Патент USA US3079438код для вставки
ite U f :1 3,079,428 a > r '2 3,679,428 ,. . metal to form an anion, the conjugate acid of said an: having The following a pKa valueof examples at least,16., are given to illustrate the in vention. Parts mentioned are‘ parts by Weight. ... 'PURE‘ICATION OFORGANIC LIQUIDS Massimo ,Baer, Longmeadow, and ,Mi'chael'F. Vignale, ,_ s, _ Fatented ‘Feb, '26, __ ,,_ ,CONTAININGACID’IMPURITIES . Spring?eld;_Mass., assignors, top'Monsantp Chemical ‘EXAMPLE I (Iompany, St. Louis; 70., a 'cnrpoi‘ation of Delaware N0 Drawing. Filed ()ct.20,~1959, Ser. No. 847,472 6 Claims. (Cl. 260—486) _ ,A suitable‘reaction Preper's?qiofi’witying vessel is chargedAgent with BTOQparts . of _ This invention relatestorinsoluble polymei'ic anionic water, followed by addition of. 1 partof'bentonite with agitation. The'slurry is heated to 65—70f’ ‘C., and}. ‘mixture of 50 parts of. vinyl fluorene, 4O partslof styrene, materials. More particularly, .the invention relatesytto .insolublepolymeric anionic materials which are ‘useful asipiurifying agents for removing acidic impurities from organic‘liquids. _ _ . _ , v, '10 parts of divinyl benzene, and'l part of benzoyl peroxide . is added thereto. The air in the-vessel is purged with ,Because of the sensitivity of anionic polymerization nitrogen, and the pressurized vessel contents are heated at 88+90° C. for '20 hours and then-‘at 1l5—120° C. for ‘systems to acidic, impurities, i.e., proton ‘donors, Which destroy‘ or consume the growing'chaius and‘ initiator, sol~ vents and monomers to be employed in such polymeriza 12 ‘hours. The batch is cooled anddischarged into a centrifuge where the suspension is collected 'andwashed _tion_systems should be substantially, free'of impurities .Wit hot water.. The polymer beads ,are‘dried in a forged __dra'ft’air oven for 12 hours at 110-120“ 'C, and washed aving apKa value lower than that of the monomers to _'be. polymerized, i.e., impurities which are more highly _with 'LZ-dimethoxYe'tha‘ne to form substantially pure acid than the monomers, Many materials known to be capable‘of reacting with the acidic impurities cannot‘ be vused to purify the solvents, and monomers, ‘because, in _ zene ‘A molar (50':40:l0)‘terpolymer. solution of sodium . naphthalene . > t. . (in v1_,i2:cl_i— t. order _to_ be suitable as a, purifying agent in this applica tion a material must satisfy these general requirements: ‘. (1) _It ,must be capable of removing the acidic inipur ities without contaminating the solvents and/or monomers methox'yethane is passed through a ‘column containing the polymer beads inorder to replace the active hy drogen atoms of "the vinyl, ?uorenefu'nits withlso'dium. The effluent from the column, a solution of diliydronaph beads of cross-linked vinyl ?uoreneéstvreneidivinyl ben with another impurity which'reacts with anionic initiators, and . , , , ,(2) It must be inert to the Iiquid‘beingJpuri?ed, e.g., it must‘ib'e'incapable of initiating polymerization of ‘the monomer being-‘puri?ed. . , l , thalene and sodium naphthalenein'LZ-dimethoXYethaiie, . 30 t tion indicates no further capacity of tthefpolymerlto react 'with'so'dium. The column of beads-is then washed with I Asiusedvthroughout the speci?cation, terms referring to acidity shouldjbe understoodas follows‘ in the's‘ense of the de?nitions derived from the proton-transfer theory of acids and bases: , V, , t , 35 . substantially, all. of the vinyl-fluorenetunits of._.the,'_cross base, a'base being any substance which, because 'of an unshared electronpair, can accept a'proton, , 40 _ (2) Conjugate acid-acid related *to'a‘pa'rticul'ar base base, M ; , _ . (3); pKa value—negative logarithm of the dissociation constant of an acid. , ,> , _._t It will be noted that, whenunderstood in this sense, the term “acid”_is not restricted to the inorganic, car lboxylic, and, ,sulfonic compounds conventionally des ignated as acids, i.e., compounds having low pKa ‘values ofup to about 10, but also embraces compounds of much higher pKa value.‘ 7 v t - _ .H_O_ne_ objectof this invention is toipr'ovide means for purifying organic, liquids of acidic'impurities, i.e., im purities having a pKa value lower than that of the organic liquid, t . _1 'Another object is to provide means for purifying organic iquids of acidic impurities without contaminating the liquids with other impurities capable ‘of reacting with anionic, polymerization initiators. V ‘.A_ further-‘object is to provide'mean's for purifying organic liquids of acidic impurities without causing'reao tion of the liquid being puri?ed. , r l _ t _ :Th‘e'se and‘other objects are attained by purifying an organic’ liquid 7 of acidic impurities by contacting the liquid with an insoluble polymeric anionic material which isinert .to the liquid, said anionic material being an alkali metal'salh or'alkaline earth metal salt of an insoluble, ero‘ssf-linkedpolymer containing anplurality ofunitslcap ‘able "of reacting with an ‘alkali metal or alkaline earth ~LZ-climethoxyethane to remove residual‘sodium naphthal ‘ene and dihydronaphthalene._ The product of thel‘tr'eat ment is an insoluble polymeric anionic material in which O. (1‘) Acid-product obtained byiadding ‘a proton‘to a in‘ being the, product obtained by adding a proton to that ‘is ‘collected in areceiver. The 'treatment'of ‘the, polymer with sodium naphthalene solution is continued until the c'onc'entrationoof sodium naphthalene‘in thee?luent solu linked vinyl ,?uor'ene-styrenejdivinyl ‘benzene’ (50:40:10) ‘ter'polymer ,_ The samehave procedureIof been converted interpolymerizingjmonomers 'to theis'odium‘sjalt, by suspensionpolymerization to form beads of'a cross linked polymer and then reacting the beads ,with'an alkali inetal‘naphthalene to form an insoluble vpolym'eric'anio'nic material'is used'to' prepare the following salts; , v ‘T (1) ‘Sodium salt of a styrene-N,N-dia1lylacrylamide (80:20)v copolymer in which substantially all of the ac ‘tive hydrogen'atoms ofthe N,N-diallylacrylamide units have been replaced with sodium, 7 p t t v,‘ . (2) :Lithium, salt of a vinyl benz’yl alcohol-divinyl ben zene (90:10,), copolymer in which substantially'all ‘of the activehydro'gen atoms of the vinyl benzyl'alcohol units have been replaced with lithium, , ’ ~ __ _ - (3), Lithium salt of a styrene-vinyl indene-divinyl ben Lz'ene‘ (6Q:30:_1O)jt_erpolyn1er in which'substantially ‘all 'of the activejhydrogen atoms of the Vinyl inderie units have been ‘replaced with lithium, ' v , . , v , h ';(4).'Potassium salt of a styrene-vinyl,?uorenedivinyl benzene (§0:30:l_()),te1'polymer in Whichsubstantiallyall of‘the active hydrogen atoms of the vinyl ?uorene units have been replaced with potassium, and _ H. ,1 ‘(5) Potassium salt ofta p-aminostyrene-styrene-divinyl il_:enze‘ne__(8"0: l0: l0)‘terpolymer in which substantiallyfall of the active hydrogen atoms of the p-aminostyrene units have ‘been replaced with potassium. EXAMPLE ”II Puri?cation of Organic-Liquids ‘organic liquids are puri?ed, using the indicated in acre/res 3 soluble polymeric anionic materials of Example I as puri tying agents: Organic liquid Purifying agent Benzene ___________________ -_ Na salt of vinyl ?ucrene-styrene-diviny benzene (50:40: 10) terpclymer. cross-linking agent may constitute the only polymeric 1,2-dimethoxyethane _______ _- Na salt of styrene-N,N-d1allylacrylam ' ide (80:20) copolymer. _ benzene (90:10) copolymer. component capable of reacting with an alkali metal or . Methyl methacrylate ______ __ Li salt of vinyl benzyl alcohol-divmyl _ _ 10 alkaline earth metal to form an anion. _ _ with which alkali metal or alkaline earth metal is re Butadiene _________________ __ K salt of styrene-vinyl ?uorene-divmyl benzene (60:30:10) terpolymer. acted to form the purifying agents of the invention is _ _ that they be insoluble, cross-linked polymers containing Isoprene ___________________ __ K salt of p-aminostyrene-styrene-d1vmyl ' benzene (80:10:10) terpolymer. In each case puri?cation is accomplished by passing the organic liquid through a column of beads of the purifying agent, andrin each case the effluent from the column is an unreacted organic liquid substantially free of acidic impurities. EXAMPLE Demonstration of E?ectiveness of Puri?cation 7 However, since the only requirement of the polymers Styrene ____________________ __ Li salt of styrene-vinyl indene-divinyl benzene (60:30:10) terpolymer. 4 which in the course of polymerization leave residual un reacted allyl groups. These cross-linking agents are co polymerized with one or more monoethylenically-unsatu rated copolymerizable monomer-s which may, if desired, also be monomers which, as a chemically-combined unit of a polymer, contain active hydrogen replaceable with alkali metal or alkaline earth metal. Alternatively, the a plurality of units capable of reacting with alkali metal or alkaline earth metal to form'an anion and that they have a pKa value at least as high as 16, and since mono mers capable of contributing such units containing active hydrogen are already well known, various other poly 20 mers utilizable in preparing the purifying agents will be obvious to those skilled in the art. The polymers usually A suitable reaction vessel is charged with half of a carefully-degassed solution of 100 parts of styrene in 980 parts of 1,2-dimethoxyethane, followed by the addition with agitation of half of a substantially pure, carefully degasscd solution of about 0.13 part of sodium naphtha should contain about l-40%, preferably 5—25%, by ‘weight of units of the cross-linking agent and at least about 10% by weight of units capable of reacting with 25 alkali metal or alkaline earth metal to form an anion. l,2-di>methoxyethane, an inert atmos- ' They can be prepared by any suitable polymerization technique, advantageously by suspension polymerization of the monomers to form polymer beads, as demonstrated in Example I, or by impregnating an inert carrier, e.g., lens in 20 parts of silica gel, alumina, calcium sulfate, carbon black, di phere being maintained in the vessel throughout the re 30 atomaceous earths, clays, etc, with the monomers and action. The reaction results in a small yield of poly then polymerizing to form a thin coating of polymer on styrene. a large surface of the inert carrier. The second half of the carefully-degassed monomer The purifying agents of the invention are prepared by solution described in the previous paragraph is passed reacting these insoluble, cross-linked polymers with a 35 through a column of beads of the sodium salt of the vinyl metal of group IA .or HA of the periodic classi?cation of ?uorene-styrene-divinyl benzene (50:40:10) terpolyme'r the elements, i.e., with Li, Na, K, Rb, Cs, Mg, Ca, Ba, or of Example I. The e?luent from the column is charged Sr, to replace the active hydrogen atoms of the polymer to a suitable reaction vessel, followed by the addition with metalrthus forming an insoluble polymeric anionic with agitation of the second half of the substantially material. This reaction can be accomplished by contact 40 pure, carefully-degassed initiator solution, an inert atmos ing the polymer in any suitable manner with a‘ solution phere being maintained ‘in the vessel throughout the re or dispersion of the metal in an inert liquid medium or, action. The' reaction results in substantially quantita more efficiently, by contacting the'polymer with a solution tive conversion of styrene to high molecular weight poly or dispersion in an inert liquid medium of an organo metallic compound of the metal whose conjugate acid is styrene. The present invention relates to novel insoluble poly 45 weaker than that contained in the insoluble polymer. Ad meric anionic materials and to their use as purifying agents vantageously, the polymer is reacted with the metal by for organic liquids containing acidic impurities. . contacting it with a solution of an ion-radical adduct, The insoluble polymeric anionic materials are the alkali c.g., sodium naphthalene, in a polar solvent ‘such as 1,2 metal salts and alkaline earth metal salts of insoluble, dimethoxyethane, as demonstrated in Example I. cross-linked polymers containing a plurality of units capa 50 The treatment of the/polymer with the metal-containing ble of reacting with an alkali metal or alkaline earth metal to form an anion, the conjugate acids of said salts having pKa values of at least 16. composition is preferably continued until the capability Exemplary of known polymers which can be reacted with the maximum number of possible sites for subsequent of the polymer to react with the alkali metal or alkaline earth metal is exhausted in order to furnish the polymer with alkali metals or alkaline earth metals to form the 55 purifying agents of the invention are copolymers of vinyl toluene, vinyl 'isopropyl benzene, vinyl benzyl alcohol, peacetylstyrene, p-aminostyrene, vinyl pyridine, ethyl reaction with acidic impurities contaminating the organic liquids to be puri?ed. However, this exhaustion of the capability of the polymer to react with alkali metal or alkaline earth metal is obviously not required to make the eniminc, or other polymerizable compound which, as a polymeric anionic ‘materials effective as’ purifying agents, chemically-combined unit of a polymer, contains an ac 60 particularly when the polymer contains a large number tive hydrogen replaceable with alkali metal or alkaline of units capable of reacting with alkali metal or alkaline earth metal, or mixtures of such compounds, with one earth metal. After completion of the treatment of the or more cross-linking agents such as divinyl benzene, di insoluble polymer with the alkali metal or alkaline vinyl toluene, divinyl xylene, divinyl ethylbenzene, diiso propenyl benzene, trivinyl benzene, divinyl naphthalene, trivinyl naphthalene, polyvinyl anthracene, etc., and op tionally with one or more other interpolymerizable mono mers, e.g., vinyl ethers, styrene, etc. Other known polymers utilizable in preparing the puri earth metal, the polymeric anionic material is preferably 65 washed with an inert solvent, e.g., liquid ammonia, to re move unreacted metal, metal compound, or residue of metal compound. The insoluble polymeric anionic materials of the in; vention are e?ective as agents for purifying organic tying agents of the invention are copolymers in which 70 liquids of acidic impurities. The invention is particularly the cross-linking agent, as a chemically-combined unit of applicable to the puri?cation of organic liquids to be em a polymer, contains active hydrogen replaceable with ployed in anionic polymerization systems, e.g., anionical alkali metal or alkaline earth metal. Such cross-linking ly-polymerizable vinylidene monomers such as styrene, agents are, for example, p-diallyl benzene, diallyl mela vinyl toluene, 0-, m-, and p-methoxy-styrenes, butadiene, 75 mine, N,N-diallylacrylamide, allyl silancs, and the like, 3,079,428 5 isoprene, methyl methacrylate, etc., or solvents such as benzene, hexane, tetrahydrofuran, 1,2-dimethoxyethane, What is claimed is: 1. A process for purifying an organic liquid of more etc., but it can also be applied to the puri?cation of any or highly acidic impurities which comprises contacting the ganic liquid which is contaminated by impurities having liquid with an insoluble polymeric anionic material which a pKa value lower than that of the liquid. 5 is inert to the liquid, said anionic material being a salt of Puri?cation of the organic liquids is accomplished by a metal of the group consisting of alkali metals and al contacting the liquid with the purifying agent in any suit kaline earth metals with an insoluble, cross-linked polymer able manner, advantageously by passing the liquid through containing a plurality of units capable of reacting with a. column of beads of the purifying agent, as demon— said metal to form an anion whose conjugate acid has a pKa value at least as high as 16. 2. A process as in claim 1 wherein the organic liquid is an anionically-polymerizable vinylidene monomer. strated in Examples 11 and 111. After being used to puri fy an organic liquid, the insoluble polymeric anionic ma terial can be regenerated by repeating the metal treat ment used in preparing the purifying agent. 3. A process for purifyirig methyl methacrylate of Since the various organic liquids which can be puri?ed more highly acidic impurities which comprises contacting of acidic impurities by the insoluble polymeric anionic the methyl methacrylate with a lithium salt of an insoluble, materials of the invention have varying degrees of reac crossalinked vinyl benzyl alcohol-divinyl benzene co— tivity with anionic materials, care must be taken in the polymer. choice of a purifying agent for a particular organic liquid 4. A process for purifying styrene of more highly acidic to insure removal of the acidic impurities without causing impurities which comprises contacting the styrene with a undesrable reaction of the liquid. The suitability of a 20 sodium salt of an insoluble, cross-linked vinyl ?uorene particular insoluble polymeric anionic material as a puri styrene-divinyl benzene terpolymer. fying agent for organic liquids can readily be determined 5. A process for purifying butadiene of more highly by routine experimentation, and in many cases this de acidic impurities which comprises contacting the butadiene termination of the suitability of the anionic material is with a potassium salt of an insoluble, cross-linked styrene~ facilitated by the fact that the reactivity or lack of re 25 vinyl fluorene~divinyl benzene terpolymer. activity of many of the organic liquids with anionic ma 6. A process for purifying isoprene of more highly terials of varying pKa values is already known. For greatest e?iciency in removing acidic impurities, the puri with a potassium salt of an insoluble, cross-linked p— fying agent should have as high a pKa value as is con aminostyrene-styrene-divinyl benzene terpolymer. acidic impurities which comprises contacting the isoprene sistent with the requirement that it be inert to the organic 30 liquid being puri?ed. The invention is particularly advantageous in that it provides novel insoluble polymeric anionic materials which, when used as purifying agents for organic liquids, enable the removal from solvents and monomers of sub stantially all of the acidic impurities which interfere with anionic polymerization without contaminating the solvents 35 References Cited in the ?le of this patent UNITED STATES PATENTS 2,609,387 2,687,383 2,704,770 2,891,916 Basdekis et al. ________ __ Sept. 2, D’Alelio ____________ __ Aug. 24, Anspon ____________ __ Mar. 22, Hwa ________________ __ June 23, 1952 1954 1955 1959 OTHER REFERENCES and monomers with other impurities which would react with anionic initiators. Ion Exchangers in Organic and Biochemistry (1957), It is obvious that many variations may be made in the 4 O pages 130-156, pages 139, 140, 143, 147, 150-151 par products and processes set forth above without departing ticularly relied upon; Interscience Publishers, Inc., New York. from the spirit and scope of this invention.