Example 12, with the exception that 1.4xl0 "5 M CoBF 2 *H 2 0 is employed. 1 H NMR analysis of the resulting polymer indicates a methacryloyl terminated poly(FOMA) having a number average molecular weight of 11,000 g/mole.
  • the polymerization is carried out as in
  • Example 12 with the exception that 0.55xl0 "5 M CoBF 2 *H 2 0 is employed.
  • X H NMR analysis of the resulting polymer indicates a methacryloyl terminated poly(FOMA) having a number average molecular weight of 14,000 g/mole.
  • a 25-mL high pressure reactor is charged with 2.0 g of methyl methacrylate, 3.0 g of methacryloyl terminated poly(FOMA) and 50 mg AIBN.
  • the cell is purged with argon and sealed.
  • Carbon dioxide is added to fill approximately one half of the cell volume and the cell is heated to 60°C for three days.
  • a cloudy phase-separated mixtures is obtained.
  • the carbon dioxide is vented and 3.3 g of polymer is collected corresponding to a 66% yield.
  • X H NMR analysis confirms that methacryloyl terminated poly (FOMA) is incorporated into the resulting polymer product.

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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)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention porte sur un procédé de polymérisation d'un monomère consistant à: (a) constituer dans un milieu de polymérisation de CO2 un mélange réactif comprenant un monomère, un précurseur de stabilisateur et un initiateur de polymérisation; (b) à polymériser dans le milieu de polymérisation le monomère et le précurseur de stabilisateur de manière à y former un mélange réactif hétérogène incluant un polymère. Le précurseur de stabilisateur se trouvant lié par covalence au polymère y produit un tensioactif intrinsèque qui le stabilise dans le mélange réactif hétérogène.
EP96940237A 1995-10-17 1996-10-10 Polymerisation heterogene dans le co 2? Ceased EP0856011A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US54426495A 1995-10-17 1995-10-17
US544264 1995-10-17
PCT/US1996/016275 WO1997014720A2 (fr) 1995-10-17 1996-10-10 Polymerisation heterogene dans le co¿2?

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US6312484B1 (en) * 1998-12-22 2001-11-06 3M Innovative Properties Company Nonwoven abrasive articles and method of preparing same
US6238449B1 (en) 1998-12-22 2001-05-29 3M Innovative Properties Company Abrasive article having an abrasive coating containing a siloxane polymer
US6191215B1 (en) * 1999-03-05 2001-02-20 Basf Aktiengesellschaft Process for the preparation of pulverulent polymers by polymerization in supercritical carbon dioxide in the presence of polyoxyalkylene-polysiloxane copolymers
US6841616B2 (en) 2003-03-28 2005-01-11 Arkema Inc. Polymerization of halogen-containing monomers using siloxane surfactant
US6869997B2 (en) 2003-05-06 2005-03-22 Arkema, Inc. Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
KR101272841B1 (ko) * 2010-12-24 2013-07-04 한국생산기술연구원 이산화탄소 용매를 이용한 초발수 공중합체의 합성과 그 응용

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WO1997014720A3 (fr) 1997-05-15
CA2233950A1 (fr) 1997-04-24
JPH11513733A (ja) 1999-11-24
WO1997014720A2 (fr) 1997-04-24

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