USRE14530E - Tebxaoixkt o office - Google Patents

Description

firstis'ection of the reissue of my Patent No. portion .of thesameinthe-composition, The

i method of forming same, which itself'is a ticns containing a solvent's omewhat broadly compositions for, moldin various articles, in the appl which constltlllles the phenol'br cresol, by condensation with forreferred to. It is formed by the reaction of rea'ctionjth'ereof with formaldehyde, prefer-. is preferably heated to complete dehydraterm a a solid solvent element or plasdehydration and removal of excess phenol it 40 pr cesses for making-the same. acetate, acetic acid, acetylene tetrachlor d,

solvent'or plasticity ingredient. gSuchprod F. It melts ab oiit 220 F. but has no sharp STATESFIATENT orrrcn.

mister-mutants; or" East onairoti, ijs' ixs'srnon 'ro connnnsrrn comf'm or AMERICA, a scare I fr'ron or new Jnnsmr.

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14,530. Y v lm i 9 i i i i Patent Rigi'ssued Oct. 8,1918; no mawing. ori-g'inalfapplicationlfileylqg14, 1909, Serial NoIABGpGO. (Patent"NQ. 1-,-102,B3Q,-)- Dividedandapplication'flledqiine 2, 1811-, Serial No. 630,894; (l atent'li'o. 1,111,285.) Divided and applicjationfled Kay 2, 1912, seen no. 694,644. (latent No. 1,087,422, dated February-11,393,) Diyidcd and this application or reissue med Ianuary 8 ,-.191fi.. seriaknqg'gghqglg- 'DIVISiON"A. Taall'whom it may concern: referred to, but a product having many of Be it known that 1, Jonas W. Arwwonrrr, the advantages of this preferred product a'citizen of the United States, and a'resident may be formed when various of the shellac of East Orange in the county of Essex and substitutes or phenol resins now known are 5 State of New ersey, have invented certain usedin the place of the: particular phenol new and useful Improvements in Plastic re's'iureferred-to. lhe' degree of plasticity Compositions, of .which the following is a ofthe composition, upon subsequent applid'escription' Y cation of heat, will vary in accordance with- .The present application constitutes the the plasticity ingredient used, and the pro- 1087422 granted February 17, 191i, which present appli'cationcontains the same claims patent is a, d'vision of my Patent No. as said'l atlnt No. 10874522 of which it con- 1,111,285, granted September 22, 191 1, en st'itutes the first section of the reissue, titled' Phenolic, condensation product and namely a generic laim covering composidivision of my Patent No. 1,102,630, granted" expressed," and spec fie claims in which the July 7 191 1, entitled Composition and procsolvent is a chloro d liYatiS'e f naphtha ess of manufacturing the same. The parentlene; Naphthalene itself is not specifically:

Patent No. 1,1 02,630,-relates to and describes claimed as a solvent herein, but is so claimed such as maybe made frd m celluloid, hard- 011(1'560131011 of the reissue;

rubber,- and kindred substances, and also'the The" fusible phenol resin, preferably used, production of synthetic resins. 'llhe latter and processes for making the same, are ful y is a hard 'fusible phenol resin made from described 1n my parent Patent, No.1,102,630,

maldehyde, and the former is an ultimate a phenol and formaldehyde in such proporinfusible oondensationproduct of" a phenol tions that the phenol is almost entirely comand formaldehyde or equiv lents, preferably bined withathe formaldehyde and there is made from the phenol resin referred to, by no un'combined or free formaldehyde. It

ablyin. polymerized form, in definite pretion before being used as an ingredient in determined percentages, The ultimate, inthe making ofthe ultimate infusible product,

fusible product referred to, is very hard which dehydration requires about 400 and chemically iert. It may have whatgi of heat at atmospheric pressure. After such ticity' ingredient incorporated therew1th, is a hard resin, very similar in texture to and my divisional Patent No. 1,111,285, recopal and kauri gum. It issoluble in all ferred to, describes and broadly claims comproportions in acetone, amyl, ethyl, methyl positions containing such an element, and and butyl alcohol, amyl, ethyl and methyl My 'said Patent No. 1087422 relates to and and mjono-nitro-benzene, (oil of mirbane), will claim such compositions containing from which it remains unchanged after naphthalene or various chlorin s'ubstituevaporation of the solvents. It is fusible and tion products of naphthalene, asthegsolid practically unchanged when heated to 420 ucts,-whileinfusible, varesufficiently plast ij, melting ,point, passing: through various deon 1 application of" heat as 'l16relIi:alIi1de{ grees of viscosity, untilat 250 F. it may scribed, to be shaped or pressed intoform I readily jbe poured -and" at ;;350 F. it becomes at suitable, temperatures. This infusible, quite?-thinly fluid- It acts as a weak acid 10C 50 thermoplastic product, as 1 term it, is towardflbases with which it combines.

preferably formed from the phenol resin-f 'will ii'ot form an infusible condensation" piesf th gphthalic anhydrid,

b11183 therewith an product when heated alone or with condensmg agents, at any tem erati'ir'e, When mixed with formaldehy e, 'paraformaldehyde or tl'ioxymeth lene, and heated, it com forms a hard infusible mass, which, if not admixed with other free p enol is less them-10 when no counteractin pressure is excessv escapes as bub les in the mass and renders the latter'useless for some purposes. As described in my patents referred to,

per cent.

used, thd

the .ultimate infusible product is preferably 1 product by counteracting the the product in the ingjheb i j above mixture the same naphthalene.-

although I do tubes,

formed by incorporating resin as described, from one, or dioxym'ethylene, which The phenol resin. is 11011- is purp oseare naphthalene and some of itschloro derivatives, such as tetra-chloro- The final prod v ment contributes greater toughness to the rittle nature of the ultunate product and renders the baking temperature, render it plastic at such temperature, and remain asa p be incorporated with the mass. ,-This element takes care of traces of water which may aking operation. a ,clearer and v more; transparent not regard the inclusion of this element as absolutely essential. Examis class are benz oic anhydrid,

and anhydrlds with the mass, and are not decomposed at temperatures used.

Having obtained the may be castin suitable molds for the formation of articles or for the formation of or slabs, or the like, from which the desired articles may subsequently bemade 7;- per cent., whenwith such a phenol 5% to 10 per centg-f of theweight of the resin of polymerized, anhydrous formaldehyde, as trioxymethylis caused to.

vated uct solvent elev operation. Such anproduct orcombine therewith at Lmerized, may be used condition of solid solution" d, a water? be expelled dur I f This results in product,.

any such organic as are soluble in and misclble the desired rods, sheets,

eating may be accom- I y casting in suitablesteamacketed time may vary ing on the thicknessof the, article and the character of the mass. ,Thin sheets and small articles may behardened in afew hile larger masses and objects of may require gradual heatthe. reaction to heating at such temperature, or at an eletemperature, for several hours. The ultimate product so formed *will not melt at anytemperature below that position, but will soften and become sulficiently plastic at from 240, to-BOO? F, to be further shaped by pressing in suit his dies or molds. The degree of plasticity may becontrolled to a certain extent by thenature of the solvent ingredient and propor- Jtions thereof, and y varyin the -proportions of the polymerized ormaldehyde, added to the phenol resin. l l

In the mixture-ofi "gre'dients the polymerized formaldehydeis used in an amount wh' h combine with nearly all the'resin, so that there maybe no excess of formaldehyde or. polymer thereof to cause bubbling of the mass during the hardening tween 5 and 7% per cent; of the phenol resin usecl Formaldehyde not polyduring the process. It is: practmal to make the phenol resin entirely ree from uncombined phenol, and the small variable percentage of phenol for the ultimate product to vary age of free phenol, ascertained combines with a much greater proportion of polymerized formaldehyde than does the phenol resin. By varying the percentage of the polymerized formaldehyde as indicated, the free phenol in the phenol resin may. all bf talgen into combination. The product t us 0 usually iIn-T 115 of its d o necessary in the formation of the'mixture tained after heating the phenol resin .120 para-formaldehyde in the mixture with the similar products, notably in that it softens sufiiciently to allow further shaping, as

stated, at a temperature between 24 and 300 F., while at the same time it is infusible at any temperature lower than that of its decomposition, and also in that it is tougher and less brittle in texture. These results are largely attributable to the presence of the solid solvent or plasticity agent described. The product also has other advantages, as described in the patents referred to, in that it can be made of exact and definite ultimate composition, under perfect control, by the process particularly described, without the necessity of counteracting pressure, and the product so formed is unusually free from as bubbles. I

The mass of the ultimate condensation product is normally of amber color and trans arent. It may be made practically color ess if special precautions are taken'to exclude color-giving impurities from the phenol and to exclude oxygen during subseuent heat treatment. It may also, if desired, be given any desired color by the addition of suitable pigments. Chemically inert cheaper substances in powdered or fibrous form may be incor orate with the mass before baking in widely varying per cents. when desired.

Preferred formulae for masses which are to be hardened in molds without subsequent pressin operations are as follows For 'ght colored and transparent products. 40' Phenol iresln- 100 parts by ei ht Na hthalene' 5 to 10 i u 1; Po ymerlzed tormaldehyden 5 to '7 Phenol resin 100 In it n Ben'zolc nnhydrld 2 to 4 H u u Naphthalene 5 t 10 u n u Tri'oxymethylene 5 t 8 u u n For non-melting plastic compositions. Phenol resin 1 0 parts by weight Naphthalene 10 to 40 araformul'dehyde 5 to ii u P1181101 resin '100 u u 4| Naphthalene 10 to 20 Benzoic anhydrid 5 u u v n Paraorma1dehyde. 5 to 10 i Phenol resin i 10 u n u vTetra-chlore-naphthalene 10 to 5 u I u u Benzoic anhydrld 1 t 5 H u Paratormaldehyde 5 t g u n The specific gravity of a similar composition, given as example, was found to be as follows? Phenol resin '100 parts by weight. Specific Tetra-chloro-naph gravity 1.324 thalene 20 O lesoent .Paratormaldehyde- S am or color.

The specific gravity of the phenol resin be 1.240. This substance and varies in tint from colorcofiee shade.

used was found to is transparent 66 le$ to a dark is heated for appreciable extent, by water,

' of the phenol resin,

In all of the formulae given above for the ultimate condensation product, the ingredients are mixed and freed from air bubbles by standing in molten condition or by vacuum treatment or by centrifugal treatment at temperatures below 250 F. or freed from air bubbles in any other suitable manner. The mass is then poured into molds and is preferably heated to a temperature 0 from 260 F. to 270 F. at which temperature it is maintained for a sufficient time to render the mass infusible, and subsequently a short time toa temperature of 300 to350 F. The ingredients may also be heated to from 320 to 350 F. under counteracting pressure, as is done in the artof vulcanizing rubber. When no counteracting pressure is used, from one-half to four hours is required before the final temperature may be reached, this time varying with the thickness of the object molded.

Naphthalene, when in solid solution with the ultimate condensation product, does not volatilize perceptibly at ordinary temperatures, when within the proportions given in the examples, although naphthalene does tend to volatilize slowly when alone. The chloro-naphthalenes referred to, when in the ultimate condensation solid solution with product, do' not volatilize either at room temperatures or at 212 F. Naphthalene and the chloro derivatives are also practically insoluble in water at room temperatures. The ractical non-water-solubility of the solvent or plasticity ingredients referred to is avaluable -feature,because such ingredients cannot be removed from the mass to any even when the mass is in comminuted form, and furthermore masses made including such ingredients are not so susceptible to the infliience of moisture in the atmosphere as are compositions containing ingredients such as glycerin, which are soluble to a very great extent in water. Condensation. products containing glycerin, for example, constantly attract moisture from the atmosphere, because of the hygroscopic nature of the glycerin. The plasticity ingredients referred to also all have 'melting poi ts substantially lower than their boiling poi ts which is an important property, since thereby all the ingredients of the composition can be mixed in fiui condition, and the plasticityingredient used will not volatilize away during the mixing or hardening reaction.

When naphthaleneor equivalent solid solvent is employed in considerable proportion, for instance, in the ratio of 10 to 40 parts by weight of naphthalene to 100 parts by weight I find that as the percentage of naphthalene approaches an reaches the maximum figure stated, the composition is' characterized by being liquid at' somewhat above normal temperatures, and

its

fiable conditiondesi'rable. At the sametime the naphthalene g for the in the therefore will be of she for Such industrial uses as may make aninitialliquid of -liqueor other solvent remains,

elastic while hot. n comfpositions using consider: able proport ons o naphthalene, the chemcal reaction under the influence of heat takes substantial evaporation, the .P

place without, final product; being an infusible, more or less gelatmons mass, so ning under the effects of heat.

} further, mg;;-'entirely the property of, heat, which imparts to it elasticity or flexi bllity. On account of its high boiling point, the solvent remains in the mass, harmless the range of unexpelledi throughout king temperatures, so 'that the objectionable reduction of volume or shrinka e a whenever low The above observations are by. evaporation which occurs unav'oidab y boiling point solvents, like alcohol are used, does not more, it brings about the a most desir ble factor, still further 'to prevent which contributes interior stresses. particularly pere second section, present reissue.

tinent with respect to th above referred to, of the The 'term fusible as qualifying a product such as my phenol I resin, denotes a product which melts and bein the claims of this ing my ultimate comes liquid, Whensufiiciently heated, under atmospheric pressure. The term infusible application, as qualifyroduct, denotes a substance which does not d ow heated to any temperature, under atmospheric pressure. en an ultimate product solvent element is added, or an excess; of phenol resin is used as a solvent for the ultimate product, as stated, the massbecomes silfiiciently plastic to be readily pressed or molded to shape, but does not fuse. This application positions containing naphthalene or various greater part at least, incorporated fVerylong application of heat "may without however removi softening by interfere; further-- increased elasticity,

appearing in the claims or become liquid, when covers, as stated, com-.

derivativesthereof as the solid solvent or plasticity ingredient The The-word phenol as employed in the c s is intended to include the equivalents of. phenol for the purposes of this invention, and the word fformaldehyde is-intended to include equivalents of formaldehyde.

ters Patent is v 1. As a new composition solution ofan ultimate infusible'fphenolic' condensation product and a solid [solvent therefor consisting of a condensed {ring compound having tWo closed "chains with carbon atoms commonto both. v

-2. As a'. new composition of matter, a solid solution 'of an ultimate infusible phethe polymers and other recognized ving now described my invention what I claim as newand desire ,to protect by; Let- Dimme an 'nolic condensation product and tetra-chloronaphthalene. v

3. As a new composition of matter, a solid solid higher chloro derivative -of naphthalene.

.This specification signed and witnessed I this 29th day of December, 1915. v

- JONAS W. AYLSWORTH. Witnesses:

Dm SMITH, I FREDERICK BAGHMANN.