Patented Apr. 21, 1942 2,280,256 UNITED STATES PATENT OFFICE 2,280,256 POLYMERIZATION OF MALEIC ACID-LIN SEED OL, FATTY ACDS - ETHYLENE GYCOL-ALLY RESN Donald G. Patterson, Stamford, Conn., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Application December 13, 1939, Serial No. 308,953. 1. Claim. (C. 260-22) This invention relates to heat- and Oxygen tile under these conditions are removed, leaving convertible polyester resins. as a residue a nearly water-white polyester of An object of this invention is to provide a relatively low viscosity and having an acid num means of obtaining low acid number heat- and ber of about 6-7. oxygen-convertible resins which contain many Eacample 2 unsaturated groups. Another object of the present invention is to About 0.2% of a suitable catalyst, e. g. benzoyl provide polymerizable materials of relatively low peroxide, is added to the polyester obtained in viscosity having good stability upon storage. Example 1. This composition is applied to paper Still another object of this invention is to pro 0 in any desired manner, for example, by dipping. vide polyesters which upon polymerization are The paper is passed through Squeeze rolls to ad substantially infusible and substantially insolu just the amount of resin carried by the paper, be. and the paper so impregnated is baked in an These and other objects are attained by esteri oven at 50-80 C. for about five minutes to sixty fying a dicarboxylic acid, preferably an or, B-un 5 minutes. The paper may then be cut into sheets Saturated dicarboxylic acid with a mixture includ of any desired size, stacked to any required thick ing a polyhydric alcohol and a straight chain un ness and molded between hot platens at about saturated monohydric alcohol which has a ter 135° C. at a pressure of about 1000-2000 lbs./sq. mina double bond. in. The compressed laminated article thus The following examples in which the propor 20 formed is cured at about 135-165 C. for about tions are given as parts by weight are given by three to five hours or until maximum strength has been attained. This procedure results in a way of illustration and not in limitation. molded article having unusual resistance to frac ture by impact. Eacample 1 Eacample 3 Parts 25 Maleic anhydride------392 About 0.2% of benzoyl peroxide and about ------130 0.04% of cobalt (added as naphthenate) is added Allyl alcohol------255 to the polyester obtained in Example 1. Coat Linseed oil fatty acids------37 ings of this composition are applied to tin and Ethylene dichloride------389 baked at about 90-150° C. for about ten to thirty p-Toluene sulfonic acid------4. minutes. A clear, hard, flexible coating is ob tained. Since such coatings are odorless and These substances are placed in a. Suitable reac tasteless they have been found to be particularly tion chamber to which a reflux condenser is suitable for use as beverage or food container attached. The reflux condenser preferably dis 3 5 coatings. In this application the polyester com charges the condensate into a trap where the position containing the catalyst may be applied water of esterification may be separated from , to the containers or to the sheet metal from which the essentially non-aqueous fraction of the con the containers are to be fabricated. densate and the latter is returned to the reaction 40 chamber. The ethylene dichloride is included Eacample 4. in order to separate the allyl alcohol from the Parts water of esterification which is formed during Maleic anhydride------392 the process. The reaction chamber and its con Sebacic acid------162 tents are heated to about 90-150° C. and main 45 Ethylene glycol------156 tained at this temperature for about forty-eight Allyl alcohol------306 to sixty hours or until the acid number of the Ethylene dichloride------508 polyester is sufficiently low. During this time the Paratoluene sulfonic acid------5 reaction is preferably carried out under an inert These substances are reacted in the same gen atmosphere, e. g., carbon dioxide or nitrogen, 50 eral manner as described in Example 1 and a etc. After sufficient reaction to obtain the de polyester having an acid number of about 6-7 is sired acid number the reaction mixture is sub obtained. This polyester is suitable for the ap jected to a vacuum distillation at about 140°-150° plications described in Examples 2 and 3, as well C. and at about 1-5 mm. of mercury absolute as in other applications, and has good flexibility pressure. All of the ingredients which are vola 55 characteristics.

2 2,280,256 Eacample 5 dient and these mixtures may in addition be ad - Parts mixed with some monocarboxylic acid. Maleic anhydride------19 The term “acid' as used herein is intended to Ethylene glycol------67 cover the acid anhydride, as well as the acid it Decamethylene glycol------35 self since either or both may be used according to availability, and convenience. Allyl alcohol------101 Of the polyhydric which may be used Linseed oil fatty acids------20 incarrying out my invention, the glycols are pre Paratoluene sulfonic acid------2 ferred. Among these the following are included: Toluene ------211 ethylene glycol, or-propylene glycol, polyethylene This composition is reacted in the same general glycols (e. g., diethylene glycol, triethylene gly manner as described in Example 1 and a poly col, tetraethylene glycol, pentaethylene glycol, ester is obtained which has good flexibility chair hexaethylene glycol, etc.) polymethylene glycols acteristics after being cured. . (e. g., trimethylene glycol, decamethylene glycol, Ecample 6 etc.) octadecandiol, 2,2-dimethyl propanediol Parts 1,3; 13 butanediol; 12 propanediol; and 2-ethyl Undecylenic acid------92 2-butyl butanediol-13. or glycerol Maleic anhydride.------196 monoethers may also be used if desirable, as well Ethylene glycol------98. as other polyhydric alcohols such as trimethyl Allyl alcohol------96 20 olpropane, nitroglycols, etc. Toluene ------241. The unsaturated alcohols which are suitable Paratoluene sulfonic acid------2-3 for the purposes of my invention are the esteri flable primary and secondary alcohols which The general procedure of Example 1 is followed have a terminal double bond and which are in reacting these substances to produce a poly straight chain hydrocarbon derivatives. Exam ester having an acid number of about 20. Films 25 ples of these are allyl alcohol, methyl vinyl car of this polyester upon curing are somewhat softer binol, allyl carbinol (CH=CH-CH-CH2OH), than those obtained from the other compositions (3-allyl ethyl alcohol (CH-CH-(CH2)3OH). described above, but are superior to those Con Esters of these alcohols may also be used, e. g., positions in flexibility and in adhesive character 30 diallyl phthalate, diallyl maleate, diallyl fuma istics. rate, etc. Eacample 7 Warious modifiers which have previously been Parts used in alkyd resins may also be incorporated. Fumaric acid------464 Ethylene glycol------135 Among these are the ordinary monobasic acids 35 and the monohydric alcohols. The addition of Allyl alcohol ------255 these alcohols or acids may serve to impart cer Linseed oil fatty acids------43 tain properties to the resinous materials to a Paratoluene sulfonic acid------4. Sufficient degree which they would not other Ethylene dichloride------449 wise have, such as plasticity, flexibility, hardness, These substances are reacted in accordance 40 solubility, rapid air-drying properties, etc. with the general procedure described in Example Among the most useful of these modifiers are 1 and a polyester having very similar charac the fatty acids or their esters and especially the teristics is obtained. drying oil fatty acids or the drying oils them selves. Among the drying oils (or the acids Eacample 8 therefrom and the esters thereof) which may be Parts 45 used, linseed oil, perilla oil, oiticica oil, sunflower Diallyl maleate ------1470 seed oil, tung oil, etc., are included. Other Maleic anhydride ------490 fatty oils or the acids derived therefrom and Ethylene glycol ------326 the esters thereof which may be used are: olein, p-Toluene sulfonic acid------0 oleic acid, stearin, stearic acid, castor oil, soya. Toluene ------1,148 50 bean oil, olive oil, etc. Various mixtures of the This composition is reacted in the same gen fatty oils or fatty oil acids may be used, as well eral manner as described in Example 1. A poly individual fatty acids derived from the fatty ester having an acid number of about 15-16 is Ols. obtained and may be used for laminating cloth Esterification of my resinous materials is pref in the same general manner as paper is laminat erably effected by heating under azeotropic con ed according to the procedure of Example 2. ditions in the presence of a suitable organic sol The laminated cloth produced from this resin vent. (usually inert) which is preferably sub has very high impact strength and is suitable stantially insoluble in water but which dissolves for the production of gears. the reactants, as well as the resulting polyester Among the dicarboxylic acids which may be 60 resin. Examples of these are: benzene, toluene, used in the preparation of my polyesters, the xylene, chloroform, carbon tetrachloride, ethyl ox, 6-unsaturated organic acids are preferred. ene dichloride, propylene dichloride, ethylene and Examples of these are maleic, fumaric, itaconic, propylene trichlorides, butylene dichlorides and citraconic, mesaconic and aconitic acids, and trichlorides, cresols, cyclohexanone, methyl cy halogenated acids such as chloromaleic acid, 65 clohexone, etc. The range of preferred concen etc. Other dicarboxylic acids which may be tration for the inert organic solvent is from used include phthalic, sebacic, adipic, azelelic, about 25% to about 50% of the total weight of terephthalic, pimelic, brassylic, etc. Any of the the reactants and organic solvent. It is also foregoing may be substituted in part with acrylic possible but not generally desirable to use a large acid, B-benzoyl , methacrylic acid, O excess of the unsaturated monohydric alcohol Al-cyclohexene carboxylic acid, cinnamic acid, which is to be used as a reactant, e. g., allyl al crotonic acid, undecylenic acid, and other mono cohol in place of or in addition to the inertor carboxylic acids. Obviously various mixtures of ganic solvent. It is to be noted, however, that the dicarboxylic acids may be used where expe 75 when an excess of allyl alcohol be used, a rela 2,280,256 3 tively large proportion of the diallyl ester will be lose esters and ethers, urea-aldehyde resins, tri produced. azine-aldehyde resins such as melamine-formal It is preferable that a suitable esterification dehyde resin, phenol-aldehyde resins, alkyd res catalyst be employed, examples of which are ins, ester gum, rubber, synthetic rubber-like prod p-toluene sulfonic acid, thymol sulfonic acid, ucts, rubber compounds, etc. d-camphor sulfonic acid, stannic chloride, stannic In some instances it may be desirable to in chloride dioxanate, etc. Only a small proportion clude a polymerization inhibitor in my polyester of catalyst is generally sufficient, e.g., about 1%- resinous compositions in order to improve the 3% of the weight of acid reacted. stability during storage or to control the reac The esterification reaction is preferably car tion velocity during polymerization. Phenolic ried out in a suitable reaction chamber which is compounds, especially the polyhydric phenols and provided with an agitator, a reflux condenser the aromatic amines act as polymerization in and preferably a trap for separating and remov hibitors. Specific examples of this group of in ing the water formed during the esterification, hibitors are hydroquinone, resorcinol, tannin, together with means for returning the essentially 5 sym. di-beta-naphthyl-p-phenylene diamine non-aqueous fraction of the distillate to the re action chamber after condensation. It is also advantageous to carry out the reaction under an inert atmosphere such as nitrogen or carbon di oxide. The reaction temperature is preferably 20 controlled so that no local overheating will occur. The reaction temperature will depend upon the and phenolic resins. Sulfur compounds, benzal inert organic solvent employed if any be used, dehyde and l-ascorbic acid are also suitable. and upon the concentration of said solvent, as The concentration of the inhibitor is prefera well as the concentration of the reactants. Gen.- : bly low and usually less than 1% is sufficient. erally the reaction temperature should range be With the preferred inhibitors only about 0.01% tWeen about 90-200 C. to about 0.1% is sufficient. The esterification reaction is continued until Resinous materials made according to my in the acid number of the polyester resin being vention have a wide variety of uses as in coat formed is sufficiently low. The inert solvent 30 ing compositions and in molding compositions. and/or excess unsaturated alcohol are removed My resins are particularly suitable for the pro by distillation and the ester of the unsaturated duction of laminated paper or cloth materials alcohol (which is formed along with the polyester used in the production of electrical insulation, resin) is distilled off under vacuum, e.g., at about gear wheels, abrasive wheels or disks, brake lin -10 mm. mercury absolute pressure. The resi ings and various other molded objects. Coating due comprises the polyester resin product. compositions containing these resins are valu Polymerization catalysts may be incorporated able for coating metallic receptacles such as bev in my resinous materials, the organic peroxides erage and food containers, for treating cloth or being particularly suitable for this purpose. paper to render the same resistant to moisture Among the preferred catalysts there are: the 40 or other chemical action, the resulting products acidic peroxides, e. g., benzoyl peroxide, phthalic being suitable for shower curtain cloth, tobacco peroxide, succinic peroxide and benzoyl acetic pouches, electrical insulating cloth, etc. Coat peroxide; fatty oil acid peroxides, e. g., lauroyl ing compositions containing my resins may also or cocoanut oil acid peroxides and oleic peroxide; be used in a wide variety of lacquers, varnishes, alcohol peroxides, e. g., tertiary butyl peroxide enamels and paints. My resins are also useful and terpene Oxides, e. g., a Scaridole. Still other in the production of gaskets and in the manufact polymerization catalysts may be used in some in ture of printing inks. stances such as Soluble cobalt salts (particularly My polyesters may be polymerized at room the linoleate and naphthenate), p-toluenesul temperature, although it is generally desirable to fonic acid, aluminum chloride, stannic chloride 5) utilize elevated temperatures. Generally if the and boron trifluoride. In many instances it may compositions contain catalysts, temperatures be be desirable to use a mixture of these catalysts, tween about 100° C. and about 165 C. are suit e.g., the combination of benzoyl peroxide with able. It may be desirable to partially cure my a cobalt salt. polyesters in some applications at somewhat The concentration of polymerization catalyst 55 lower temperatures, e. g., 50-80 C. but in order employed is usually small, i. e., for the preferred to effect the final cure more rapidly temperatures catalysts, from about 0.1% to about 2% of the between about 135°-165 C. are desirable. The polyester. If a polymerization inhibitor be pres optimum range of polymerization temperatures ent, up to 5% or even more of catalyst, may be obviously will vary for each polyester, as well as necessary according to the concentration of in 50 with the type of application, i. e., molding, cast hibitor. Where fillers are used which contain ing, laminating, surface coating, etc. Polymeri high concentrations of substances which act as zation or curing of my polyesters in an inert at inhibitors, e. g., wood flour, cork, granules, etc., mosphere has been found to be advantageous in the concentration of catalyst necessary to effect some instances. polymerization may be well above 5%. The rate of polymerization of my polyesters is My polyester may be mixed with one or more accelerated when they are subjected to ultra-vio of the various fillers, e.g., wood flour, wood fiber, let light, infra-red and other light radiations. paper dust, clay, Zein, glass Wool, mica, granite They may be heated simultaneously With the dust, asbestos, casein, silk flock, cotton flock, ... light radiation to further increase the rate of steel wool, carborundum, paper, cloth, sand, polymerization. white, black or colored pigments, etc. Further Obviously many modifications and variations more, suitable dyes may also be used for color in the processes and compositions described herein ing purposes if desirable. Compatible natural may be made without departing from the spirit and Synthetic resins may also be admixed with and scope of the invention as defined in the ap my new resinous materials, e. g., shellac, celiu- 5 pended claim. 4. 2,280,256 I claim: distilling a mixture including allyl alcohol, water A process which comprises polymerizing by and the inorganic solvent, and separating the heating in the presence of benzoyl peroxide a water from the distillate and returning the non resin obtained by the esterification of maleic acid aqueous fraction of the condensate to the reac and linseed oil fatty acids simultaneously with tion chamber, the esterification being continued ethylene glycol and allyl alcohol, the molal ratio until the acid number is about 6-7 and distilling of the maleic acid, linseed oil fatty acids, ethyl off volatile material at about 140-150° C. at about ene glycol and allyl alcohol being about 1-5 mm. of mercury absolute pressure, said heat 4:0.13:2.1:4.4 respectively, said esterification be ing being continued until a hard resinous mate ing effected by heating the reactants in admix l0 rial is obtained. ture with an inorganic-solvent and azeotropically DONALD G. PATTERSON. CERTIFICATE OF CORRECTION Patent No. 2,280,256. April 21, 1942.. DONALD G PATTERSON It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, sec ond column, line 28, for "(CH2-CH-(CH2)OH)" read --(CH2=CH-(CH2)OH)-; and that the said Letters Patent should be read with this correction there 'n that the same may conform to the record of the case in the Patent Office. Signed and sealed this 9th day of June, A. D. 1942.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.