Patented Sept. 2, 1943 2,330,033

UNITED STATES PATENT OFFICE 2,330,033 METHOD OF PRE PARNG METYLENE MALONCESTERS Gaetano F. D'Alelio, Pittsfield, Mass, assignor to General Electric Company, a corporation of New York No Drawing. Application November 16, 1939, Serial No. 304,783 6 Claims. (C. 260-485) This invention relates to the production of Or the said composition. The general reaction Inay, ganic plastic masses having valuable and char be written graphically as follows: acteristic properties that make them especially CO OR COOR ? OH- - ? + suitable for use in industry, for example in mold CE * - CHO - HOCH-C are-m-d ing, laminating, casting, coating and adhesive N - HO applications and for other purposes. The inven COOR Co-oR tion is concerned more particularly with a novel cooR method of preparing methylene malonic esters. This application is a continuation-in-part of Chi-c. my copending application Serial No. 224,799, 10 coor filed August 13, 1938, now Patent No. 2,277,479, or, with a molecular excess of formaldehyde, . issued March 24, 1942, wherein the methylene COOR OCH COOR malonic esters (ethylene compounds in which ? OH- N H+ both bonds of the beta carbon atom of the ethyl ene molecule are attached to two carbon atoms 5 COOR HOCH CO-OR which are at least double bonded) were shown to be very active polymerizing substances. Applica CH-C coor-- CHO tion Serial No. 224,799 is a continuation-in-part of my copending applications Serial No. 169,465, COOR fled October 16, 1937, now Patent No. 2,239,440, 20 In the above equations R, represents an aliphatic issued Apr. 22, 1941, and Serial No. 205,007, filled or aromatic hydrocarbon radical such as methyl, April 29, 1938, now Patent No. 2,276,828, issued ethyl, propyl, isopropyl, butyl, amyl, hexyl, Octyl, March 17, 1942. All of these applications are allyl, methallyl, crotyl, phenyl, cyclohexyl, meth assigned to the same assignee as the present in Oxy ethyl, etc. vention. 25 by the above method I have been able to obtain To the best of my knowledge and belief Only not only methylene dimethyl and methylene di dimethyl and diethyl methylene malonic esters ethyl malonates, but also new and heretofore un heretofore have been known (see Berichte 22, known esters of methylene malonic acid. These 3295, Annalen 273, 43, and Proceedings of the esters are useful not only in themselves but I Chemical Society, 73,333-340), these having been 8 have found that they are particularly adapted for prepared either from sodium diethyl malonate the production of new and useful copolymers by and methylene iodide, or by the reaction of di copolymerizing the monomeric or partially poly methyl or diethyl malonate with formaldehyde merized ester with other monomeric or partially in the presence of a base. These methods have 5 polymerized organic compounds containing a not been satisfactory, since, the results were erratic and yielded an average of not more than /N N. 10 or 12 per cent of methylene malonic ester, grouping, more particularly a accompanied by a considerable amount of tar. I have discovered that improved yields of methylene malonic esters, more particularly 40 yields of the order of 30 per cent and higher, can grouping, a fact heretofore also unknown. be obtained by reacting (condensing) a malonic Illustrative examples of some of the methylene ester with formaldehyde in the ratio of one mol malonic esters which advantageously may be of the former to at least one mol of the latter and 45 prepared by practicing this invention are methyl under alkaline conditions to form a methylol de ene dipropyl malonate, methylene diisopropyl rivative, acidifying the mass, dehydrating the malonate, methylene dibutyl malonate, methyl acidified mass to obtain a composition comprising ene di- (secondary amyl) malonate, methylene a methylene malonic ester, and separating the d-(secondary butyl carbinyl) malonate, methyl methylene malonic ester, as by distillation, from 50 ene di- (diethyl carbinyl) malonate, etc.

2 2,330,033 Illustrative examples of some of the malonic esters, many of which are new, which I have pre carbonate, potassium hydroxide and carbonate, pared and which may be reacted with formalde barium hydroxide, calcium hydroxide, ammonia, hyde as above briefly described to obtain sub methyl amines such as trimethyl amine, etc., di stantial yields of the corresponding methylene ethyl amine, triisopropyl amine, ethanol amines 5 Such as mono-, di- and tri-ethanol amines, malonic esters are: pyridine, morpholine, triisopropanol amine, etc. Mixtures of bases also may be used. I prefer to use as the basic catalyst inorganic bases and basic Malonic ester Bolling point, C. tertiary nitrogen compounds. O Methylmalonate.------Ethylmalonate------198. 8. To effect acidification of the alkaline con Propyl malonate------98.5-99 at 4 mm. pressure. densation product (methylol derivative of the Isopropylmalonate.----Butylmalonate------93-95 at 12nn. pressure. malonic ester) any Suitable organic or inorganic Secondary amylmalonate - 128-133 at 5.5 mm. pressure. acid may be used, for example hydrochloric, sul 2-ethylbutylmalonate.---- - 106-109 at 1 mm. pressure. Hexylmalonate------129-137 at 2.5 mm. pressure. furic, phosphoric, oxalic, acetic, acrylic, malonic, Methyl isobutyl carbinylmalonate- 123-137160-166 at 46 Inn.nin. pressure.pressure. Crotonic, propionic, chloroacetic, chlorosulfonic, Octyl malonate------188-193 at 4.5 mm. pressure. etc. Substances which liberate acids in aqueous Allyi malonate------118-122 at 10 mm. pressure. Alpha ethylhexylmalonate. 160-195 at 4.5 mm. pressure. Solution also may be used, for instance phos Isobutyl carbinyl malonate. 143-146 at 4 mm. pressure. phorus trichloride, phosphorus pentachloride, etc. Secondarybutyl carbinylmalonate- 142-149 at 3.5 nm. pressure. Diethyl carbinyl nalonate------129-135 at 4 mm. pressure. AC acidifying agents also may be used acid salts Methyl propyl carbinyl malonate. 119-123 at 4 mm. pressure. 20 such, for example, as sodium diacid phosphate, Ethoxyethyl malonate.------145-149 at 4.5 mm. pressure. Butoxyethylmalonate.----- 165-170 at 4.5 mm. pressure. etc. Mixtures of acidifying agents also may be Methoxyethyl II) alonate--- - 129.5-30 at 2 mm. pressure. used. MethoxyOnate. diethylene glycyl, mal- 190-205 at 1.5 Inn. pressure. The methylol derivative is dehydrated by heat Ethoxy diethylene glycylmalonate 180-187 at 2.0 mm. pressure. ing at atmospheric or reduced pressures in suit Butoxy diethylene-glycylmalonate 200-222 at 1.5 mm. pressure. 25 able apparatus, with or without stirring to facili tate the removal of the water, and in the presence In carrying the present invention into effect a or absence of dehydrating agents such, for ex malonic ester is reacted with formaldehyde or a ample, as zinc sulfate, oxalic acid, zinc chloride, polyoxymethylene which engendersformaldehyde 30 etc.monium sulfate, anhydrous copper sulfate, such as paraformaldehyde, trioxymethylene, etc., The methylene malonic esters have boiling at a pH above 7.0 to form a methylol malonic points only slightly higher than the correspond ester, the said reactants being employed in the ing malonic esters, and differ therefrom only ratio of at least one mol formaldehyde per mol within about a 10-degree range. malonic ester. Usually the malonic ester is 35 caused to react with the formaldehyde or its In producing organic plastic masses the methy equivalent in the ratio of one mol of the former lene malonic esters may be polymerized sepa to from one to two mols of the latter. The use rately, or mixed with each other, or mixed with of higher amounts, for example two and One-half other polymerizable bodies. The homogeneous or three dr more mois formaldehyde per mol 40 and heterogeneous polymers vary from viscous malonic ester is not precluded, but no particular masses to rubbery and hard, solid bodies, depend advantage appears to accrue therefrom. After ing upon the extent of polymerization and the the methylol derivative has formed, further re particular polymerizable or other modifying action between the components is retarded by agent, if any, which is incorporated therewith. bringing the reaction mass to a pH below 7.0. 45 Heat, light, or heat and light may be used to ef Thereafter the acidified mass is dehydrated to fect polymerization, although under such condi convert the methylol derivative to the corre tions the rate of polymerization of most of the sponding methylene derivative. methylene malonic esters is relatively slow. In most cases the methylol-forming reaction is Hence, to accelerate the polymerization, I prefer Carried out at a temperature not exceeding Sub 50 to use a catalyst, accompanied by heat, light, or stantially 50° C., preferably between about 0° C. heat and light. Examples of catalysts which may and about 35° C. and in the presence of an in be used are oxygen, Ozone, hydrogen peroxide, hibitor of polymerization such as copper, copper sulfuric acid, aluminum chloride, boron fluoride, acetate, hydroquinone, resorcinol, catechol, etc. superoxides such as aliphatic acyl peroxides, e.g., If desired, the mixed reactants may be heated to 55 acetyl peroxide, stearyl peroxide, etc., peroxides the boiling point of the mixture to form the of the aromatic acid Series, e.g., benzoyl peroxide, methylol derivative but by such procedure the etc. Benzoyl peroxide is the preferred catalyst yields of the methylene derivative are, in gen because of its ease of handling, its relative free eral, somewhat lower than when the methylol dom from explosive hazards and its ready Solu malonic ester is formed by reacting the con 60 bility in the monomeric or partially polymerized ponents within the temperature range of 0 to methylene malonic esters. The rate of poly 50° C. merization is a function of the temperature and In producing the higher molecular weight may be carried out at from room temperature methylene malonic esters a mutual solvent for 85 (20-30° C.) to temperatures materially above the reactants advantageously may be employed. 100° C., for example about 130° C. Of course, if desired, any of the malonic esters The methylene malonic esters of the Saturated may be caused to react with formaldehyde or aliphatic (including the cycloaliphatic) and the equivalent substance in the presence of a mutual aromatic hydroxy compounds, when polymerized solvent to produce the methylol derivative. 70 alone, form thermoplastic materials, that is, ma Any organic or inorganic substance having terials the shape of which can be changed easily basic properties may be used in obtaining the by heat. In contrast therewith, most of the alkaline conditions necessary to form the meth methylene malonic esters of unsaturated aliphatic ylol derivatives of the malonic esters. Illustra alcohols yield, when polymerized alone, insoluble, tive of such compounds are sodium hydroxide and 75 infusible or insoluble and infusible bodies, 2,330,033 3 In general, the properties of the methylene glycol dimethacrylate, allyl methacrylate, meth malonic esters depend upon the number of car ally methacrylate, etc., or mixtures of such sub bon atoms in, and the structure of, the ester stances. grouping. Some of the completely polymerized in order that those skilled in the art better may esters are clear, colorless, rubbery and somewhat understand how the present invention may be ductile resinous bodies. Others are soft, free carried into effect, the following illustrative ex flowing, viscous masses at temperatures of about amples are given. All parts are by weight. 100° C., yet highly viscous or soft, slightly mobile maSSes at room temperature. Some possess prop Eacample 1 erties intermediate elastic solids and dense, mo 10 bile, viscous masses. While still others, as above Parts indicated, are insoluble, infusible or insoluble and Diethylmalonate ------50,0 infusible bodies. Aqueous formaldehyde (37.2%) neutral --- 30.22 In many applications the normally viscous, Sodium hydroxide in 3.6 perts water ------0.15 mobile polymers of high plastic flow are excep Acetic acid ------0.45 tionally valuable, particularly where non-volatil izing materials that can accommodate themselves The Sodium hydroxide solution was added to to the form of the container are required. Par the diethyl malonate, followed by the slow addi ticularly are they valuable when used alone, or tion of the aqueous solution of formaldehyde so when dissolved or dispersed in other dielectric that the temperature did not exceed substantially materials including a liquid hydrocarbon such as 20 10 C. The resulting mass (pH above 7.0) was mineral oil. This property of high plastic flow allowed to/stand for 24 hours at 5 to 25 C. can be used to great commercial advantage in to form methylol diethyl malonate. Thereafter molding processes by interpolymerizing these the acetic acid was added and the solution (pH monomers with other bodies of low plastic flow, below 7.0) distilled in the presence of 0.1 part thereby imparting the desired flow characteristics 2 5 copper sulfate or acetate. Forty-three (43) parts to the end-product. of a water solution, boiling at 95-98 C. and In other cases, for example where it is desired containing methylene diethyl malonate, was first to prepare products of higher softening point or isolated by distillation at atmospheric pressure. of decreased brittleness and solubility, or to pro- : Distillation was then carried out at reduced pres duce insoluble, infusible products, this may be sure and there was obtained 33.24 parts of a dis done by copolymerizing a selected monomeric or tillate having a boiling point of 93-47 C. at 1.5 partially polymerized methylene malonic ester to 3.5 mm. pressure. The pure methylene malonic with one or more other polymerizable unsaturated . ester was isolated from these two fractions by dis materials in monomeric or partially polymerized : tillation, or it may be isolated by other methods state, for example an ester or esters of a polybasic well known to those skilled in the production of acid in which at least two ester groups each Con pure organic chemical compounds. Only 7.6 parts tain an aliphatic unsaturated (ethylenic or of a tarry mass was formed as a residue of the acetylenic) hydrocarbon radical, more particu distillation. larly a Methylene dimethyl malonate was prepared in 40 a similar manner. Eacample 2 radical such as vinyl, ally, methallyl, etc. Also, Same formula as in Example 1. The sodium copolymers of valuable properties may be ob hydroxide was added to the aqueous formalde tained by copolymerizing methylene malonic hyde solution and the resulting solution then esters with one or more other monomeric or partly added slowly to the diethyl malonate while cool polymerized compounds COntaining a ing the mass. The temperature was checked at 33 C. When all the formaldehyde had reacted 5 O with the diethyl malonate, the acetic acid was -CH=c? added and the Solution distilled as described under Example 1, leaving 8.5 parts of a tarry grouping, specifically a residue. 55 Eacample 3 Parts N Dipropylmalonate------0.0 grouping, for example, dimethyl itaconate, di Aqueous formaldehyde (37.2%) neutral--- 5.15 ethyl itaconate, itaconic esters of unsaturated al Sodium carbonate------0.3 cohols, for instance diallyl itaconate, etc., vinyl Acetic acid------0.34 and allyl esters of saturated and unsaturated GO mono- and poly-carboxylic acids, etc., more par were mixed, and refluxed for 3% to 4 hours to ticularly polymerizable materials containing a form methylol dipropyl malonate, then allowed to cool. The acetic acid was added and the solu / tion treated as described under Example 1. CH-C Methylene dipropyl malonate was isolated from the fraction boiling between 83° and 155° C. at grouping, for example monomeric or partly poly 2.5 mm. pressure. This ester started to poly merized styrene, vinyl esters such as the acetate, merize spontaneously in the absence of inhibitors. chloride, bromide, fluoride, etc., vinyl ketones, In a manner similar to that above set forth, methvinyl ketones, vinylidene halides as the chlo numerous other methylene malonic esters were ride, bromide and fluoride, acrylic and metha prepared. In all cases the yields were materially crylic esters, e.g., methyl acrylate, ethyl acrylate, higher than when following the practice men propyl acrylate, butyl acrylate, ethyl metha tioned in the literature for the preparation of crylate, propyl methacrylate, butyl methacrylate, 75 methylene dimethyl and diethyl malonates.

4. 2,880,088 PRODUCTION OF COPOYMERS Part3. (c) Methylene dipropyl malonate------AO Eacample 4 Parts Vinyl acetate------60 EthylMethylene methacrylate------diethyl malonate------waaaaasa O 5 to give a stringy, elastic copolymer. PaS were mixed and treated with 1 part benzoyl per- (d) Methylene dipropyl malonate------40 oxide at 50 C. for 174 hours and 334 hours at Diallyl oxalate------60 100° C. to give a hard, water-white, glass-clear copolymer. The ethyl methacrylate was replaced 10 to give a Soft, friable gel. by methyl methacrylate and propyl methacrylate Parts to give similar products. Isobutyl methacrylate (e) Methylene dipropyl malonate------80 likewise gave a hard copolymer, only slightly Dibutyl taconate------40 softerMethacrylic than nitrilethe ethyl gave methacrylate a hardcopolymerization copolymer. to give a moderately viscous copolymer. product, while the copolyner with butyl meth- Eacample 10 acrylate had definite rubbery characteristics. Eacample 5 These examples illustrate some of the copoly Parts mers obtained by treating 20 parts methylene di Methylene diethyl malonate------10 20 Elaeoatl, and another polymerable Diallyl itaconate------90 g were mixed with 1% benzoyl peroxide and heated -CH=c? for 174 hours at 50 C. and 334 hours at 100° C. - to give a hard, clear, insoluble and infusible 2 grouping, specifically a - copolymer. Methally methacrylate gave a sim- / ilar product, while the copolymer with glycol di- CH=C methacrylate was opaque. Eacample 6 grouping, with 1 part benzoyl peroxide under the Parts 30 influence of heat: Methylene diethyl malonate------10 a Vinyl acetate------an as up o - as a so- 90 (E) 80Ethy methacrylate gave a hard were treated with 1% benzoyl peroxide at 50° C. (b) 80 parts ethyl acrylate gave a stiff, rubbery for 17% hours and at 100° C. for 334 hours. The 35 copolymer. copolymer Was quite hard, Methyl acrylate and (c) 80 parts vinyl acetate gave a stringy, fairly ethyl acrylate gave gummy, rubbery products. stiff copolymer. Eacample 7 (d) 80 E gally oxalate gave a friable, re Methylene diethyl malonate------Parts 10 40... (e) soilethylst y icona t e gave a rubbery, Dimethyl itaconate ------90 gy copolymer. were treated similarly to Example 6. A fairly Eacample 11 hard copolymer was obtained. Diethyl itaconate gave a softer product; dibutyl itaconate, a very 20 parts methylene dibutyl malonate when viscous copolymer; dioctyl itaconate, di-isobutyl mixed with 80 parts carbinyl itaconate, di-isoamyl itaconate, and di (a) Methyl methacrylate dodecyl itaconate gave moderately viscous resins. (b) Ethyl acrylate, or Eacample 8 (c) Dibutyl itaconate Parts 50 Methylene diethyl malonate.------O and treated with i part benzoyl peroxide at 50° Diallyl succinate------90 100° C. for 24-72 hours gave, respectively: were treated similarly to mixtures of Examples (a) A hard copolymer. . 4, 5 and 6 to give resilient, rubbery, friable gels. (b) A stiff, rubbery copolymer. The dially succinate was replaced by diallyl 55 (c) A viscous copolymer. phthalate, triallyl tartrate, diallyl maleate, di ally malonate, trially tricarballylate, diallyl Eacample 2 glutarate, diallyl oxalate, triallyl citrate, dially alpha ally malonate, diallyl azelaate, diallyl 20 parts methylene di-(secondary amyl) malo adipate, and diallyl alpha dimethyl malonate to 60 nate, when mixed with 80 parts give similar products. (a) Ethyl acrylate Eacample 9 (b) Methyl methacrylate Illustrative copolymers of methylene dipropyl (c) Allyl oxalate malonate were prepared in the presence of 1 part 65 (d) Vinyl acetate, or benzoyl peroxide from: (e) Diethyl taconate Parts (a) Methylene dipropyl malonate------20 and treated with 1 part benzoyl peroxide at 50° Methyl methacrylate------80 100 C. for 9 to 48 hours gave, respectively: 70 to give a hard copolymer. (a) A fairly stiff resilient copolymer. Parts (b) A hard copolymer. (b) Methylene dipropyl malonate.------30 (c) A resilient friable gel. Ethyl acrylate------70 (d) A stiff, rubbery, stringy copolymer. to give a rubbery copolymer. 5 (e) A gunny, rubbery copolymer.

2,330,088 5 Eacample 18 Eacample 13 Parts 20 parts methylene dihexylmalonate, when Methylene di - (secondary butyl carbinyl) malonate ------20 mixed with 80 parts Diethylene glycol maleate resin prepared as (d) Diethyl itaconate described in Example 14------80 . (b) Diallyl oxalate Benzoyl peroxide ------1 (c) Vinyl acetate (d) Ethyl acrylate, or were heated for 2 hours at 90° C. to give a soft (e) Methyl methacrylate 10 gel, which became a hard copolymer after 17 hours. - and treated with 1 part benzoyl peroxide at Eacample 19 50-100° C. for 9-54 hours gave, respectively: Parts (a) A moderately viscous copolymer. Methylene diethyl carbinyl malonate------20 (b) A rubbery gel. 5 Diethylene glycol maleate resin prepared as (c) A Soft, translucent gel, described in Example 14------80 (d) A stiff, rubbery copolymer. Benzoyl peroxide------(e) A hard, opaline Copolymer. Were heated for 1 hour and 5 minutes at 90° C. Similar copolymers were obtained when meth 20 to give a soft gel. When heated for 17 hours ylene di- (secondary butyl carbinyl) malonate or at 90° C. a hard copolymer was formed. methylene di- (methyl carbinyl) malonate was Illustrative examples of other polyhydric al used in place of methylene dihexyl itaconate. cohol esters of alpha, unsaturated alpha beta polycarboxylic acids which may be copolymerized Eacample 14 25 with methylene malonic esters to provide new Parts and useful compositions, which are claimed in Methylene dibutyl malonate------20 my divisional application Serial No. 485,178, filed Benzoyl peroxide ------1. April 30, 1943, are: ethylene glycol maleate, tri Polyhydric alcohol ester of an alpha, unsatu ethylene glycol maleate, glyceryl maleate, ethyl rated alpha beta, polycarboxylic acid ---- 80 30 ene glycol fumarate, diethylene glycol fumarate, triethylene glycol fumarate, propylene glycol 1 Note.--This polyhydric alcohol ester was prepared by effecting reaction between equal molar parts of Inaeic anhydride and di fumarate, glycol itaconate, diethylene -glycol ethylene glycol. The reactants were mixed in a suitable apparatus and the temperature raised to 200° C. over a period of one hour. itaconate, triethylene glycol itaconate, tetra Heating was continued for six hours at 200 to 210°C., at the end of ethylene glycol itaconate, glyceryl itaconate or which time there was obtained a viscous pourable resin having an 35 modifications of these esters produced by in acid number of about 27. corporating therein non-ethylenic polybasic acids The methylene dibutyl malonate was copoly such as the saturated aliphatic acids, e. g., nerized with the above-described polyhydric al malonic, succinic, glutaric, adipic, pimelic, cohol ester at 90° C., yielding a soft gel at the Suberic, sebacic, etc., the aromatic polybasic acids end of 40 minutes and a hard copolymer within 40 Such as phthalic, di-, tetra- and hexa-hydro two hours. This copolymer was exceptionally phthalic, naphthalene dicarboxylic, etc., or mix tures of such acids. y hard and abrasion-resistant after heating for a The addition of as little as 0.1 part of a poly total of 17 hours at 90' C. allyl ester of a polycarboxylic acid, specifically Eacample 15 45 diallyl itaconate, to mixed monomers or partial Parts polymers of a methylene malonic ester and at . Miethylene diisopropyl malonate------20 One other polymerizable compound contain Diethylene glycol maleate resin prepared as ng a described in Example 14------80 50 / Benzoyl peroxide ------N were treated at 90° C. for 1 hour and 50 minutes grouping, as for instance esters of acrylic and to give a soft gel-like copolymer. Continued alkacrylic acids, vinyl compounds such as vinyl heating for 17 hours at 90° C. gave a hard co acetate, etc., yields upon copolymerization of the polymer. 55 mixture interpolymers of increased solvent-re Eacample 16 sistance, heat-resistance or heat- and solvent Parts resistance. By suitably increasing the percent Methylene di- (secondary amyl) malonate--- 20 age proportion of such diallyl esters, as for in Diethylene glycol maleate resin prepared as stance to proportions of the order of 10% to 50% . described in Example 14------80 60 or more by weight of the whole, insoluble in Benzoyl peroxide ------1. fusible interpolymers can be produced. were heated together at 90° C. for 17 hours to The methylene malonic esters, as well as the give a hard copolymer. interpolymers obtained by copolymerizing these 65 esters with other polymerizable bodies, have a Eacample 17 wide range of properties. Their hardness and Parts solubilities may be varied over a considerable Methylene dihexyl malonate------20 range from fluid compositions of varied intrinsic Diethylene glycol maleate resin prepared as viscosity or soft, flexible bodies to hard, rigid described in Example 14------80 70 masses that can be SWelled or dissolved in many Benzoyl peroxide ------1. volatile and non-volatile solvents, even those of were heated at 90° C. for 40 minutes to give a a hydrocarbon nature. By suitable selection of soft gel which became hard within two hours. the starting monomeric or partly polymerized When heated at 90° C. for 17 hours, it was ex materials, interpolymers can be obtained in an ceptionally hard. 75 insoluble, infusible state practically resistant to.

6 2,380,033 the destructive effect of other chemical bodies When the monomers of this invention are co such as acids, bases, solvents and the like. polymerized with, for example, diallyl itaconate When a plasticizing effect is desired in Some in the presence of another non-polymerizable other synthetic or natural plastic or potentially body which acts as a solvent for these monomers, plastic material, the methylene malonic esters 5 there results a homogeneous gelled material which containing at least three carbon atoms in the firmly binds the solvent so as to reduce to a alcohol residue of the ester are particularly suit minimum evaporation losses of the Solvent. - able for that purpose. High molecular weight lustrative of non-polymerizable bodies which thus bodies such as polyvinyl halide, e. g., polyvinyl may be gelled are butyl alcohol, benzene, ethylene chloride, etc., cellulose esters such as the acetate, U dichloride, the monohalogenated aromatic hydro propionate, butyrate, etc., cellulose ethers such carbons or mixtures of halogenated aromatic hy as ethyl cellulose, benzyl cellulose, etc., poly drocarbons, ethylene glycol, mineral oils including methyl methacrylate, polystyrene, etc., may be lubricating oils, etc. plasticized by incorporating therewith such The term "formaldehyde' as used generally methylene malonic ester in monomeric, partially 5 herein and in the appended claims is intended polymerized or completely polymerized state, in to include within its meaning formaldehyde, the presence or absence of a catalyst such as HCHO, and polymeric modifications thereof. benzoyl peroxide when the monomeric or par What I claim as new and desire to secure by tially polymerized forms are used. The methyl Letters Patent of the United States, is: ene malonic ester may be incorporated into the 20 1. The process of producing a composition high molecular weight body to be plasticized by comprising a methylene malondc ester which simple mechanical agitation or by the use of comprises reacting a malonic ester with form mutual solvents, followed by the standard me aldehyde in the ratio of one mol of the former to chanical processes known in the plastics art. . at least One mol of the latter and under alkaline These bodies then may be subjected to further 25 conditions to form a methylol derivative, acidify heat and pressure treatment if desired. ing the mass and dehydrating the acidified mass The methylene malonic esters may be con to obtain a composition comprising a methylene verted to polymers or interpolymers in maolds malonic ester. with or without the application of pressure, in 2. The process of preparing a methylene the presence or absence of a material which is a 30 malonic ester which comprises effecting reaction solvent for the monomer but not for the polymer, between a malonic ester and formaldehyde in or one which is a solvent for both monomer and the ratio of one mol of the former to at least one polymer, or one which is not a solvent for either mo) of the latter and under alkaline conditions to the monomer or polymer so that spongy or gran form a methylol derivative, acidifying the mass, ulated polymeric modifications are obtained. dehydrating the acidified mass to obtain a com The solid, thermoplastic polymers and copoly position comprising a methylene malonic ester mers of this invention, with or without modify and separating the methylene malonic ester from ing agents, may be used in injection, compres the said composition. sion, or transfer molding processes to make nul 3. The method of preparing a methylene merous articles for industrial, technical and 40 malonic ester which comprises forming a mixture novelty use and other applications. having a pH above 7.0 and comprising a malonic As modifying agents various fillers may be ester and formaldehyde in the ratio of one mol used, for example wood flour, alpha flock, sand, of the former to at least one mol of the latter, asbestos, mica, paper, cloth, cellulose derivatives 45 effecting reaction between the components of such as cellulose itself, regenerated cellulose, the said mixture at the said pH to form a methylol cellulose esters, cellulose ethers, natural and Syn derivative, said reaction being carried out at a thetic filaments or fibers, etc., in continuous, temperature not exceeding substantially 50° C. shredded, or comminuted form. Pigments, dyes, retarding the reaction between the said com opacifiers, plasticizing substances, such as di ponents by bringing the reaction mass to a pH butyl phthalate, esters of monobasic and poly below 7.0, dehydrating the resulting mass to form basic acids, etc., may be incorporated into the a composition comprising methylene malonic polymers and copolymers to modify the same. ester and separating the methylene malonic ester Natural and synthetic resins, gums, oils, Waxes, from the said composition. polyhalogenated aromatic derivatives, etc., like 5 5 4. The method of preparing a methylene wise may be added as modifying agents. malonic ester which comprises reacting, at a pH In solvents, or without solvent utilizing a melt above 7.0, an aqueous solution of formalde process, the fusible polymers may be used in ad hyde with a malonic ester in the ratio of one hesive and laminating applications to bond mol of the malonic ester to at least one mol of paper, wood, mica flakes, glass sheets, rubber formaldehyde thereby to form a methylol malonic 60 ester, said reaction being carried out at a tem sheets, etc., fibrous materials such as silk, as perature between about 0° C. and about 35° C. bestos, glass fibers, synthetic fibers in filament, and in the presence of an inhibitor of polymeriza thread or fabric (woven or felted) form, etc., tion, bringing the resulting mass to a pH below cellulose derivatives in sheet, comminuted or 7.0 to retard further reaction between the said fiber form, etc. In the form of liquid coating 65 components, and distilling the resulting mass to compositions such as lacquers, enamels, var dehydrate the same and to obtain therefrom a nishes, etc., they find application in Surface pro methylene malonic ester. tective coatings, such as for walls, desks, wire, 5. The process of preparing methylene di concrete, porcelains, etc. In a flowable condi methylmalonate which comprises effecting reac tion without the use of solvents they may be 70 tion between dimethyl malonate and formalde used as impregnants for many porous bodies, hyde in the ratio of one mol of the former to at such as cork, pottery, felts, or fabricated bodies least one mol of the latter and under alkaline with interstices, such as the windings of electri conditions to form methylol dimethyl malonate, cal coils, netted fiber, interwoven fibrous mate acidifying the mass, dehydrating the acidified rials, etc. 75

2,880,088 7 mass to obtain a composition comprising methyl mol of the latter and under alkaline conditions ene dimethyl malonate and separating the meth to form methylol diethyl malonate, acidifying the ylene dimethyl malonate from the said compo mass, dehydrating the acidified mass to obtain sition. a composition comprising methylene diethyl 6. The process of preparing methylene diethyl malonate and separating the methylene diethyl malonate which comprises effecting reaction be malonate from the said composition. tween diethyl malonate and formaldehyde in the ratio of one mol of the former to at least One GAETANO F. D'ALELIO.