Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
  • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
• • 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
  • C08F14/18—Monomers containing fluorine
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
  • C08G18/3861—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur containing sulfonamide and/or sulfonylhydrazide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
  • C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6826—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
  • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to the preparation of organic compounds in a fluorinated ether as reaction medium.
• Organic reactions for the preparation of organic compounds are in many instances carried out in a reaction medium which is often in liquid form under the reaction conditions.
• the reaction medium often acts as a solvent for one or more of the reactants that are involved in the preparation of a desired organic compound.
• Many different organic reactions are known and they include reactions such as polymerization, including free radical polymerization, polycondensation, additions, substitutions, reduction and oxidation. It is well recognized that the reaction medium plays an important role in the preparation of an organic compound and in particular may have an influence on the yield of the organic product.
• Many different reaction media have heretofore been proposed and used for the preparation of various organic compounds. Such reaction media include both "hydrocarbon" type media which are substantially free of fluorine as well as certain fluorinated reaction media.
• the disclosed hydrofluorocarbon solvents are saturated and: optionally, contain one carbon-carbon double bond; contain carbon, fluorine, at least one hydrogen atom bound to a carbon atom, and optionally one or more ether oxygen atoms or one or more alcohols or one or more ether oxygen atoms and one or more alcohols; contain at least as many fluorine atoms as hydrogen atoms; optionally, contain one or more ⁇ CF 2 OCH 3 group(s); contain no more than two adjacent ⁇ CH 2 —groups; and have no hydrogen atoms on any primary carbon.
• Other solvents described for use in the polymerization of various fluoromonomers are compounds containing (besides carbon): chlorine, fluorine and hydrogen (see for example U.S. Patent Nos.
• U.S. Patent. No. 3,616,371 discloses the use of various fluorinated solvents for use in the polymerizations to form homo- or copolymers of vinylidene fluoride.
• U.S. Patent. No. 4,123,602 discloses the use of various fluorocarbon type solvents.
• Perfluorocarbons have also been proposed as solvents for these polymerizations. Many of the fluorinated solvents proposed so far for the polymerization of fluoromonomers have a fairly low solubility for many organic compounds including fluorine-free comonomers. Moreover, the chlorofluorocarbons (CFCs) have been linked to ozone depletion while the perfluorocarbons contribute to the green house effect.
• CFCs chlorofluorocarbons
• the compositions are alleged to be useful for a variety of applications including the use as polymerization medium.
• the exemplified hydrofluoroethers there is mentioned trifluoromethyl methyl ether which has a boiling point of -24.2°C. Summary of the Invention
• the present invention provides a method for preparing a desired organic compound by reacting one or more reactants in a reaction medium, said reaction medium comprising a fluorinated ether compound comprising at least 3 carbon atoms and a perfluorinated moiety that is linked through ether oxygen atoms to one or more hydrocarbon moieties.
• the term "desired organic compound” means an organic compound that is purposely prepared for an envisaged application or as an intermediate in the preparation of another organic compound.
• the organic compound can be a simple organic compound which may be polymerizable or not, a polymeric compound or an oligomeric compound.
• ether compound includes compounds containing one or more ether oxygen atoms.
• fluorinated ethers are useful as reaction medium in a variety of reactions for preparing an organic compound.
• the fluorinated ethers employed in the invention have good solvency power and can be used to dissolve many different organic reactants.
• the desired solvency of the fluorinated ether can be tailored by appropriate selection of the perfluorinated moiety and hydrocarbon moiety making it possible to select a fluorinated ether that is a better solvent for the reactants than for the desired organic compound. This allows the desired organic product to be readily separated from the reaction medium which is particularly advantageous where the desired organic product is a polymer.
• the fluorinated ethers employed in the invention are highly inert solvents.
• the fluorinated ethers can also be selected to have low or no flammability under the reaction conditions employed. As taught in GB 2274462, hydrofluorocarbons, perfluorocarbons and fluorinated alkyl ethers are generally non-flammable if the number of C-F bonds exceeds the sum of the number of C-H and C-C bonds. However for safety considerations, the flammability and flash points of such compounds should be experimentally determined.
• the fluorinated ethers employed in the invention are also much less toxic than many organic solvents used as reaction media, are available in a wide variety of boiling points and are liquids over a wide temperature range at atmospheric pressure.
• 1-methoxynonafluorobutane has a freezing point of -135°C and a boiling point of 60°C thus providing a liquid working range of 195°C with very little change in viscosity.
• the fluorinated ethers also have a low water solubility (typically less than 10 ppm) making them especially suitable in reactions that are sensitive to water.
• the fluorinated ethers have a vapor considerably denser than air and they can therefore be used to create a gaseous reaction environment free of oxygen and other ambient unwanted gasses.
• the fluorinated ethers comprise a perfluoroaliphatic moiety linked to one or more alkyl moieties through ether oxygen atoms.
• the perfluoroaliphatic moiety may contain one or more catenary heteroatoms such as oxygen, nitrogen or sulfur, although oxygen and nitrogen are preferred if present. More preferably, the perfluoroaliphatic moiety comprises two to ten carbon atoms and may optionally contain either oxygen and/or nitrogen catenary heteroatoms, and the alkyl moieties comprise one to four carbon atoms.
• Particularly preferred fluorinated ethers correspond to the following formula: wherein: x is 1 or 2; Rj, represents an alkyl group having 1 to 4 carbon atoms;
• R f represents a perfluorinated aliphatic group comprising at least two carbon atoms, preferably between 2 and 9 carbon atoms, and optional catenary heteroatoms such as oxygen, nitrogen and sulfur atoms.
• R f preferably is selected from the group consisting of linear or branched perfluoroalkyl groups, perfluorocycloalkyl groups containing a perfluoroalkyl group, perfluorocycloalkyl groups, linear or branched perfluoroalkyl groups having one or more catenary heteroatoms, perfluorocycloalkyl groups containing a perfluoroalkyl group having one or more catenary heteroatoms and perfluorocycloalkyl groups having one or more catenary heteroatoms.
• catenary heteroatoms include oxygen or nitrogen atoms.
• R f is preferably selected from the group consisting of linear or branched perfluoroalkylene groups, perfluorocycloalkyl groups containing a perfluoroalkylene group, perfluorocycloalkylene groups, linear or branched perfluoroalkylene groups having one or more catenary heteroatoms, perfluorocycloalkyl groups containing a perfluoroalkylene group having one or more catenary heteroatoms and perfluorocycloalkylene groups having one or more catenary heteroatoms.
• Particularly preferred heteroatoms include oxygen and nitrogen atoms.
• R f is selected from the group consisting of linear or branched perfluoroalkyl groups having from 3 to about 9 carbon atoms, perfluorocycloalkyl-containing perfluoroalkyl groups having from 5 to about 7 carbon atoms, and perfluorocycloalkyl groups having from 5 to about 6 carbon atoms;
• R h is a methyl or ethyl group;
• Rf can contain one or more catenary heteroatoms; and the sum of the number of carbon atoms in Rf and the number of carbon atoms in Rh is greater than or equal to 4.
• fluorinated ethers suitable for use in the processes and composition of the invention include the following compounds: n-C 4 F 9 OCH 3 , n-C4F 9 OCH 2 CH 3 , CF 3 CF(CF 3 )CF 2 OCH 3 , CF 3 CF(CF 3 )CF 2 OC 2 H 5 , C 8 F 17 OCH 3 , CH 3 O-(CF 2 ) 4 -OCH 3 , C 5 F n OC 2 H 5 , C 3 F 7 OCH 3 , CF 3 OC 2 F 4 OC 2 H 5 ,
• the fluorinated ethers suitable for use in the process of the invention can be prepared by alkylation of perfluorinated alkoxides prepared by the reaction of the corresponding perfluorinated acyl fluoride or perfluorinated ketone with an anhydrous alkali metal fluoride (e.g., potassium fluoride or cesium fluoride) or anhydrous silver fluoride in an anhydrous polar, aprotic solvent.
• anhydrous alkali metal fluoride e.g., potassium fluoride or cesium fluoride
• anhydrous silver fluoride in an anhydrous polar, aprotic solvent.
• a fluorinated tertiary alcohol can be allowed to react with a base, e.g., potassium hydroxide or sodium hydride, to produce a perfluorinated tertiary alkoxide which can then be alkylated by reaction with alkylating agent.
• a base e.g., potassium hydroxide or sodium hydride
• Suitable alkylating agents for use in the preparation include dialkyl sulfates
• alkyl halides e.g., methyl iodide
• alkyl p-toluenesulfonates e.g., methyl p-toluenesulfonate
• alkyl perfluoroalkanesulfonates e.g., methyl perfluoromethanesulfonate
• Suitable polar, aprotic solvents include acyclic ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, diethyl carbonate, propylene carbonate, and ethylene carbonate; alkyl nitriles such as acetonitrile; alkyl amides such as N,N-dimethylformamide, N,N-diethylformamide, and N-methylpyrrolidone; alkyl sulfoxides such as dimethyl sulfoxide; alkyl sulfones such as dimethyl sulfone, tetramethylene sulfone, and other sulfolanes; oxazolidones such as N-methyl-2-oxazolidone; and mixtures thereof.
• acyclic ethers such as diethyl ether, ethylene glyco
• Perfluorinated acyl fluorides for use in preparing the fluorinated ethers can be prepared by electrochemical fluorination (ECF) of the corresponding hydrocarbon carboxylic acid (or a derivative thereof), using either anhydrous hydrogen fluoride (Simons ECF) or KF.2HF (Philips ECF) as the electrolyte.
• ECF electrochemical fluorination
• Perfluorinated acyl fluorides and perfluorinated ketones can also be prepared by dissociation of perfluorinated carboxylic acid esters (which can be prepared from the corresponding hydrocarbon or partially-fluorinated carboxylic acid esters by direct fluorination with fluorine gas).
• Dissociation can be achieved by contacting the perfluorinated ester with a source of fluoride ion under reacting conditions (see the method described in U.S. Patent No. 3,900,372 (Childs)) or by combining the ester with at least one initiating reagent selected from the group consisting of gaseous, non-hydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.
• a source of fluoride ion under reacting conditions
• at least one initiating reagent selected from the group consisting of gaseous, non-hydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.
• Initiating reagents which can be employed in the dissociation are those gaseous or liquid, non-hydroxylic nucleophiles and mixtures of gaseous, liquid, or solid, non-hydroxylic nucleophile(s) and solvent (hereinafter termed "solvent mixtures") which are capable of nucleophilic reaction with perfluorinated esters.
• solvent mixtures gaseous or liquid, non-hydroxylic nucleophiles
• Suitable gaseous or liquid, non-hydroxylic nucleophiles include dialkylamines, trialkylamines, carboxamides, alkyl sulfoxides, amine oxides, oxazolidones, pyridines, and the like, and mixtures thereof.
• Suitable non-hydroxylic nucleophiles for use in solvent mixtures include such gaseous or liquid, non-hydroxylic nucleophiles, as well as solid, non-hydroxylic nucleophiles, e.g., fluoride, cyanide, cyanate, iodide, chloride, bromide, acetate, mercaptide, alkoxide, thiocyanate, azide, trimethylsilyl difluoride, bisulfite, and bifluoride anions, which can be utilized in the form of alkali metal, ammonium, alkyl-substituted ammonium (mono-, di-, tri- , or tetra-substituted), or quaternary phosphonium salts, and mixtures thereof.
• Such salts are in general commercially available but, if desired, can be prepared by known methods, e.g., those described by M. C. Sneed and R. C. Brasted in Comprehensive Inorganic Chemistry, Volume Six (The Alkali Metals), pages 61-64, D. Van Nostrand Company, Inc., New York (1957), and by H. Kobler et al. in Justus Liebigs Ann. Chem. 1978, 1937. l,4-diazabicyclo[2.2.2]octane and the like are also suitable solid nucleophiles.
• the reaction medium used in the preparation method of the present invention comprises the fluorinated ether optionally in combination with additional compounds.
• the reaction medium is comprised of those compounds that are substantially inert and do not substantially participate in the reaction to prepare the organic compound. It is further preferred that the reaction medium is non-flammable.
• Compounds that actively participate in an organic reaction include for example the reactants, a catalyst, scavengers, precipitation aids, initiators, chain terminators and chain transfer agents.
• Suitable additional compounds for use together with the fluorinated ether as reaction medium are co-solvents that can increase the solvability of one or more of the reactants.
• co-solvents can be hydrocarbon solvents such as ketones, esters, alcohols and ethers.
• hydrocarbon co-solvent may vary widely but it is preferred to use hydrocarbon co-solvent in an amount such that the reaction medium is non-flammable.
• Particularly suitable co-solvents for use with the fluorinated ether are those that are able to form an azeotropic mixture with the particular fluorinated ether. It is furthermore possible to use a mixture of two or more fluorinated ethers as the reaction medium.
• the reaction medium comprises at least 50% by weight and more preferably at least 90 % by weight of the fluorinated ether.
• the fluorinated ethers of the present invention can be used in a variety of organic reactions. Such organic reactions include free radical polymerizations, polycondensations, oxidation and reduction reactions, radical addition reactions, nucleophilic addition reactions, electrophilic addition reactions and nucleophilic and electrophilic substitution reactions.
• the organic reactions can be of the type that require a catalyst. Such catalyst can be of acidic or basic nature or they may operate on an oxido-reduction mechanism.
• the fluorinated ethers are most suitable for use with acidic or weak basic catalysts or for use with catalysts that operate on an oxido-reduction mechanism.
• the fluorinated ethers are particularly suitable for use in organic reactions that involve one or more reactants that are fluorochemical compounds since the fluorinated ethers have good solvent properties for fluorochemical compounds.
• the fluorinated ethers however are also good solvents for many non-fluorinated compounds which makes them especially suitable for use as reaction medium in reactions that involve both a fluorochemical and a non-fluorochemical reactant.
• the fluorinated ethers can be used as a reaction medium, in particular as a liquid solvent, in the polymerization of a fluorochemical monomer.
• the polymerization is a free radical polymerization.
• a fluorochemical monomer that can be polymerized in the reaction medium of the invention typically comprises a fluorinated group and an ethyl enically unsaturated group free of fluorine.
• the fluorochemical monomer corresponds to the formula: Mrl ⁇ E (II) wherein
• M f represents a partially fluorinated or perfluorinated aliphatic group
• L 1 represents an organic divalent linking group
• E represents an ethylenically unsaturated group.
• the ethylenically unsaturated group of preferred fluorochemical monomers is free of fluorine atoms.
• a fluorochemical monomer according to formula (II) can be homopolymerised or copolymerized with other fluorochemical monomers of formula (II) and/or hydrocarbon monomers.
• hydrocarbon monomer means any substantially fluorine free monomer that contains hydrogen and carbon and optionally one or more non- interfering substitutents.
• such hydrocarbon monomer corresponds to the formula Mh-E' wherein Mh represents a fluorine free moiety and E' represents an ethylenically unsaturated group also free of fluorine atoms.
• the fluoroaliphatic radical , Mf, in the fluorochemical monomer is a fluorinated, stable, inert, preferably saturated, non-polar, monovalent aliphatic radical. It can be straight chain, branched chain, or cyclic or combinations thereof. It can contain heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen.
• M f is preferably a fully-fluorinated radical, but hydrogen or chlorine atoms can be present as substituents if not more than one atom of either is present for every two carbon atoms.
• the Mf radical has at least 3 and typically up to 18 carbon atoms, preferably 3 to 14, especially 6 to 12 carbon atoms, and preferably contains about 40% to about 80% fluorine by weight, more preferably about 50% to about 78% fluorine by weight.
• the terminal portion of the M f radical is a perfluorinated moiety, which will preferably contain at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, F 5 SCF 2 -.
• Suitable monomers that can be polymerized in the present reaction medium are those of which the M radicals are fully or substantially fluorinated and are preferably those perfluorinated aliphatic radicals of the formula C n F 2n+ ⁇ - where n is 3 to 18.
• linking group L 1 links the fluoroaliphatic group M f to the free radical polymerizable group E.
• Linking group L 1 preferably contains from 1 to about 20 carbon atoms.
• L 1 can optionally contain oxygen, nitrogen, or sulfur-containing groups or a combination thereof, and L 1 is preferably free of functional groups that substantially interfere with free-radical polymerization (e.g., polymerizable olefinic double bonds, thiols, and other such functionality known to those skilled in the art).
• linking groups L 1 include straight chain, branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carboxyamido, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene.
• Typical linking groups are selected from the group consisting of alkylenes, poly(oxyalkylenes) having 1 to 4 oxyalkylene groups and organic divalent linking groups according to the following formula:
• R 3 represents a linear or branched alkylene having 2, 3 or 4 carbon atoms
• R 4 represents an alkyl having 1 to 4 carbon atoms.
• E and E' are free radically polymerizable groups that typically contain an ethylenically unsaturated group capable of polymerization with itself or each other.
• a particularly preferred ethylenically unsaturated group is an ⁇ , ⁇ ethylenically unsaturated carbonyl group such as in an acrylate or methacrylate.
• Suitable groups include, for example, moieties derived from vinyl ethers, vinyl esters, allyl esters, vinyl ketones, styrene, vinyl amide, acrylamides, maleates, fumarates, acrylates and methacrylates. Of these, the esters of alpha, beta unsaturated acids, such as the acrylates and methacrylates are preferred.
• Fluorochemical monomers Mf-L'-E as described above and methods for the preparation thereof are known and disclosed, e.g., in U.S. Patent No. 2,803,615, which description is incorporated herein by reference .
• Examples of such compounds include general classes of fluorochemical acrylates, methacrylates, vinyl ethers, and allyl compounds containing fluorinated sulfonamido groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, acrylates or methacrylates derived from fluorochemical carboxylic acids, and perfluoroalkyl acrylates or methacrylates as disclosed in EP-A-526 976, which description is incorporated herein by reference.
• R methyl, ethyl or n-butyl.
• Suitable hydrocarbon monomers are also well known and generally commercially available. Examples of such compounds include general classes of ethylenic compounds capable of free-radical polymerization, such as, for example, allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinyl ether, dodecylvinyl ether, 2-chloroethylvinyl ether, ethylvinyl ether; unsaturated acids such as acrylic acid, methacrylic acid, alpha- chloro acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and their anhydrides and their esters such as vinyl, allyl, methyl, butyl, isobutyl, octadecyl, hexyl, heptyl, 2-ethyl-he
• Preferred co-monomers which can be copolymerized with the above-described fluorinated monomers include those selected from octadecylmethacrylate, laurylmethacrylate, butylacrylate, N-methylol acrylamide, isobutylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, glycidyl methacrylate, vinylchloride and vinylidene chloride.
• Free radical polymerization of the above fluorochemical monomers optionally in combination with one or more hydrocarbon monomers can be thermally or photochemically initiated.
• the polymerization is initiated by a free radical initiator.
• Typical examples thereof include azo compounds such as azobisisobutyronitrile, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]- dihydrochloride; 2,2'-azobis[N-(4-hydroxyphenyl)-2- methylpropionamidine]dihydrochloride; 2,2'-azobis[N-(4-aminophenyl)-2- methylpropionamidine]tetrahydrochloride; 2,2'-azobis[2-methyl-N-2- propenylpropionamidinejdihydrochloride; 2,2'-azobis[N-(2-hydroxyethyl)-2- methylpropionamidine]dihydrochloride; 2,2'-azobis[2-methyl-N-(2- hydroxyethyl)propionamide]; 2,2'-azobis[2-(hydroxymethyl)propionitrile]; 2,2'- azobis(2,3-dimethyl valeronitrile) 2,2'-
• the polymerization in the fluorinated ether as reaction medium typically can yield high molecular weight polymers. Furthermore, due to the good solvent properties of the fluorinated ether for both hydrocarbon and fluorochemical monomer, copolymers can be prepared that are otherwise difficult to prepare.
• the fluorinated ethers are excellent solvents for the copolymerization of fluorochemical (meth)acrylates with hydrocarbon (meth)acrylates and especially for copolymerization with (meth)acrylic acid.
• the resulting fluorochemical compositions comprising (a) a copolymer of a fluorochemical monomer comprising a fluorinated group and an ethylenically unsaturated group free of fluorine and a non-fluorinated monomer and (b) the fluorinated ether are particularly suitable for use as protective coatings.
• the fluorochemical composition can be applied to a substrate such as for example copper, aluminum, steel, tin and glass.
• the fluorochemical composition is applied to an electronic component. Typical application methods include dipping, brushing or spraying. Dipping is typically preferred as it yields a uniform film.
• the resulting film is chemically inert and provides good repellency properties, in particular the resulting film is readily repellent to water, oils (including silicone oils) and solvents including heptane and toluene.
• the fluorochemical composition typically comprises an amount of 0.01% by weight to 50% by weight of the copolymer. Further, the copolymer may be dissolved or dispersed in the fluorinated ether. Preferably, the fluorochemical composition comprises between 1 and 10% by weight of the copolymer.
• the fluorinated ether used in the fluorochemical composition for use as a protective coating may further be blended with a perfluorinated hydrocarbon or trans- dichloroethylene.
• the polymerization may further be carried out in the presence of an end- capping agent or chain transfer agent to tailor the molecular weight of a polymer prepared or to prepare an oligomer which comprises only a few monomer units, typically from 2 to 50 monomer units.
• an end- capping agent or chain transfer agent to tailor the molecular weight of a polymer prepared or to prepare an oligomer which comprises only a few monomer units, typically from 2 to 50 monomer units.
• Such compound can be functionalized for further reaction which is particularly desirable in case an oligomer is prepared.
• Suitable functional groups for inclusion in the end-capping agent include hydroxy, amino, halo, epoxy, haloformyl, aziridinyl, acid groups and salts thereof , quaternary ammonium groups and salts thereof.
• chain transfer agents include:
• 2-mercaptoethanol mercaptoacetic acid, 2-mercaptobenzimidazole, 2-mercaptobenzoic acid, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercapto-2-butanol, 2-mercaptosulfonic acid, 2-mercaptoethyl ether, 2-mercaptoethylsulfide, 2-mercaptoimidazole, 8-mercaptomenthone,
• 2-mercaptonicotinic acid 4-hydroxythiophenol, 3-mercapto-l,2-propanediol, l-mercapto-2-propanol, 2-mercaptopropionic acid, N-(2-mercaptopropionyl)glycine, 3-mercaptopropyltrimethoxysilane, 2-mercaptopyridine, 2-mercaptopyridine-N-oxide, 2-mercaptopyridinol, 2-mercaptopyrimidine, mercaptosuccinic acid, 2,3-dimercaptopropanesulfonic acid, 2,3-dimercaptopropanol, 2,3-dimercaptosuccinic acid, 2,5-dimercapto-l,3,4-thiadiazole, 3,4-toluenedithiol, o-, m-, and p-thiocresol, 2-mercaptoethylamine, ethylcyclohexanedithiol, p-menthane
• Preferred functionalized end-capping agents include 2-mercaptoethanol, 3-mercapto-l,2-propanediol, 4-mercaptobutanol, 11-mercaptoundecanol, mercaptoacetic acid, 3-mercaptopropionic acid, 12-mercaptododecanoic acid, 2-mercaptoethylamine, 1 -chloro-6-mercapto-4-oxahexan-2-ol, 2,3-dimercaptosuccinic acid, 2,3-dimercaptopropanol, 3-mercaptopropyltrimethoxysilane, 2-chloroethanethiol, 2-amino-3-mercaptopropionic acid, and compounds such as the adduct of 2-mercaptoethylamine and caprolactam.
• Non-functionalized end-capping agents or chain transfer agents are those that contain a group capable of terminating a radical chain reaction (e.g., a thiol) but no further functional groups.
• a radical chain reaction e.g., a thiol
• Such compounds include mono, di, and polythiols such as ethanethiol, propanethiol, butanethiol, hexanethiol, n-octylthiol, t- dodecylthiol, 2-mercaptoethyl ether, 2-mercaptoimidazole, and the like.
• the fluorinated ethers of the present invention are also excellent reaction media for the homo- or copolymerization of hydrocarbon monomers not involving a fluorochemical monomer.
• Suitable hydrocarbon monomers that can be homo- or copolymerized in a reaction medium comprising the fluorinated compound are those listed above.
• the fluorinated ethers used in the present invention allow for the preparation of very high molecular weight polymers of hydrocarbon monomers and due to their excellent solvent properties for these monomers, copolymers can be prepared of hydrocarbon monomers which in other solvents might otherwise be difficult or impossible to prepare.
• the fluorinated ethers of the present invention are particularly suitable to prepare copolymers of alkyl acrylates wherein the alkyl group contains at least 4 carbon atoms and/or alkyl methacrylates wherein the alkyl group contains at least 4 carbon atoms and acrylic or methacrylic acid. It was found that such polymers could be readily prepared in the fluorinated ether and could be easily separated therefrom after polymerization. This stands in contrast to other common solvents such as ethylacetate used for this polymerization that may yield nonhomogenous polymers, in particular when methacrylic acid is the comonomer.
• long chain alkyl(meth)acrylates that can be copolymerized with acrylic or methacrylic acid
• examples of long chain alkyl(meth)acrylates that can be copolymerized with acrylic or methacrylic acid include n-butyl, n-pentyl, n-hexyl, cyclohexyl, isoheptyl, n-nonyl, n-decyl, isohexyl, lauryl, octadecyl, isobornyl, 2-ethyloctyl, iso-octyl, n- octyl and 2-ethylhexyl acrylates and methacrylates.
• copolymers prepared in the fluorinated ether as reaction medium can be separated therefrom as stable polymer beads despite the absence of a stabilizer which is normally required to prepare such beads.
• polymer beads of a copolymer of iso- octylacrylate and methacrylic acid can conveniently be prepared in this way. These polymers whether in the form of beads or not may be used to formulate a pressure sensitive adhesive.
• the present invention therefore also provides a mixture of a fluorinated ether of the present invention and a copolymer of a fluorine free acrylate or methacrylate and acrylic or methacrylic acid.
• the present invention provides a mixture of a fluorinated ether and a copolymer of an alkyl acrylate or methacrylate of which the alkyl group has at least 4 carbon atoms and acrylic or methacrylic acid.
• the amount of solids of such a mixture will typically be in the range of 20% by weight to 60% by weight and more preferably between 30% by weight and 55% by weight.
• fluorinated ethers can also be used as reaction medium for the polymerization of so called "fluoromonomers".
• fluoromonomers are meant compounds that may be free radically polymerized, that contain at least one vinylic fluorine atom attached to the vinyl group that undergoes polymerization, and the compounds 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene.
• the fluoromonomer may be polymerized alone to form a homopolymer if the fluoromonomer usually can be homopolymerized, or may be polymerized with one or more other fluoromonomers or other monomers which are not fluoromonomers to form a copolymer. If a copolymer is to be formed, the monomers chosen must be able to copolymerize. Such copolymerizable monomer combinations are known, see for example D. P. Carlson and W. Schmiegel, in W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed , vol. All, VCH Verlasgesellschaft GmbH, Weinheim, 1988, p.
• fluorinated ethers are also suitable for use as the reaction medium of polycondensation reactions which typically involve such flammable solvents as ethylacetate or methyl ethylketone.
• the fluorinated ether can be used as the reaction medium for the polycondensation of a polyol, in particular a diol, and a compound having at least two acid groups, in particular carboxylic acid groups.
• Suitable polyols include alkane diols such as 1,4-butanediol, 1,3- propanediol and glycol, polyester diols and polyether diols.
• Suitable compounds containing two or more acid groups include dicarboxylic acids such as adipic acid, maleinic acid, succinic acid and barbituric acid.
• a catalyst in particular an acid catalyst such as p- toluenesulphonic acid.
• the fluorinated ethers are particularly suitable when the polycondensation involves a fluorochemical reactant.
• the polyol used is a fluorochemical polyol of the following formula (III):
• R' f is a fluoroaliphatic radical, for example as described above for M f ; and L 2 is an organic trivalent linking group, such as an alkylene, or an organic trivalent linking group corresponding to one of the following two formulas:
• L 3 , L 4 and L 5 each independently represent an organic divalent linking group such as a linear or branched alkylene or an arylene.
• fluorochemical diols include those mentioned in U.S. Patent
• the fluorinated ethers are further suitable for use as a reaction medium in a polycondensation of an epoxide and an alcohol to form a polyether.
• Suitable epoxides that can be used include epichlorohydrine, ethylene oxide and propylene oxide.
• Suitable alcohols include alkanols such as ethanol, propanol and butanol. Such reactions are preferably catalyzed using a catalyst such as SnCl .
• the fluorinated ethers are particularly preferred as the reaction medium of a polycondensation of a fluorochemical alcohol and an epoxide.
• Suitable fluorochemical alcohols include monoflinctional fluoroaliphatic alcohols such as the N-alkanol perfluoroalkylsulfonamides described in U.S. Patent No. 2,803,656 (Ahlbrecht et al.) (which description is incorporated herein by reference).
• fluoroaliphatic alcohols are the following: N-ethyl-N-(2- hydroxyethyl)-perfluorooctanesulfonamide, N-propyl-N-(2-hydroxyethyl)- perfluorooctanesulfonamide, N-ethyl-N-(2-hydroxyethyl)- perfluorodecanesulfonamide, N-ethyl-N-(2-hydroxyethyl)- perfluorododecanesulfonamide, N-ethyl-N-(2-hydroxyethyl)- perfluorocyclohexylethanesulfonamide, N-propyl-N-(2-hydroxyethyl)- perfluorobutylcyclohexanesulfonamide, N-ethyl-N-(2-hydroxyethyl)-perfluoro-4- dodecylcyclohexanesulfonamide
• Still other alcohols include the perfluoroalkyl-substituted alkanols of the formula C leverageF 2n+ ⁇ CH 2 OH, where n is 4 to 10 (e.g., C 4 F 9 CH 2 OH), described, for example, in U.S. Patent No. 2,666,797 (Husted et al.) (which description is incorporated herein by reference), and of the formula Rf (CH ) m OH where R f is a perfluoroalkyl radical having from 4 to 10 carbon atoms and m is an-integer from 1 to 4.
• the fluorinated ether can further be used in a polycondensation reaction involving the use of a polyisocyanate.
• the fluorinated ethers can be used as the reaction medium of a polycondensation of a polyisocyanate and a fluorochemical alcohol, including fluorochemical polyols and/or a hydrocarbon alcohol including hydrocarbon polyols.
• fluorochemical alcohols include those listed above.
• hydrocarbon alcohols include methanol, ethanol, ethylhexanol and the polyols exemplified above.
• Suitable polyisocyanates include aliphatic and aromatic isocyanates.
• aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4,6-di- (trifluoromethyl)- 1,3 -benzene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenylether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,5'-diphenyldiisocyanate, 4,4'- diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'- diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphen
• isocyanates containing internal isocyanate-derived moieties such as biuret-containing tri-isocyanates such as that available from Bayer as DESMODURTM N-100, isocyanurate-containing tri-isocyanates such as that available from Huls AG, Germany, as IPDI- 1890, and azetidinedione-containing diisocyanates such as that available from Bayer as DESMODURTM TT.
• other di- or tri-isocyanates such as those available from Bayer as DESMODURTM L and DESMODURTM W, and tri-(4-isocyanatophenyl)-methane (available from Bayer as DESMODURTM R) are suitable.
• the fluorinated ethers are also suitable as a reaction medium in esterification reactions, in particular when one of the reactants, typically the alcohol is a fluorochemical reactant.
• the fluorinated ethers can be used as the reaction medium in the preparation of an ester through the reaction of an alcohol and an acid chloride.
• alcohols that can be used are those listed above, including the fluorochemical alcohols listed above.
• Suitable acid chlorides include acrylol and methacryloyl chloride which allow for the preparation of a fluorochemical monomer as described above, acetic acid chloride, phtaloylic acid chloride and benzoic acid chloride. These reactions are typically carried out in the presence of a basic catalyst capable of scavenging the hydrochloric acid formed during the reaction.
• a typical catalyst is triethylamine.
• esters can be prepared by reacting an acid with an alcohol preferably in the presence of a catalyst such as p-toluenesulphonic acid.
• the fluorinated ether has been found to be a suitable reaction medium.
• Transesterifications wherein an ester is reacted with an alcohol typically in the presence of a catalyst, for example an acid catalyst, may also be carried out in the fluorinated ether as reaction medium.
• a catalyst for example an acid catalyst
• the fluorinated ether used as reaction medium is immiscible, at least at ambient temperature, with the alcohol formed during the reaction. This facilitates the separation of the reaction product.
• the fluorinated ethers are further a suitable reaction medium for the preparation of an enamine from a ketone and an amine.
• the fluorinated ether can be used to react morpholine with cyclohexanone to prepare the corresponding enamine.
• Such reaction is preferably carried out with the aid of a catalyst such as p-toluenesulphonic acid.
• a catalyst such as p-toluenesulphonic acid.
• Molecular weights of the polymers were determined by means of a Waters GPC equipped with a refractive index detector. Hexafluoroisopropanol was used as a solvent and polymethylmethacrylate was used as a reference standard.
• a 2% solution of polymer in fluorinated ether was prepared.
• a glass plate of 3 cm x 10 cm was dipped into the solution and dried at room temperature.
• the contact angle for different solvents was measured using an Olympus TGHM goniometer.
• the inherent viscosity of the polymers was measured by conventional means using a Cannon-Fenske 50 viscosimeter in a water bath controlled at 25°C to measure the flow time of 10 ml of a polymer solution (0.15 g of polymer in 100 ml methylethyl ketone). Inherent viscosity is recorded as dl/g.
• V-65 2,2'-azobis(2,4-dimethyl valeronitrile), available from Wako
• BuFOSE C 8 F 17 SO 2 N(Butyl)CH 2 CH 2 OH
• PAPI polymethylenepolyphenylisocyanate, available from Dow Chemical
• AMA allyl methacrylate
• MA Maleic anhydride
• AAEMA 2-hydroxyethyl methacrylate ester of acetoacetic acid, available from Lonza
• DCPOEMA dicyclopentenyloxy ethyl methacrylate, available from Wako
• IOTG isooctyl thioglycolate, available from Elf Atochem
• UvecrylTM P-36 benzophenone derivative of acrylic acid, available from UCB
• VCL 2 vinylidenechloride
• Example 2 Using essentially the procedure of Example 1, the flask was charged with methacrylic acid (8.6 g, 0.1 mole), allyl alcohol (5.8 g, 0.1 mole), p-toluenesulfonic acid monohydrate (0.6 g) and perfluorobutyl methyl ether (70 g). The mixture was heated to reflux for four hours, filtered, and distilled to recover the perfluorobutyl methyl ether. The residue was then distilled under vacuum to yield allyl methacrylate (10 g, b.p. 70-TC at 5 torr, purity 93% by GC).
• Example 8 Using essentially the procedure of Example 1, the flask was charged with morpholine (8.7 g, 0.1 mole) and hexanone (10.1 g, 0.1 mole) in perfluorobutyl ethyl ether (60 g). After refuxing for ten hours, the fluorinated ether was removed by flash distillation and water (20 mL) was added to the residue. The resultant mixture was extracted with diethyl ether, the combined ether extracts washed with water, dried over magnesium sulfate and distilled to yield the desired enamine (10.6 g, b.p. 73-4°C at 0.35 torr).
• Example 2 Using essentially the procedure of Example 1, the flask was charged with PhCO 2 C 3 H 7 (34 g, 0.2 mole), 1,4-butane diol (9.1 g, 0.1 mole) and p- toluenesulfonic acid monohydrate (0.5 g) and perfluoroheptyl methyl ether (160 g).
• a 500 ml three necked reaction flask, equipped with a stirrer, a thermometer, a condenser and a heating mantle was charged with 80 g (0.2 moles) C 7 F 15 CH 2 OH, 80 g perfluorobutyl methyl ether and 22.2 g triethylamine (0.22 moles). The mixture was cooled to 5°C in an ice bath under nitrogen atmosphere.
• Examples 12 to 15 illustrate the versatility of hydrofluoro ethers as reaction medium for the copolymerization of fluorochemical acrylate monomers with fluorine free monomers.
• Examples 13 to 15 were made following the same procedure as for Example 12, using the monomers as given below.
• Example 15 MeFOSEMA (8.55 g) + BMA (3.3 g) + LMA (3.0 g) + MAA (0.15 g)
• the polymerization procedure of Example 12 was repeated, but the perfluorobutyl methyl ether was replaced by HCF 2 CF 2 CH 2 OCH 3 as the reaction medium.
• GLC analysis indicated a conversion of 92%o.
• the fluorinated ether was replaced by butylacetate and a perfluorocarbon, respectively.
• the polymers prepared in Examples 12 to 15 were evaluated for their contact angle and their molecular weight and compared to polymers of Examples C-1 to C-3. The results are given in Table 1.
• the fluorinated ethers are suitable as reaction medium for the polymerization of a fluorochemical monomer and a non- fluorochemical monomer. Similar contact angles and molecular weight was obtained for polymers prepared in the fluorinated ether of the invention as compared to a polymer prepared in a perfluorocarbon solvent or butylacetate. Compared to the ether of Example C-1, much higher molecular weight polymers were obtained.
• Example 16 illustrates the use of the fluorinated ether as reaction medium for a ring opening reaction.
• Example 17 This example demonstrates the use of the fluorinated ethers as reaction medium in condensation reactions.
• a fluorochemical urethane was made starting from the following reactants:
• fluorochemical acrylates were homopolymerized or copolymerized with fluorine-free monomers, using perfluorobutyl methyl ether as reaction medium.
• the polymers were made at 30% solids using 0.3% AIBN as initiator.
• the reactions were run at 70°C, for 16 hours.
• the monomer compositions are given in Table 2.
• fluorochemical copolymers could be made in the fluorinated ether, even if one of the monomers, e.g., ODMA was not soluble in the reaction medium.
• Examples 26 to 36 essentially the same procedure as for Examples 18 to 25 was used to prepare copolymers of fluorochemical acrylates with various non- fluorochemical monomers described in Table 3.
• the polymers were made at 30% solids, using 1.2 parts lauroylperoxide as initiator and 0.3 parts n-octylmercaptane as chain transfer agent. The reactions were run at 70°C for 20 hours.
• Example 29 After polymerization, all polymer solutions were viscous clear solutions, except for Example 29 which was a hazy viscous solution.
• fluorochemical polymers were made using vinylidene chloride as comonomer.
• the reactions were carried out at 30% solids in a mixture of perfluorobutyl methyl ether (66.5 parts) and n-butylglycidylether (3.5 parts ; added to stabilize the vinylidene chloride containing polymer formed).
• 1.2 parts lauroyl peroxide was used as initiator and 0.3 parts n-octyl mercaptane were added as chain transfer agent.
• the reactions were run at 70°C during 20 hours. The composition and appearance after reaction are given in Table 4.
• Examples 41 and 42 illustrate the use of the fluorinated ethers as reaction medium to make non-fluorochemical polymers.
• IOA/AA 90/10 and IOA/MAA 90/10 monomer mixtures were polymerized under nitrogen atmosphere in perfluorobutyl methyl ether, at 40% solids, using 0.2% V-65 as initiator. The reaction was carried out for 24 hours at 45°C. While the monomer mixtures were soluble in the reaction medium, during the reaction the polymers formed precipitated and could be easily separated from the solvent. After polymerization, the polymers were isolated and dried in an oven. The polymers formed were not soluble in common used solvents, such as ethylacetate, THF or MEK, indicating high molecular weight polymer was made. Examples 43 to 45
• Examples 43 to 45 were carried out following essentially the same procedure used in examples 41 and 42, but with lower amount of solids.
• the polymers were made at 45°C at 30% solids, using 0.2% V-65.
• Comparative Examples C-4 to C-6 were made in ethylacetate as solvent. The results are given in Table 5.
• Comparative Examples C-4 and C-6 formed viscous polymer solutions, which were soluble in MEK and for which IV could be measured.
• Comparative Example C-5 a very nonhomogeneous mixture with high viscous solution and some solid polymer was formed. This shows that for certain monomer compositions such as IOA/MAA, with MAA used at rather high concentrations, it was not possible to make a copolymer in ethylacetate, whereas the mixture can be polymerized in the fluorinated ether.
• Examples 46 to 48 were carried out essentially according to the procedure of Examples 43 to 45. In order to further lower the molecular weight, a chain transfer agent was added. The polymers were made at 30% solids using 0.2% V-65 and 0.5% IOTG. The reaction was run at 45°C for 24 hours. Comparative Examples C-7 to C-9 were made in the same way, but using ethylacetate as solvent. The composition of the polymers and the results are given in Table 6.

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