Патент USA US2407414код для вставки
I‘ ; 2,4c7,413 Patented Sept. 10,1946 '7 t ' V 2,407,413‘v _ V _,; i, . rms'rroizien smash-Mamie RESIN‘ ., , I I COMPOSITION I e a r Howard "Pittsburgh L. GerharteMilwaulrec, :Plate >Glassv, Company, Wis; assignoritq' Allegheny _' County, Pa., acorporation:.otl’cnnsylvania»' v _ 7:' .“No'Drawing'. ' '~ ‘SerialNo.395,062 Application‘MayM', ,5 1941," - i 5 ii‘ Claims. (oi. 204%158) before’ solidi?cation, withoutobiectionable effects ' The present inventionrelates to-arti?cial resins and it has particularrelation to such resins as‘ are obtained by reacting ‘substituted or unsub upon, the reaction. The, resin, under. appropriate ' donditionasetsinto a transparenhhard, bubble “ jfree,iiand weilplasticized solid, which is" not sub~ stituted ethylenea-wsdicarboxylic acids or an hydrides thereof». with' a] poly'merizable ole?n. " One objectfof the- inventionvv is to provide a vEject toi‘warping- and, cracking and which main» tains'its properties well upon aging. - ' I The reaction to form the new resins is typi?ed clear, hard, toughystable and well, plasticized by that between'maleic acid or maleic acid an -' resin or the above type which is relativelyzfree yhydride' and styrene. The two'com'pounds, along from bubbles or cavities; withfanv ester oilevulinic acid, are ,simpiy'ad A second object of the marinara Mayne» ~10 mixed directly or are introducedinto a solvent a resinifying‘?uid material thatYc'an be cast,",or :suchas triacetin. and are then caused to react canvb'e employed]as'anl'investment median and’ by .actinic irradiationatq'atemperature within they range of about 20 to 50° Irradiationgof vformedlinto' clear, hard, durable'and tough‘ bodies at low temperatures andfwith but‘. little ‘distortion. A third object of the; inventionis'to provide the reactants may be continued throughout the period of reaction, but it ‘maybe discontinued , an; improved method of.‘ incorporating?a,fplas- ticizer with the resin; _ I . > _ - after the ‘reaction hasl started. It is also‘ pos sible to introduce a smallamountle-g. 1 tomes) V vThese and other objects will be apparent from of preliminarily irradiated reactants into the '7 consideration of the?following specification; and the appended claims. v a‘ main batch and thus to obviate further irradia- _ . - It has heretofore beenproposed to heat an un *ti'on. or its anhydr’ide and'a: polymerizableole?n such as styrene to Obtain polymerization products of ' > . . _ . ~ , ,, "Reactionimay also be initiated by application saturated dicarboxylic acidfsuchjas maleic acid .of-heatandafter it has progressed su?iciently ' far,'heating- isldiscontinued. , .If very hard prod whitev powdery character, which are soluble‘ in v25 ucts'iare desired the mass‘may ,be,,?nally heat acetone and dilute alkalies; ' ’ ' ‘treated at a-suitable temperature (e_._ g, 100- - ~ My copending application ,Serial .No. 242,127, 200°? C.) until the desired stage is reached. .The filedNovember-23, 1938, nowPatent'No. 2,297,351, is based upon the-discovery that unsaturated di carboxylic acids of the type of jmaleic‘acid, or maleic anhydride, or fumaric acid, or substituted hour or less, but byyreduvcing the degree or time reaction can be brought to completion within an , of~irradiation it is possible to extend it ofv'er a period of several days. . ~ . ; _- » ' - The reaction product obtained from maleic an— ‘ ,maleic or fumaricacid and polymerizable .oleflns of the typelof'styrene will under the in?uence of _ "hydride and styrene may be represented by the v‘formula. actinic. radiation react to form clear and hard resins which are relatively insoluble and substan ‘ tiallyjfree of 'voids} Theseresins are well adapted for molding, cutting, pressing, or'otherwise form-'‘ 'ing into bodies of great beauty. The resin-form Where :0 represents the number of the foregoing Y ing reaction may be carried out completely or at groupsin the molecule and is of ‘variable value.’ ‘Since the reaction isgeneral in character and applies to many unsaturated dicarboxylic acids or anhydrides; ‘i. e., substituted maieic or fumaric least in its final stages bycasting the'reacting - mass in a suitable mold, thus obtaining directly the ?nally desired object. _ However, considerable dimculty has been ex perienced in adequate plasticization of'the resin in order? to obtain clear, hard and tough, bodies, that maintain that condition over long periods of time. Very few plasticizers are adequately com ' acid and to' many of the polymerizable ole?ns, the 3 product may be represented by the type formula: patibleito admit of'satisfactory use and those that are compatible usually are too volatile to ad mit of permanent plasticization. ' ' ' ., where the groups R1, R2, ‘R3, R4, R5, R6, may be practically any of the possible substituent groups. The present invention is based upon the dis covery that methyl‘ levulinate is of outstanding Ex'amplesof a few. of the possibilities include hy ' merit as a plasticizer for resins of the foregoing type. It can be incorporated with the reactants ' prior to or during polymerization, but preferably 'drogen and chlorine, carbonyl, carboxyl, alkyl, ' aromatic and the like groups. Examples of pos $407,413 4 under heat and pressure, or the comminuted ma slble ethylene a p dicarboxylic acids or ethylenic dicarboxylic acids which are transi'ormable to a 5 form, which may be'employed, include 'maleic acid (above described), fumaric acid, the mono terial may be mixed with further polymerizable ‘ ' material which by appropriate treatment will be converted into hard bonding resins. Oil-soluble ' V UK ' dyes, such as Thodamin B. Victoria Green and pigments such'as titanium dioxide may be incor- ' alkylated maleic and fumaric ' acids, such as or di chloro substituted maleicland fumaric acids, porated into the resins prior to ?nal solidification. The ‘new resins may be employed in the for itaconic, citraconic acid, mesaconic acid,'mono and di phenyl maleic acid, benzyl maleic, dibenzyl mation of optical lenses, jars, or lids for jars for maleic, ethyl maleic, or any similar acids con taining ‘a doublebond in the chain between the 10 cosmetics, drugs,’ foods and the like. They may be cast or cut to form an in?nite variety of han two carboxyl groups. dles, buttons, and objects of similar nature, or The number of polymerizable ole?nic com-.4 pounds is also very large and of general charac ter. It includes styrene above described, vinyl acetate, vinyl chloride, methyl styrene, parahy cast about specimens or objects of art to effect an embedment thereof. They may also be used 15 for the formation of panels and coverings for electrical apparatus of a great variety. Application of the principles of the invention droxy styrene, acrylic acid, methyl, ethyl, or other esters of acrylic acid, acrolein, unsaturated ke _ is illustrated by the following example: tones, such as methyl vinyl ketone, indene, cou marone and the like. It is to be understood that anyone or‘ more of 20 Example I v y . ' Grams the dicarboxylic acids can be combined with any Maleic anhydride __________ ______; _______ __ 25 one or more of the ole?nic compounds, to pro Styrene 35 _____ _~_ ________________________ .. vide resins in great variety. The ratio of the di Methyl levulinate _______________________ __ 30 carboxylic acid to the ole?nic compound is sus In the above example the mixture was Prefer ceptible of wide variation, but for purposes of 25 ably brought to a temperature sufficient to ob illustration may be considered as approximately 'tain mutual solution of the components. Poly molar. \ merization'was then effected by irradiation with ‘ As previously stated, the reaction can be con-. The rate of polymerization was ducted in the absence of solvents. However, in controlled by increase or decrease of the intensity some instances it may be preferable to dissolve or 30 of irradiation and/or; the temperature. It can be admix the reactants and the plasticizer with sol brought to completion by irradiation with direct vents such as triacetin, acetone, methyl ethyl ke ‘sunlight for a few minutes (15 or 20), followed tone, ethyl aceto acetate, diacetone, acetic anhy by exposure to ‘subdued light for some six hours. dride, mesityl oxide, or any other solvent for the These exposures may take place at room tem reactants. ‘ ' actinic rays. 35 oxidizing agents such as benzoyl peroxide‘may . be employed to speed up reaction of the resins forming materials. Reducing agents, such as hy droquinone pyrogallol, tannic acid, etc., maybe ‘ employed to retardreaction. The solvents in many cases are imbibed in the resinous reaction product without dissolving the latter and when so incorporated can not readily be removed ‘by evaporation. Therefore, they may perature oi: slightly above, if so desired. The product, may also be ‘further hardened by heating. But slight distortion takes place during poly merization. The resin is of exceptional clarity and is not subject to change of color upon aging. All of these qualities combine to provide a resin par excellence for embedding specimens, such as insects, flowers and biological specimens. An ob ject, such as a beetle can be introduced into a be retained as permanent components of the res 45 solution of styrene and maleic acid or anhydride inous body. The bodies still retain their clarity, aplasticizer in a container'of suitablev hardness and toughness and usually are bubble _ containing size and shape and. the reaction to form the solid free. The solvated resins may be hardened by resin effected, at temperatures sufliciently low to baking them for a shorttime. obviate damage to the specimen, merely by mild As previously stated, the resinous bodies are in 50 irradiation. There is no damage to the specimen, soluble, but it is possible to cast incipiently poly due, to shrinkage and distortion of the medium merized masses into molds in which hardening during setting. The reaction is sufficiently rapid to final form is effected. It is also possible to to be commercially feasible. I conduct polymerization in molds formed of soft Example II glass, Pyrex, or other material transparent to ac 55 tinic rays. Likewise it is possible to introduce A sample of a solution from Example I was reactive mixtures containing at least a portion of ‘placed between two glass plates of soft gloss and irradiated material into opaque molds of rubber irradiated for one hour as described. The resin or plaster and then to complete polymerization. 1 formed as a thin film between the plates which / It is also possible to heat the resins .to the soft 60 were not easily separated. . ' ening point and then to press them to shape. A further application of the invention consists , ' '7 _ Example III, A portion of the solution of Example I was in providing a layer of» polymerizable materials irradiated for ?ve minutes until it had congealed and plasticizer between two sheets of glass. By irradiating this glass, it is possible to form a film 65 to incipient gellation (the mass could still be poured). This enabled more of the material to of transparent closely adherent resin between the be placed between the plates. During the second glass sheets, thus forming a safety glass. The 15 minutes of irradiation,‘pressure was applied materials may be partially polymerized prior to to the plates: The ?nished plates adhered well application to glass. In a similar manner this ' class of resins maybe employed in the lamina 70 and shattered with difficulty. In the foregoing examples the vdicar'boxylic tion of wood, fabrics or other materials. acids and their anhydrides are to be considered Resinous bodies can be cut to any’ desired as equivalents, since each anhydride is derived form and then polished to provide a great variety from the acid merely by elimination of a mole of’ articles. . The resins and‘ scraps. of the resin. may be shredded lor powdered and then molded 75 of water and, the ester. is the. same regardless 2,407,413 5. A method of forming a hard, strong plas 01' whether the acid or the anhydride is employed. Therefore, the term anhydride in the claims in ' vticized 'styrene-maleic anhydride resin which comprises conjointly polymerizing about 35 parts cludes the acids and the term acid includes the anhydrides. by weight styrene and about 25 parts by weight The embodiments of the invention herein de- . scribed are merely exemplary and numerous mod i?cations may be madetherein without departure of maleic anhydride in solution in methyl levu linate to form a resinous body in which the methyl levulinate is imbibed as a plasticizer. 6. A process as de?ned in claim 5 in which , from the spirit of the invention or the scope of the appended claims. the methyl levulinate is in a ratio of about 30 - 10 parts by weight. What I claim is: 1. A method of forming clear; hard and strong maleic acid and methyl levulinate and then sub-. 7. A process as de?ned in claim~5 in which the polymerization is‘ effected by irradiating the solution with light at about 20 to 50° C. a.v A process as de?ned in claim 5111 which jecting the styrene and maleic acid to polymer polymerization is e?'ected by heating the solu- ‘ ization‘to form the-resin in the presence, of dis, tion to reaction temperature. plasticized bodies ofv styrene-maleic anhydride resin, which method comprises admixing styrene, 9. A process as de?ned in claim 5 in which solved methyl levulinate. I about 30 parts by weight of methyl levulinate is 2. A process as de?ned in claim 1, ‘in which polymerization is effected byv irradiation of the reactants with actinic rays. ‘ a 20 3. A method of fanning clear, hard and strong rplasticized bodies of styrene-maleic anhydride employed and the polymerization is effected by irradiating the ingredients with actinic rays at a temperature of about 20 to 50° C. ~' 10. A process as de?ned in claim 5 in which polymerization is effected by heating the mate , resin, which method comprises mutually dissolv rials approximately to the range of 100 to 200° C. ' mg heating ‘maleic anhydride, styrene and 11. A process as de?ned in claim 5 in which , methyl levulinate, then polymerizing the maleic 25 ‘the methyl levulinate is in a ratio of about 30 anhydride and styrene in the solution to form said resin‘. , - ' ' 4. A process as de?ned in claim 3, in which the polymerization is effected by irradiation with actinic rays 'at a temperature 01 about 20 to 30 50° C. ‘ ~< parts by weight and polymerization is effected by heating the materials up to a temperature within the approximate range of 100 to 200° C, HOWARD L. GERHART.