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WO1996006118A1 - Polymerisation cationique en presence de dioxyde de carbone - Google Patents

Polymerisation cationique en presence de dioxyde de carbone Download PDF

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Publication number
WO1996006118A1
WO1996006118A1 PCT/US1995/010607 US9510607W WO9606118A1 WO 1996006118 A1 WO1996006118 A1 WO 1996006118A1 US 9510607 W US9510607 W US 9510607W WO 9606118 A1 WO9606118 A1 WO 9606118A1
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Prior art keywords
carbon dioxide
cationic polymerization
reaction mixture
monomers
monomer
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PCT/US1995/010607
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English (en)
Inventor
Joseph M. Desimone
Michael R. Clark
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The University Of North Carolina At Chapel Hill
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Filing date
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Application filed by The University Of North Carolina At Chapel Hill filed Critical The University Of North Carolina At Chapel Hill
Priority to EP95930232A priority Critical patent/EP0776341A1/fr
Priority to JP8508245A priority patent/JPH10504602A/ja
Priority to MX9701248A priority patent/MX9701248A/es
Priority to AU33691/95A priority patent/AU3369195A/en
Publication of WO1996006118A1 publication Critical patent/WO1996006118A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent

Definitions

  • the present invention relates to the polymerization of a monomers, and more specifically relates to the cationic polymerization of monomers in carbon dioxide.
  • cationic polymerization refers to a positively charged (cationic) polymer chain resulting from the reaction of an initiator with a monomer.
  • Proper selection of initiators for cationic polymerization is essential to the generation of polymers.
  • the proper selection of the cationic polymerization initiator in turn depends upon the monomer to be polymerized.
  • Kennedy et al . Polymer Bull etin 15:317 (1986) , reported the cationic polymerization of isobutylene using an initiating system including boron trichloride with tertiary esters in chloromethane, methylene chloride, chloroethane, and mixtures of chlorinated solvents in ⁇ -hexane.
  • the present invention provides a method of carrying out the cationic polymerization of a monomer in carbon dioxide.
  • the method includes the steps of (a) providing a reaction mixture comprising carbon dioxide, a monomer, a catalyst and a cationic polymerization initiator, wherein the cationic polymerization initiator is capable of initiating the cationic polymerization of the monomer; and (b) polymerizing the monomer in the reaction mixture to form a polymer.
  • Carbon dioxide as a polymerization solvent medium provides a number of significant advantages to polymerization systems.
  • cationic polymerization were conducted in a dry, inert solution dispersing medium; typically an organic solvent or a chlorinated organic solvent .
  • an environmentally sound solvent alternative for cationic polymerization namely, carbon dioxide.
  • the polymer can be easily isolated from the carbon dioxide solvent (i.e. the continuous phase) at the termination of polymerization, as the carbon dioxide can simply be vented from the reaction vessel .
  • the density and viscosity of carbon dioxide can be tuned over a large range of conditions due to its compressibility, particularly in the supercritical phase, and thus the particle size and morphology of the polymer may be controlled.
  • U.S. Patent No. 5,312,882 to DeSimone et al. discloses the use of supercritical carbon dioxide as a suitable solvent for heterogeneous polymerization of hydrophobic monomers.
  • PCT Patent Application No. PCT/US93/01626 discloses the use of supercritical carbon dioxide as a suitable solvent for the homogeneous polymerization of fluoromonomers as well .
  • Cationic polymerizations of the present invention may take place heterogeneously or homogeneously.
  • heterogeneous polymerization refers to a polymerization carried out through the use of media that create at least two separate phases (i.e., a continuous phase and a dispersed phase) .
  • homogeneous polymerization refers to a polymerization reaction carried out through the use of media which do not create more than one phase, and which are identified by being optically transparent.
  • Heterogenous polymerizations include suspension polymerizations in which an initiator is solubilized in the dispersed phase, emulsion polymerizations in which an initiator is solubilized in the continuous phase, and dispersion and precipitation polymerizations which are initially homogeneous polymerization reaction ' s but which nucleate particles precipitate out of solution to form a heterogeneous polymerization.
  • the present invention is directed to a method of carrying out the cationic polymerization of a variety of monomers in carbon dioxide.
  • the method comprises (a) providing a reaction mixture comprising carbon dioxide, one or more monomers, a catalyst and a cationic polymerization initiator, wherein the cationic polymerization initiator is capable of initiating the cationic polymerization of the monomer (s) , and (b) polymerizing the monomer (s) in the reaction mixture.
  • the carbon dioxide can be employed in a liquid, vapor, or supercritical phase.
  • “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 (1984) ; therein, it is stated that the critical temperature of carbon dioxide is about 31°C. If liquid carbon dioxide is employed, the temperature of the reaction will be below 31°C. Preferably, the carbon dioxide is in a liquid phase.
  • the reaction temperature should be chosen to provide sufficient heat energy to initiate and propagate the polymerization, without leading to unwanted side reactions.
  • the reaction temperature will be between -50°C and 200°C, and most preferably between -50°C and 31°C.
  • a wide variety of monomers may be employed in the method of the instant invention.
  • the method may be employed for the polymerization of a single monomer or the copolymerization or block polymerization of two or more monomers.
  • Monomers may be substituted or unsubstituted, saturated or unsaturated, linear or branched, cyclic or aromatic.
  • the selection of monomer or monomers to be employed will affect the choice of appropriate cationic polymerization initiators, as discussed below.
  • Suitable monomers may be selected from a wide variety of monomers which are known to those skilled in the art as capable of undergoing cationic polymerization.
  • Some exemplary monomers include vinyl ether monomers, cyclic ether monomers, oxazoline monomers, hydrocarbon olefin monomers, cyclic carbonate monomers, and formaldehyde.
  • diene comonomers may be employed in copolymerization systems.
  • Suitable vinyl ether monomers include alkyl vinyl ethers such as methyl vinyl ether and isobutyl vinyl ether.
  • Suitable cyclic ether monomers include alkyl, alkoxy, and halo substituted cyclic ethers having a general formula selected from the group consisting of
  • R ⁇ and R 2 are independently selected from the group consisting of H, alkyl and preferably C 1 -C 8 alkyl, alkoxy and preferably C 1 -C 9 alkoxy, haloalkylalkoxy of the formula (CH 2 0 (CH 2 )_C x F 2x+1 ) wherein m is 1-3 and x is 1-8, amine, amide, and alkylhaloamine of the formula (CH 2 ) Z NF 2 wherein z is 1-3, and n is a number from 1 to 5.
  • Suitable cyclic ether monomers for use in the instant invention include 3,3- (bisethoxymethyl)oxetane, 3- (1' , 1' - dihydroheptafluorobutoxymethyl ) - 3 -methyloxetane , tetrahydrofuran, trioxane, ethylene oxide.
  • Cyclic ethers have previously been cationically polymerized in nitromethane, methylene chloride, ethylene chloride, carbon tetrachloride, and halogenated aromatic hydrocarbons. See, U.S. Patent No. 4,393,199 to Manser, and E. Goethals, Makromol . Chem . , Macromol .
  • cyclic ether monomers can be prepared using conventional methods known to those skilled in the art, such as the methods described in U.S. Patent No. 5,210,153 to Manser et al. , and H. Mark, et al . , Encyclopedia of Polymer Science and Engineering, 2d ed. 10:654 (1985) , the disclosures of which are incorporated herein by reference in their entirety.
  • Suitable oxazoline monomers include alkyl, alkoxy, and halo substituted oxazolines having a general formula
  • R 3 and R 4 are independently selected from the group consisting of H, alkyl and preferably C 1 -C 8 alkyl, alkoxy and preferably C- t -C,, alkoxy, haloalkylalkoxy of the formula (CH 2 0(CH 2 )_C x F 2xtl ) wherein m is 1-3 and x is 1-8, amine, amide, and alkylhaloamine of the formula (CH 2 ) Z NF 2 wherein z is 1-3, and n is a number from 1 to 5.
  • Exemplary cyclic ether monomers for use in the instant invention include 2-ethyl oxazoline, 2-methyl oxazoline, 2- (1, 1, 2, 2-tetrahydroperfluorooctane) oxazoline.
  • Suitable hydrocarbon olefin monomers include substituted or unsubstituted styrene, such as p-methoxy styrene and alkylene monomers such as isobutylene and propene.
  • Suitable cyclic carbonate monomers include compounds having the formula
  • R 5 and R 6 are independently selected from the group consisting of H, alkyl and preferably C 1 -C 8 alkyl, alkoxy and preferably C 1 -C 9 alkoxy, and haloalkylalkoxy of the formula (CH 2 0(CH 2 ) m C x F 2x+1 ) wherein m is 1-3 and x is 1- 8.
  • Suitable diene comonomers include butadiene, and isoprene.
  • the cationic polymerization is typically catalyzed by the addition of one or more cationic polymerization catalysts.
  • the catalysts may be provided independently of the other reactants, or may be premixed or coupled with the initiator. Suitable catalysts will depend upon the particular polymerization system (i.e., monomer (s) and initiator) to be polymerization.
  • Suitable cationic polymerization catalysts for the polymerization of vinyl ether monomers include ethyl aluminum dichloride.
  • the ethyl aluminum dichloride catalyst and the initiator are provided in the reaction in the form of a catalyst/initiator couple.
  • the catalyst and initiator are premixed and coupled prior to reaction with the vinyl ether monomer.
  • Suitable cationic polymerization catalysts for the polymerization of cyclic ethers and oxazolines include boron trifluoride tetrahydrofuranoate.
  • Suitable cationic polymerization catalysts for the polymerization of hydrocarbon olefins include tin tetrachloride, titanium tetrachloride, boron trichloride, boron trifluoride.
  • Suitable cationic polymerization catalysts for the polymerization of cyclic carbonates and formaldehyde include boron trifluoride.
  • the polymerization is initiated by the addition of a cationic polymerization initiator.
  • a suitable cationic polymerization initiator will necessarily depend upon the monomer or monomers to be polymerized, and their compatibility with carbon dioxide.
  • the polymerization of vinyl ether monomers is typically initiated by the addition of a cationic polymerization initiator comprising an ester initiator and a Lewis base deactivator.
  • the ester initiator comprises an adduct of acetic acid and isobutyl vinyl ether.
  • Suitable Lewis base deactivators include ethyl acetate.
  • the polymerization of cyclic ether monomers is typically initiated by the addition of a cationic polymerization initiator comprising a strong acid, a Lewis acid, or a preinitiator.
  • a strong acid for use in as cationic polymerization initiators of cyclic ethers include triflic acid.
  • Suitable Lewis acid initiators include boron trifluoride.
  • Suitable preinitiators include water, alcohols, ethers and esters.
  • One preferred preinitiator is butanediol .
  • the polymerization of oxazoline monomers is typically initiated by the addition of a cationic polymerization initiator comprising a strong acid, a Lewis acid, or a preinitiator.
  • a strong acid e.g., a Lewis acid
  • preinitiators e.g., preinitiators
  • the polymerization of hydrocarbon olefin monomers is typically initiated by the addition of a cationic polymerization initiator selected from the group consisting of 1-chloro-l-phenyl ethane, 2-chloro-2, 4,4- trimethylpentane, tertiary ethers, Lewis bases, or 2- methoxy-2-propyl benzene.
  • a cationic polymerization initiator selected from the group consisting of 1-chloro-l-phenyl ethane, 2-chloro-2, 4,4- trimethylpentane, tertiary ethers, Lewis bases, or 2- methoxy-2-propyl benzene.
  • Lewis bases include dimethyl sulfoxide, acetamide, or ethyl acetate.
  • the initiator may also comprise a deactivator, such as tetrabutylammonium chloride or the like.
  • styrene is cationically polymerized using 1-chloro-l-phenyl ethane and tetrabutylammonium chloride as the initiator.
  • isobutylene is cationically polymerized using 2-chloro-2, 4 , 4- trimethylpentane as the initiator.
  • the polymerization of cyclic carbonate monomers is typically initiated by the addition of a cationic polymerization initiator comprising methyl triflate, methyl iodide, or benzyl bromide.
  • a cationic polymerization initiator comprising methyl triflate, methyl iodide, or benzyl bromide.
  • the use of these initiators in the cationic polymerization of cyclic carbonate monomers in methylene chloride was previously reported in T. Endo, et , al . , J. of Poly. Sci . . - Part A : Poly. Chem . , 31:581 (1993) the disclosure of which is incorporated herein by reference in its entirety.
  • the polymerization of formaldehyde is typically initiated by the addition of a cationic polymerization initiator comprising strong acids or Lewis acids and a preinitiator.
  • a strong acid is hydrochloric acid.
  • a suitable Lewis acid is boron trifluoride.
  • a suitable preinitiator is water. The use of this initiator system was previously reported in M. Stevens Polymer Chemistry, 2nd ed. , Oxford University Press, 355-
  • the reaction mixture may be homogeneous or heterogeneous depending upon the monomer or monomers to be polymerized.
  • the polymerization is a dispersion polymerization meaning that the reaction mixture may initially be homogeneous and becomes heterogeneous as the polymer nucleates a particle which is not soluble in the solvent.
  • the polymerization reaction mixture may include other additives and reactants known to those skilled in the art.
  • the process of the invention includes the addition of surfactant for stabilizing the monomer and polymer in the polymerization medium.
  • the surfactant should be one that is surface active in carbon dioxide and thus partitions itself at the carbon dioxide-monomer interface. Suitable surfactants are described in detail in U.S. Patent No. 5,312,882 to DeSimone et al . , the disclosure of which is incorporated herein by reference in its entirety. Such a surfactant should lower the interfacial tension between the carbon dioxide polymerization medium and the polymer, and thus create a dispersed phase.
  • the surfactant is generally present in the reaction mixture in a concentration of from about 0.001 up to about 30 percent by weight.
  • the surfactants can be nonreactive in the polymerization or can react with and thereby be included with the forming polymer. See, e . g . , U.S. Pat. Nos . 4,592,933 and 4,429,666 for exemplary reactive surfactants .
  • the surfactant should contain a segment that is soluble or interfacially active in carbon dioxide ("C0 2 - philic”) .
  • Exemplary C0 2 -philic segments include a fluorine-containing segment, such as can be found in fluoropolymers or copolymers of fluoropolymers, or a siloxane-containing segment, such as can be found in siloxane polymers or copolymers of siloxane polymers.
  • a fluoropolymer has its conventional meaning in the art.
  • Exemplary fluoropolymers are those formed from: fluoroacrylate monomers such as 2- (N- ethylperfluorooctanesulfonamido) ethyl acrylate ("Et-
  • MeFOSEA 2- (N-methylperfluorooctanesulfonamido) ethyl methacrylate
  • MeFOSEMA 2- (N-methylperfluorooctanesulfonamido) ethyl methacrylate
  • FOA 1, l-Dihydroperfluorooctyl acrylate
  • FOMA 1, 1-dihydroheptafluorobutoxy methyl oxetane
  • FOMA 1, l-Dihydroperfluorooctyl acrylate
  • fluoroolefin monomers such as tetrafluoroethylene
  • fluorostyrene monomers such as a- fluorostyrene, ⁇ - fluorostyrene, a , ⁇ -difluorostyrenes, ⁇ , j ⁇ -difluorostyrenes, a , ⁇ , j ⁇ -trifluorostyrenes, a-
  • C0 2 -phobic group along with a C0 2 -soluble group, such as a fluoropolymer.
  • the C0 2 -phobic group may be a hydrophobic group, such as a polystyrene group, or a hydrophillic group such as carboxylic acid.
  • Such copolymers can take many forms; exemplary forms are graft copolymers, random copolymers, and block copolymers.
  • the x and y values are chosen to adjust the balance between "C0 2 -philic" and "C0 2 -phobic" to tailor the surface activity of the reagents .
  • silicone-containing surfactants i.e., siloxane polymers or copolymers
  • 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.
  • the polymerization reaction is carried out in a suitable high pressure reaction vessel of about 24 mL and capable of withstanding pressures on the order of up to about 8000 psi.
  • the reaction vessel typically includes a cooling system. Additional features of the reaction vessel used in accordance with the invention include heating means such as an electric heating furnace to heat the reaction mixture and mixing means, i.e., stirrers such as paddle stirrers, impeller stirrers, or multistage impulse countercurrent agitators, blades, and the like.
  • the reaction begins by cooling the reaction vessel to a temperature below about 31°C.
  • the initiator, monomer or monomers, and carbon dioxide are added to the vessel. Typically the mixture is allowed to polymerize for between about 2 and 24 hours, and preferably is stirred as the reaction proceeds. At the conclusion of the reaction, the polymer can be collected by methods such as venting of the carbon dioxide or by fractionation. After separation, the polymer can be collected by conventional means. In addition, the polymers of the present invention may be retained in the carbon dioxide, and sprayed onto a surface. After the carbon dioxide and solvent evaporate, 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.
  • M means molar concentration
  • NMR nuclear magnetic resonance
  • MHz means megahertz
  • GPC gas phase chromatography
  • A means angstroms
  • UV means ultraviolet
  • G means grams
  • mol means moles
  • M means milliliters
  • C means degrees Centigrade
  • S means seconds
  • h means hours
  • psig means pounds per square inch (gauge)
  • M means number average molecular weight
  • M D means molecular weight distribution
  • f means functionality
  • ppm means parts per million
  • T g means glass transition temperature
  • nm means nanometers
  • mg means milligrams
  • rpm means revolutions per minute
  • mm Hg means millimeters of mercury
  • psi means pounds per square inch.
  • Monomers of isobutyl vinyl ether, styrene, and 3, 3 ' -bisethoxymethyl oxetane were provided by Dr. Gerald Manser of Aerojet Corporation.
  • Bisethoxymethyl oxetane (BEMO) was vacuum distilled at 5 X 10 "2 mm Hg, with the fraction distilling at 54°C to 57°C being collected.
  • Styrene was vacuum distilled from calcium hydride at 5 x 10 ⁇ 2 mm Hg and 50°C.
  • Isobutyl vinyl ether was distilled twice from calcium hydride under an argon atmosphere at about atmospheric pressure and a temperature of 82°C.
  • Lewis acid catalysts ethyl aluminum dichloride (1.0 M in hexanes, obtained from Aldrich) and tin tetrachloride (obtained from Aldrich) were used without further purification.
  • Lewis acid catalyst boron trifluoride tetrahydrofuranoate (BF 3 -THF) was prepared by stirring boron trifluoride diethyletherate (obtained from Aldrich) with prechilled tetrahydrofuran (obtained from Mallinckrodt) for two hours at 25°C.
  • BFC 3 -THF was purified by distillation at 100° under argon to remove volatiles, followed by vacuum distillation with the fraction distilling at 70°C being isolated.
  • the acetic acid/isobutyl vinyl ether adduct was prepared as described by T. Hagashimura et al . Macromolecules 22(3) : 1009 (1989) .
  • Isobutyl vinyl ether (IBVE) was treated with acetic acid for three hours at 60°C and atmospheric pressure, then the adduct was distilled twice under vacuum at 5 x 10 ⁇ 2 mm Hg with the middle fraction, which is distilled over at about 60°C, being collected both times to prepare the ester initiator.
  • Initiators 1 , 4 -butanedio1 , 2, 2, 2- trifluoroethanol, and 1-phenyl-l-chloroethane (obtained from Aldrich) were used without further purification.
  • the deactivator, ethyl acetate was obtained from Aldrich and was distilled twice from calcium hydride under an argon atmosphere.
  • Cyclohexane was obtained from Phillips Petroleum and was stirred over concentrated sulfuric acid for two weeks, decanted, and distilled from sodium metal under an argon atmosphere.
  • Methylene chloride was obtained from Mallinckrodt, and, was distilled twice from calcium hydride under an argon atmosphere .
  • Carbon dioxide was obtained from Matheson, 99.99% was passed through copper oxide catalyst column to remove trace amounts of oxygen and then through a 3A molecular sieve column to remove trace amounts of moisture.
  • the high pressure reactor was constructed from Hastelloy C-22, having a volume of 24 mL and a pressure capacity of up to about 8000 psi and was obtained from Haynes International .
  • the temperature of the flask is maintained near 40°C using a water bath, and stirring is achieved using a stir plate.
  • Ethyl acetate (3 mL) and EtAlCl 2 (0.46 mL, 0.46 mmol) are added to the high pressure cell via syringe under an argon atmosphere.
  • the cell is equipped with a teflon coated stir bar and heated to 40°C.
  • Carbon dioxide is added to the cell using a high pressure syringe to achieve a cell pressure of 4500 psi.
  • IBVE (3 mL, 2.304 g) is added to the cell using a high pressure syringe.
  • the reaction continued for fourteen (14) hours and was accompanied by a pressure drop, to a final pressure of 3683 psi. During the course of the reaction, polymer could be seen forming and precipitating from the carbon dioxide fluid.
  • the temperature of the flask is maintained near 40°C using a water bath and stirring is achieved with a stir plate.
  • Ethyl aluminum dichloride (EtAlCl 2 ) (0.40 mL, 0.40 mmol) is added via syringe to catalyze the polymerization.
  • IBVE Isobutyl vinyl ether
  • IBVE Isobutyl vinyl ether
  • EtAlC12 (0.2 mL, 0.2 mmol) , and the ester initiator (0.04 mL, 0.23 mmol) are combined in the cell.
  • carbon dioxide and IBVE (3 mL, 2.304 g) are added to the cell to a pressure of 5000 psi.
  • the reaction proceeds for twelve hours at 40°C, during which time the pressure drops to 3300 psi.
  • the catalyst boron trifluoride tetrahydrofuranoate (0.06 mL, 0.58 mmol) is added via syringe to catalyze the polymerization, with trace amounts of water being added as the initiator.
  • the reaction proceeds for four hours at which time a solution of aqueous sodium hydroxide is added to the flask to terminate the reaction.
  • the resulting polymer is precipitated into methanol, filtered, and dried in vacuum overnight .
  • Table 2 summarizes the results obtained in methylene chloride.
  • Hastelloy C-22 dish to allow both monomer and catalysts to be added to the cell before the carbon dioxide and not premix.
  • BEMO 4.8 mL, 4.8 g
  • BF 3 -THF 0.28 mL, 0.69 mmol
  • the cell is equipped with a stir bar and the temperature is maintained near -10°C using a sodium chloride/ice bath.
  • Carbon dioxide is added to the cell using an ISCOTM high pressure syringe pump to a pressure of 4300 psi. The reaction proceeds for four hours, during which time the pressure drops to 3500 psi.
  • Carbon dioxide is added to a pressure of 4800 psi.
  • BDO/BF 3 -THF solution (0.22 mL, 0.69 mmol) is injected into the dish within the cell. Carbon dioxide is added to a pressure of 4200 psi. Poly(BEMO) (0.840 g) is recovered.
  • Polymers of styrene are prepared in methylene chloride using a method outlined by T. Higashimura et al . , Macromolecules 26:744 (1993) .
  • Styrene (4.0 mL, 3.64 g) , the initiator, 1-chloro-l-phenyl ethane (0.5 mL, 0.70 mmol) , the deactivator, tetrabutyl ammonium chloride (2.4 mL, 1.40 mmol) , and methylene chloride (20 mL) are added to the flask via syringe.
  • the temperature of the flask is maintained near -10°C using an ice bath and stirring is achieved with a stir plate.
  • the catalyst, tin tetrachloride (0.7 mL, 3.49 mmol) is added to the cell via syringe.
  • the reaction proceeds for 3 hours at -10°C, at which time the reaction is terminated by the addition of a solution of sodium methoxide and methanol.
  • the high pressure cell is equipped with a Hastelloy C-22 dish to allow both monomer and catalysts to be added to the cell before the carbon dioxide without premixing.
  • Styrene 5.0 mL, 4.55 g
  • 1-chloro-l-phenyl ethane 0.1 mL, 0.87 mmol
  • tetrabutylammonium chloride 1.9 mL, 1.7 mmol
  • Tin tetrachloride 0.9 mL, 4.41 mmol
  • the cell is equipped with a stir bar and temperature is maintained near 0°C using a NESLABTM circulating bath equipped with a refrigeration unit and a solution of water and ethylene glycol as the coolant.
  • Carbon dioxide is added to the cell using an ISCOTM high pressure syringe pump to a pressure of 4500 psi.
  • polymer can be seen forming and precipitating out of solution in the reactor.
  • the polymerization proceeds for 3 hours near 0°C, during which time the pressure drops to approximately 4000 psi.
  • the carbon dioxide is then slowly vented off and the reaction is terminated by the addition of a solution of sodium methoxide and methanol.
  • the polymer is dissolved in tetrahydrofuran, precipitated into methanol, filtered, and dried under vacuum overnight.
  • Isobutylene is polymerized with an initiator system including 2-chloro-2 , 4 , 4-trimethylpentane (TMPC1) /titanium tetrachloride (TiCl4) /Lewis bases, where the Lewis base include dimethyl sulfoxide, acetamide, or ethyl acetate, in liquid and supercritical carbon dioxide using the procedure of Example 23 above.
  • TMPC1 4-trimethylpentane
  • TiCl4 titanium tetrachloride
  • Lewis base include dimethyl sulfoxide, acetamide, or ethyl acetate
  • Styrene is copolymerized with isobutylene using 2-methoxy-2-propyl benzene and titanium tetrachloride in the presence of di-t-butyl pyridine using the method described in Example 23 above with one change.
  • the second monomer (styrene) is added to the cell using a high pressure syringe once the isobutylene has been consumed in the reaction. It is known that these two monomers can form copolymers cationically in the mixed solvent system methyl chloride/methyl cyclohexane. See, J. Kennedy, et al . Makromol . Chem . , Macromol . Symp . 51:1269 (1991) .
  • Isobutylene is cationically block copolymerized with methyl vinyl ether using the TMPCl/TiCl4 initiating system described in Example 25 in the presence of tetrabutylammonium chloride in liquid and supercritical carbon dioxide using the procedure described in Example 26, where methyl vinyl ether is the second monomer. It is known that these monomers can form block copolymers cationically in mixed solvent systems such as methyl chloride/n-hexane or methylene chloride/n-hexane. See, J. Kennedy, et al . , Macromolecul es 25:1642 (1992) .
  • Isobutylene is cationically block copolymerized with isoprene using cumyl acetate or boron trichloride in liquid and supercritical carbon dioxide using the procedure described in Example 26.
  • Isoprene is the second monomer. It is known that these monomers can form block copolymers cationically in methyl chloride. See, J. Kennedy, et al . Macromolecules 25:1771 (1992) .
  • Cyclic carbonates are polymerized cationically using methyl triflate, methyl iodide, or benzyl bromide in liquid or supercritical carbon dioxide according to the method described in Example 17 above.
  • Oxetanes are polymerized cationically using strong acids or Lewis acids and preinitiators such as alcohols, ethers, and esters in liquid and supercritical carbon dioxide as described in Example 17 above.
  • Oxetanes are copolymerized cationically with cyclic carbonates using methyl triflate or boron trifluoride diethyl etherate in liquid and supercritical carbon dioxide as described in Example 17 above, with one exception.
  • the oxetane and the cyclic carbonate are added simultaneously to the cell.
  • the initial cell temperature is held at 0°C until the oxetane monomer is consumed.
  • the temperature is then raised to 30°C while the cyclic carbonate monomer is consumed. It has been previously known that these monomers could be copolymerized in methylene chloride and deuterated chloroform. See, T. Endo, et al . , Macromolecules 26:7106 (1993) .
  • EXAMPLE 32 Cationic Copolymerization ofOtherCyclic Monomers
  • Cyclic monomers such as oxiranes, tetrahydrofuran, trioxane, and oxazolines are polymerized cationically using: (1) triflic acid or (2) Lewis acids and some proton source such as water or alcohols, in liquid and supercritical carbon dioxide as described in Example 17 above. It has been known that these monomers could be cationically polymerized in solvents such as nitromethane, methylene chloride, and carbon tetrachloride. See, E. Goethals, Makromol . Chem. , Macromol . Symp . 42/43:51 (1991) .
  • the high pressure cell is equipped with a hastelloy C-22 dish to allow both monomer and catalyst to be added to the cell before the carbon dioxide while avoiding premix.
  • Poly(1,1 dihydroheptafluorobutoxy methyl oxetane) (p(F0X7)) (0.9902 g) is added to the cell.
  • BEMO 4.8 mL, 4.8 g is added to the body of the cell via syringe under an argon atmosphere.
  • Boron trifluoride tetrahydrofuranate (BF 3 -THF) (0.28 mL, 0.69 mmol) is added to the hastelloy dish via syringe under an argon atmosphere.
  • the cell is equipped with a mechanical stirrer to allow the contents to be agitated during the reaction and temperature is maintained near 5°C using a circulating cold bath and a cooling coil around the cell.
  • Carbon dioxide is added to the cell ' using an ISCO high pressure syringe pump, to achieve a pressure of 4267 psi.
  • the reaction proceeds for six hours during which time the solution changes from clear to an opaque, "milky" dispersion.
  • the reaction is terminated by venting the dispersion into deoxygenated, deionized water and injecting 2 mL of water into the cell.
  • Example 34 Dioxide in the Presence of Surfactant Reaction is set up as described in Example 34, except poly(1, 1-dihydroperfluorooctyl acrylate) (p(FOA)) is used as the surfactant instead of poly(F0X7) .
  • Carbon dioxide is added to a pressure of 4200 psi. Stirring is halted after 4 hours, 25 minutes has elapsed. The "milky" dispersion described in Example 34 did not precipitate after termination of stirring.
  • Reaction is terminated after a total reaction time of 4 hours, 35 minutes by venting into deoxygenated methanol and addition of 4 mL of deoxygenated methanol to the depressurized cell.
  • Presence of Surfactant p(FOA) (0.8403 g) is added to the high pressure reactor.
  • Tin tetrachloride (0.05 mL, .43 mmoles) is added to the cell via syringe under an argon atmosphere.
  • Carbon dioxide is added as described in Example 34 to a pressure of 1285 psi.
  • Cell temperature was 1.2°C.
  • Isobutylene (3.4 g, 0.06 moles) is added slowly using a high pressure syringe pump to a final cell pressure of 4150 psi. The reaction began clear, but became increasingly cloudy as the reaction proceeds.
  • GPC indicated a product of bimodal molecular weight, with peak molecular weights of 1.8 x 10 3 g/mol and 3.9 x 10 3 g/mol.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un procédé de polymérisation cationique d'un monomère en présence de dioxyde de carbone. Le procédé consiste: a) à réaliser un mélange de réaction comprenant du dioxyde de carbone, un monomère, un catalyseur et un amorceur de polymérisation cationique capable d'amorcer la polymérisation cationique, et b) à polymériser le monomère dans le mélange de réaction pour constituer un polymère.
PCT/US1995/010607 1994-08-18 1995-08-18 Polymerisation cationique en presence de dioxyde de carbone WO1996006118A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95930232A EP0776341A1 (fr) 1994-08-18 1995-08-18 Polymerisation cationique en presence de dioxyde de carbone
JP8508245A JPH10504602A (ja) 1994-08-18 1995-08-18 二酸化炭素中のカチオン重合
MX9701248A MX9701248A (es) 1994-08-18 1995-08-18 Polimerizacion cationica en dioxido de carbono.
AU33691/95A AU3369195A (en) 1994-08-18 1995-08-18 Cationic polymerization in carbon dioxide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US29242494A 1994-08-18 1994-08-18
US45117695A 1995-05-26 1995-05-26
US451,176 1995-05-26
US292,424 1995-05-26

Publications (1)

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WO1996006118A1 true WO1996006118A1 (fr) 1996-02-29

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WO (1) WO1996006118A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034667A1 (fr) * 1999-11-12 2001-05-17 North Carolina State University Procede continu de fabrication de polymeres dans du dioxyde de carbone
WO2002034794A1 (fr) * 2000-10-24 2002-05-02 Willow Holdings Inc. Ameliorations apportees a des procedes de polymerisation
US6806332B2 (en) 1999-11-12 2004-10-19 North Carolina State University Continuous method and apparatus for separating polymer from a high pressure carbon dioxide fluid stream
US6914105B1 (en) 1999-11-12 2005-07-05 North Carolina State University Continuous process for making polymers in carbon dioxide
EP1339755A4 (fr) * 2000-10-09 2006-03-22 Univ North Carolina Procedes de preparation de polymeres a fonctionnalite reactive dans du dioxyde de carbone
CN103732649A (zh) * 2011-08-12 2014-04-16 株式会社理光 聚合物产物、聚合物成型体、用于医疗用途的聚合物成型体、调色剂和聚合物组合物
WO2014095861A3 (fr) * 2012-12-21 2014-09-12 Bayer Materialscience Ag Procédé de production de copolymères formaldéhyde/co2
CN104769036A (zh) * 2012-09-14 2015-07-08 株式会社理光 聚合物组合物
CN105189602A (zh) * 2013-01-28 2015-12-23 株式会社理光 聚合物产物和其制造方法、以及聚合物产物制造设备
US9469723B2 (en) 2012-10-10 2016-10-18 Ricoh Company, Ltd. Particle manufacturing method, particles, and particle manufacturing apparatus
US9534090B2 (en) 2012-12-21 2017-01-03 Covestro Deutschland Ag NCO-modified polyoxymethylene block copolymers
US9546316B2 (en) 2012-11-12 2017-01-17 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
EP3149068A4 (fr) * 2013-11-21 2017-06-21 Ricoh Company, Ltd. Procédé de production de polymère
US9688814B2 (en) 2012-12-21 2017-06-27 Covestro Deutschland Ag Functionalized polyoxymethylene block copolymers
CN115322357A (zh) * 2022-09-02 2022-11-11 浙江皇马科技股份有限公司 一种利用超临界二氧化碳制备四氢呋喃均聚醚的方法

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JP2006233146A (ja) * 2005-02-28 2006-09-07 Sanyo Chem Ind Ltd アルキレンオキシド重合体の製造方法
JP5644405B2 (ja) * 2010-11-18 2014-12-24 株式会社リコー トナー
US8642719B2 (en) * 2011-02-28 2014-02-04 Corning Incorporated Solvent mixture for molecular weight control
JP6060803B2 (ja) * 2013-04-30 2017-01-18 株式会社リコー ポリマー生成物、フイルム、成型品、シート、粒子、繊維、及びポリマーの製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1172713A (en) * 1966-05-19 1969-12-03 Sumitomo Chemical Co A Novel Method for Polymerizing a Vinyl Compound.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1172713A (en) * 1966-05-19 1969-12-03 Sumitomo Chemical Co A Novel Method for Polymerizing a Vinyl Compound.

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034667A1 (fr) * 1999-11-12 2001-05-17 North Carolina State University Procede continu de fabrication de polymeres dans du dioxyde de carbone
US6806332B2 (en) 1999-11-12 2004-10-19 North Carolina State University Continuous method and apparatus for separating polymer from a high pressure carbon dioxide fluid stream
US6914105B1 (en) 1999-11-12 2005-07-05 North Carolina State University Continuous process for making polymers in carbon dioxide
US7410620B2 (en) 1999-11-12 2008-08-12 North Carolina State University Apparatus for continuous production of polymers in carbon dioxide
EP1339755A4 (fr) * 2000-10-09 2006-03-22 Univ North Carolina Procedes de preparation de polymeres a fonctionnalite reactive dans du dioxyde de carbone
WO2002034794A1 (fr) * 2000-10-24 2002-05-02 Willow Holdings Inc. Ameliorations apportees a des procedes de polymerisation
EP2742081A4 (fr) * 2011-08-12 2015-03-18 Ricoh Co Ltd Produit polymère, corps compact en polymère, corps compact en polymère à usage médical, cartouche d'encre, et composition polymère
CN103732649A (zh) * 2011-08-12 2014-04-16 株式会社理光 聚合物产物、聚合物成型体、用于医疗用途的聚合物成型体、调色剂和聚合物组合物
CN104769036A (zh) * 2012-09-14 2015-07-08 株式会社理光 聚合物组合物
US9469723B2 (en) 2012-10-10 2016-10-18 Ricoh Company, Ltd. Particle manufacturing method, particles, and particle manufacturing apparatus
US10400158B2 (en) 2012-11-12 2019-09-03 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US9546316B2 (en) 2012-11-12 2017-01-17 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US11060014B2 (en) 2012-11-12 2021-07-13 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US10047276B2 (en) 2012-11-12 2018-08-14 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
WO2014095861A3 (fr) * 2012-12-21 2014-09-12 Bayer Materialscience Ag Procédé de production de copolymères formaldéhyde/co2
US9469715B2 (en) 2012-12-21 2016-10-18 Covestro Deutschland Ag Method for producing formaldehyde/CO2 copolymers
US9534090B2 (en) 2012-12-21 2017-01-03 Covestro Deutschland Ag NCO-modified polyoxymethylene block copolymers
US9688814B2 (en) 2012-12-21 2017-06-27 Covestro Deutschland Ag Functionalized polyoxymethylene block copolymers
CN105189602A (zh) * 2013-01-28 2015-12-23 株式会社理光 聚合物产物和其制造方法、以及聚合物产物制造设备
EP3149068A4 (fr) * 2013-11-21 2017-06-21 Ricoh Company, Ltd. Procédé de production de polymère
CN115322357A (zh) * 2022-09-02 2022-11-11 浙江皇马科技股份有限公司 一种利用超临界二氧化碳制备四氢呋喃均聚醚的方法

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CA2197303A1 (fr) 1996-02-29
MX9701248A (es) 1997-05-31
JPH10504602A (ja) 1998-05-06
EP0776341A1 (fr) 1997-06-04
AU3369195A (en) 1996-03-14

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