Патент USA US2404213код для вставки
2,404,213 UNITED STATE 5 PATEN r OFFICE Patented July 16, 1946 2,404,213 .ROSIN CARBONATES Joseph N. Borglin, Wilmington, Del., assignor to Hercules Powder Company,‘ Wilmington, Del., a corporation of Delaware ' No Drawing. Application December‘9, 1942, Serial No. 468,427 -' 5 Claims. (01’. 260—100) 1 This invention relates to a new composition of matter and to the processior obtaining it and and wherein a halo formyl alkyl ester is caused to be reacted with an alkali metal rosin alco particularly to a rosin carbonate.’ holate or a rosin alcohol. ‘ In accordance with: the present ‘invention rosin’ alcohols and their alcoholates and esters may be reacted with a derivative of carbonic acid; to produce‘rosin esters‘ of‘carbonic acid. The rosin’ carbonates may contain two rosin groups‘ and may be referred to as neutral rosin In general, the rosin alcohols and their esters ‘ and alcoholates that may be used in accordance with this invention may be derived from ordinary rosinw and‘ the speci?c rosin acid components thereof as, for example, abi'etic' acid, sapinic acid,‘ d-pimaric‘ acid; l-pimaric. acid-,etcq' also carbonates. The rosin carbonates may contain 10. they: may be: derived‘ from-"chemically modi?ed rosin as, for example, polymerized Wood, hy drogenated rosin, dehydrogenated rosin, rosin one rosin group and vone alkyl, aryl', or aralkyl group and may be‘ referred to as mixed neutral rosin carbonates. Again the rosin carbonates which has been subjected to a heat treatment at about 250° C. to about 350°C’. and rosin which may contain one rosin group and; one halo group and maybe. referred‘ to as halo rosin carbonates. 15 has been subjected to a .heat treatment at about The neutral‘ andvmixed‘ neutral rosin carbon 100° C. to about 300°C. in the presence of a suit- ‘ ' ates may be preparediin general by means of an ester interchange wherein an ester of a rosin The methodv in accordance with this inven alcohol and a. dialkyl carbonate are caused’ tobe tion is'illustrated by the following speci?crex reacted together with or without'the presence 20 amples; all parts and percentages being by weight of an alkalim'etal alcoholate. Further, the neu unless otherwise speci?ed; tral and mixed neutral rosin carbonates may be preparedv by means of’ an alcohol interchange ’ Example 1‘ _ ‘ wherein a rosin alcohol and ‘a dialkyl carbonate Fifty grams of ~ hydrogenated abietyl' alcohol are caused to be reacted together in" the presence were dissolved in 50 grams of xylene.v Twenty ' of an effective, amount of an alkali metal alco grams of phosgene were passed through the solu holate as a catalyst; ‘Again, vthese ‘neutral and tion for two hours ‘at, room temperature. An nriiin-Id'v neutral" rosin‘ ‘carbonates. may‘ be prepared‘ exothermic reaction took, place resulting in the by means of.’v an, acid halide] reaction wherein ‘an; acid halidejas‘; Ior‘exampl‘e, ‘a’ halo formyl‘ halide‘ ' evolution of a relativelysmall amount of heat. able catalyst. - r y , r w al'co‘h‘ol'ate or a rosinalc'oh'ol‘ or'wherein a halo forinyl'falkyl ester is caused to .be reacted‘ with The xylene was removed by means of vacuum distillation carried out at a maximum distilla tion temperature‘ of’ 160° C‘. ' Fortye?ve grams: of an alkali metal’ rosin al'coholate or a ‘rosin . a brown semi-viscous, saponi?ab‘le l-iquid- were is caused to be reacted with an alkali metalv rosin alcohol‘ 7 ‘ ' " ' _ "I'ne'halb rosin; carbonates maybe prepared, obtained. The liquid contained about. 6mm chlorohydroabietyl carbonate and about 37% by. in gerieralfbyfrheans of an acid halide reaction wherein. an acidhalide; as, forv example,' a halo dro‘abietyl carbonate. form‘ylhalide‘jis caused to ‘bereacted with an out in a manner substantially, as described with ' ' Each of the following“ examples ‘was carried alkall‘nietal‘rosin alcoholate or a‘rosin alcohol‘, 49 reference to Example 1:‘ 2,404,213 . 3 , . 4' The mixed neutral and the neutral rosin car . Carbonic acid derivatives operable in accord 'ance with the present invention having the general formula bonates may be prepared by means ‘of an ester are the esters - interchange wherein an’ ester of arosin alcohol and an ester having the general formula ' o=o " /O—R ' 0-R 0:0 / 05R’ ' '7 ‘ wherein R, and R" are alkyl, aryl, or aralkyl rad wherein R and R’ are alkyli'aryl, or aralkyl rad-Q l0 icals, are caused to be‘reacted together with or icals as, for example, methyl, ethyl, propyl, iso _ _ Without the presence of an alkali metal alcoholate. amyl, isobutyl, etc., and speci?callydiethyl .car-" .The ester interchange reaction may be carried bonate, diisoamyl carbonate, diisobutyl carbonate, ’ dimethyl carbonate, diphenyl carbonate, ' ethyl - out by heating a rosin alcohol ester as, .for ex ample, rosin, alcohol acetate with a dialkyl car methyl carbonate, dibenzyl carbonate, etc; halo 15 bonate as, for examplegfdiethyl carbonate in a formyl halides having the general formula suitable solvent, as for example, benzenepxyl'ene, etc. The proportions of neutral and mixed neu tral rosincarbonates formed depend in part upon. thelreaction time and-‘temperature. ‘Ordinarily, 20. when the reaction is carriedout at room temper-V ature, a mixture of-vryneutralv and“. mixed neutral; rosin carbonates are formed with the mixed neu wherein X and X’ 'are’halogen radicals as,- for tral rosin carbonates predominating._ The Iquan» example, chloro, bromo, etc., and speci?cally‘ tity of neutral rosin carbonates increases with phosgene, bromo ‘formyl bromide, chloro forrnyl, increased reaction time and increased. temper.-, bromide,'bromo formyl chloride, etc.;"halo alkyl‘ Generally, the 7reaction time-may. vary, ature. ' esters having the general formula ' ' from about 1 hour to aboutlZ-hours- and will usually reach equilibrium in from about 5 hours to about 10 hours.’ The temperature-may vary. 30 from about 100? C. and about 250° C..and usually isbetween about 150$> ‘C. andabout 200‘? C‘. The concentration of the ro'sin- alcoholesterin bene, zene or any other suitable solvent may vary ' wherein X is a‘halogen radical as, for.‘ example, from about 10% to about 60% andpreferably‘ chloro, bromo, etc., and-R is- an alkyl radical as,‘ ‘ vfor example, methyl, ethyl, propyl, isoamyl, etc., 35 may Thebeneutral between andabout mixed15% neutral androsin about carbonates 30%. and speci?cally chloro‘ ethyl carbonate, chloro.‘ may be prepared by meanslof an~alcfohol inter methyl carbonate, bromo ethyl carbonate, bromo change wherein a rosin alcoholand an"esterjjcarév methyl carbonate, chloro propyl carbonate, chloro‘ isopropyl carbonate, chloro isoamyl carbonate,‘ etc.; and alkali metal salts?represented by the general formula‘ ' ‘ ' .' ' . " > - bonate of the type hereinbefore referred. toare; 40 caused to be reacted together in the presence'jof an effective amount of an alkali metal alcoholate ‘ as the catalyst. , 'Where ,dimethyl. carbonate is 1 the ester carbonate 'usecl incarryingout .the al-. cohol» reaction with a rosin alcohol, ,methylalm 45 cohol will-distillout of the reaction mixture. as the reaction progresses, under. the. in?uence - of heat when .using‘ sodium/methylate as, the, catalyst. The reaction may be carried out atja temperature. between about 60‘? .c. and about 250° C..but is-prer. ample,‘ sodium,‘ potassium, lithium,v etc., and wherein R represents an alkyl, aryl,’ or aralkyl 50, erably carried out at a temperature between about wherein M represents an alkali metal asyfor ex radical.‘ ; f '1 "' ' - ' The rosin alcohols and their ester, and alco holate derivatives operable-in-accordance with this invention'may be ‘prepared from any of the natural and chemically modi?edrosins by any; 100° C. and about 200° C. , Generally, the reaction time may vary, from about 1 hountor'about‘fll ’ hours and will, usually reach'equilibrium' in from. about 5 hours to about 10 hours. Gvenerall?whe'nx the reaction is carried out at the iowergtemperae tures‘and fora shorter period of time,'a greater I ~-=percentage of the mixed neutralrosin carbonates" .is. formed. When the reaction is carried out at. the higher temperaturesand for a greater period in the art to produce the rosin alcoholsand their: ,00 of time, a greater percentage ofneutral rosin car ester and-alcoholate derivatives.- 7 ~ ,g -'_.‘ Chemically zmodi?ed rosins which may be"E bonates'is formed._ In either case, a' mixture of treated in'accordance with procedure well known l the neutral‘ and the mixed neutral rosinjcar in the art to form the chemically modi?ed rosin bonates is produced when a rosin alcohol ‘and ‘a of the methods well known in the art. Any one ‘ ' may-be of the more treated than according 50 di?‘erent to methods isomeric wellknown rosin acidsp"~ alcohols?and their ester, and alcoholate' 'derivar-q ' carbonic acid derivative are caused to be reacted rosins, the dehydrogenated rosinls, the polymer 10% to about 60% and preferably-,emayrbelbh tives may be any rosin which has been treated 05 iri'accorda'noe with the present invention. The r to’ modify its ‘chemical structure; Rosins whichi ' :rconcentration, of the rosin‘ alcohol in benzene or fall within this general class are the hydrogenated ' “any other suitable solvent-may vary from: about ized rosins,- those rosins'which have been heat‘ ' tween about :15 %_ and about 30%‘. treated. at about 250° C. to about 350° C., those 70 The neutral rosin carbonates,,the' mixed neu-r 'traTrosin carbonatesyan’d the halo rosin car rosins'which have been heat treated at about 100°‘ C. to about 300° C. in. the presence ,of a suitable bonates maybe preparedby means [of 'an' acid catalyst, polymerized ‘crystallized vrosins, hydro; " halide‘reaction wherein'jan acidjhalideas, for ex;-~ genated crystallized resins, and heat treated crys-'. ‘ ample, a halo formyl‘ halide may be‘ caused to tallized rosins. -> be reacted Withatosin- alcohol; > The acid halide ' Q 5 2,404,213 reaction may be carried out by causing a rosin alcohol or an ester or alcoholic derivative thereof to be reacted with a halo iormyl alkyl, aryl, or aralkyl ester. It is preferred to use the rosin al coholate when carrying out the reaction. A suit able halo formyl ester may be the chloroethyl ester of carbonic acid. It is preferred to use an excess of the chlorocarbonic acid‘ ester, for ex through a suitable solvent solution of a rosin al coho1 causes the formation of the various rosin carbonates. ‘Ordinarily, when the reaction is car ried out at room temperature, a mixture of neu- I tral and halo rosin carbonates is formed wherein ' the halo rosin carbonates predominate. A greater percentage of the neutral rosin carbonates is . formed when the halo formyl halide-rosin alcohol ample, about 25% excess which is slowly added to ‘ reaction is carried out at the increased reaction the rosin alcohol during mild stirring of the-mix 10 temperatures and reaction time. Generally, the ture. An exothermic reaction takes place-with time required to carry out the halo-formyl ester the evolution of a relatively large amount of heat. rosin alcohol and the halo-formyl halide rosin The resulting solution may be vacuum ?ltered to alcoho1 reaction may vary between about 1/2 hour remove the sodium chloride precipitate.- Excess . and about 10 hours but, in general, equilibrium is chlorocarbonic acid. ester and solvent may be re 15 reached in from about 1 to about 2 hours. The moved by means of distillation. The time of the temperature for thesetwo types of reactions may reaction may vary from about 3 minutes to about vary from about 10° C. to about 100° C. but the 1 hour but, in general, the reactionwill take place reaction usually takes place at about 20° C- to in about 10 to about 20 minutes. The reaction about 40° C. ‘ ~ temperature may vary from about 10° C. to about 20 The rosin carbonates are useful in the manu 100° C. The proportion of neutral rosin car facture of adhesive compositions; 7 bonates and halo rosin carbonates in the reaction “What I claim and desire to protect by Letters mixture will depend in part upon the conditions Patent is: of reaction including temperature, time, and re l. A mixed ester of carbonic acid and a hy action components. Generally, the lower tem 25 drogenated rosin alcohol and an alkyl alcohol. peratures and relatively shorter periods of re 2. A mixed ester of carbonic acid and a hy action time are more conducive to the formation drogenated rosin alcohol and methyl alcohol. of the halo rosin carbonates than to the forma 3. A method of producing a rosinyl carbonate tion of the mixed and neutral rosin carbonates. which comprises reacting a haloformyl halide with The concentration of the rosin alcohol in benzene a rosin compound selected from a group consist ' or any other suitable solvent may vary from about ing of a rosin alcohol, its acetate and its al 10% to about 60% and preferably, may be be coholate. tween about 15% and about 30%. 4. A mixed ester of carbonic acid and a poly When the acid halide reaction is carried out merized rosin alcohol and an alkyl alcohol. using a halo formyl halide and a rosin alcohol, a 35 5. A mixed ester of carbonic, acid’and an alkyl mixture of halo rosin carbonates, neutral car alcohol and a rosin alcohol selected from the bonates and mixed neutral carbonates result group consisting of a hydrogenated rosin alcohol, wherein the neutral rosin carbonates predominate. A preferred halo formyl halide in this reaction polymerized rosin alcohol, dehydrogenated rosin alcohol and heat-treated rosin alcohol. is, for example, phosgene, which, when passed 40 JOSEPH N. BORGLIN.