[1]Uni'ted St..,,qtes Patent Office 21 09,1 6 2,809,186 NEW POLYOLS FROM POLYALDEHYDES, THEIR PREPARATION AND DERIVATI[VEI S 5 Curtis William Smith, Berkeley, and Theodore W. Evans, Oaldand, Calif., assignors to Shell Development Conipany, New York, N. Y., a corporation of Delaware NoDrawing. ApplicationAugustl6,1954, 10 Serial No. 450,210 14 Claims. (Cl. 260-73) This im;ention relates to new polyols, i. e,, polyhydroxy 15 compounds, and to their preparation. More particularly, the invention relates to a new class of p6lyols, to a process for preparin,- the polyols from polyaldehydes, and to certain v2tiable derivatives of the polyols. Specifically, the inve@ition provides new polyols having 20 unexpectedly h-gh functionality, said polyols being prepared by reacting a polyaldehyde with formaldehyde in aii amount suimcient to furnish at least 2 moles of formaid.ehyde per mol of polyaldehyde and preferably at least one mole of formaldehyde for every aldehyde group and 25 for every labile hydrogen on the carbon atom adjacent to the aldehyde group on the polyaldehyde molecule, and then hydrogenatnig the resulting product. The invention ful-tlier provides valuable derivatives of the abovede-@ scribed polyols and particularly their monorneric and 30 polymeric esters. It is an object of the invention to provide a new class of polyols. It is a further object to provide new polyols havitig a high d--gree of functionality and a process for prepari,.ig ttic polyols from polyaldehydes. It is a fur35 ther object to provide new polyols having properties whicli make them particularly useful and valuable in industry. It is a further object to provide new polyols which are particularly useful as lubricants and blending agents. It is a further object to provide new pol I yols 40 which ar@- particularly valuable in the preparation of modifi.-d a-.kyd resins. It is a further object to provide new polyols which are useful in the preparation of ester plasti--izers. Other objects and advantages of the inven. 45 tion will be apparent from the following detailed description thereof. It has now been discovered that new polyols having aTi unexpectedly high functionality are obtained by con. densing a polyaldehyde with formaldehyde in a mole ratio of at least 1:2 and then hydrogenating the result50 ing product. The aldehydes to be used in the preparation of the new polyols c6niprise those compounds having at least two aldehyde groups, i. e., at least two 55 C=O grorps and preferably those having at least one aldehyde group attached to a carbon atom bearing a labile hydrogen atom. These polyaldehydes may be open-chain or cyclic, 60 saturated or unsaturated and may be substituted with various substitutents, such as halogen atoms, alkoxy radicals and the like. E-xamples of these polyaldehydes include, among others, glutaraldehyde, adipaldeh3rde, 65 piinelaldehyde, suberaldehyde, glutaconaldehyde, alpha hydroxyadipaldehyde, beta-methoxyadipaldeh de, alpl@a,- I Y gamma-dimethvl-alpha-(methoxymethyl) glutaraldehyde, beta - allyloxy - pimelaldehyde, 1,4- cyclohexanedicarboxaldehyde, 3 - cyclohexene -1,5 - dicarboxaldehyde, I 1 5- pentanetricarboxaldehyde and 1,3,6- octanetricarboxa,lde- 70 hyde. A preferred group of polyaldehydes to be used in the Patented Oct. 8, 1957 2 p.reparation of the new polyols comprise glataraldehyde and hydrocarbyl-substituted glutaraldehydes, such as those of the formula: H R R 1 O=C-CH2-@H- ICH-CHO wh@-rein each R is hydrogen Gr an alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or an aralkyl group. Examples of these dialdehydes include beta-methyl-glutaraldehyde, beta,gamma - dibutylglutaraldehyde, betaphenylglutaraldehyde, beta,gamma - dibenzylglutaraldehyde, betaallylglutaraldehyde, beta,gamma-dicyclohexylglutaraldehyde, and beta-isopropylphenylglutaraldehyde. A detailed description of how to prepare these aldehydes may be found in Smith et al.-U. S. 2,546,018. Another preferred group of polyaldehydes to be used in preparation of the polyol comprise the ether-substituted dialdehydes, such as those obtained by reacting a suitable alpha - mothylene monoaldehyde, such as methacrolein, with an alcohol under controlled conditions and in the presence of a basic condensation catalyst. The overall reaction which is effected in the execution of this process may be exemplified by the following equation: RI RI RI ROH + 2CH,=C-CHO R-0-CH2--@-CH2-C, H I CHO CHO In this equation, ROH signifies an alcohol confaining the organic radical R which is preferably a hydrocarbon radical, and Ri represents a hydrocarbon group, pre ably an alkyl, cycloalkyl, aryl ' alkaryl or aralkyl group. For enample when R is allyl and Ri represents methyl, the product is alpha,gamma-dimethyl-alpha(allyloxymethyl) glutaraldehyde. Other examples of these preferred aldehydes include alpha,gamma-dimethylalpha(methoxymethyl) gltitaraldehyde, alpha,gamma-dimethylalpha -(propoxymethyl) glutaraldehyde, alpha,gammadimethyl-alpha(hydro-yethoxymethyl) glutaraldehyde, alpha,gammadimethyl-alpha-(butoxymethyl) glutaraldehyde, alpha,gammadiethyl -alpha -(phenoxymethyl) glutaraldehyde, alpha,gammadicyclohexyl-alpha-(methallyloxymethyl) glutaral@dehyde, alpha,gamma-dibutyl-alpha(dodecyloxymethyl) glutaraldehyde, and alpha,gammadioctyl - alpha - (octadecenyloxymethyl) glutaraldehyde. Especially preferred menibers of this group are those of the formula: Ri RI CHO @1310 wherein R is a hydrocarbon or hydroxy-substituted hydrocarbon radical, and particularly an alkyl, alkenyl, cycloalkyl or cycloalkenyl rad;cal and their hydroxysubstituted derivatives, and Ri is an alkyl, alkenyl, cycloalkyl or cycloalkenyl radical, wherein all of the foregoing radicals preferably coiitain no more than 8 carbon atoms. A detailed description of the method for preparing the above-described pref,-rred polyaldehydes m. ay be found in col)ending -patent application of Smith and Norton, Serial No. 16,617, filed March 23, 1948, now Patent No. 2,702,823. Another preferred group of polyaldehydes to be used rin- the polyols of the present invention comin.prepa . prise the hydroxy-substituted dialdehydes and particularly the alpha-hydroxy-substiti,,ted adipaldehydes, such as, for example, alpha - hydroxyaldipaldehyde, alpha - hydroxygamma, deltadimethyladipaldehyde, alpha-hydroxy-gamiiia-ethyl-deltaisopropyl-adipaldehyde, and alpha-hydoxygamma-deltadioctyladipaldehyde. A detailed description for preparihg some of these polyaldehydes from substiA
[2]tuted dihydro-1,4-pyrans may be found in Whetstone et al.-U. S. 2,639,297. Another group of preferred polyaldehydes to be used in the preparation of the new polyols comprise those obtained by condensation of methacrolein in the presence of aqueous alkali as described in J. Am. Chem. Soc. 60, 1737 and 1911 (1938), and polyaldehydes obtained by condensing acrolein with alcohols in the presence of a basic catalyst as described in German Patent 554,949. Still another group of preferred polyaldehydes to be used in the preparation of the polyols of the invention comprise the polymers and copolymers obtained by polymerizing unsaturated aldehydes. Examples of such unsaturated aldehydes include, among others, acrolein, alpha-methyl acrolein, alpha-ethyl acrolein, alpha-propyl acrolein, alpha-isobtityl acrolein, alpha-n-amyl acrolein, alpha-n-hexyl acrolein, alphabro@-no acrolein, crotonaldehyde, alpha@chlorocrotonaldehyde alpha-bromocrotonaldehyde, alpha-beta-dimethylacrol@in, alphamethyl-betaethyl acrolein, alphaethyl-beta-propylacrolein, aiad the like. Preferred unsaturated aldehydes to be used in preparing theso polymers include the alphabeta-ethylenically unsaturated aldehydes, and particularly the 2-alkenals containing no more than 8 carbon atoms. - Monomers that can be copolymerized with the abovedescribed unsaturated aldehydes to form polyaldehydes comprise those compounds containing a pblymerizable unsaturated linkage, and preferably a single CH2=C= group, such as, for example, styrene, alphamethyl styrene, vinyl chloride, vinylidene chloride, methyl methaciylate, ethyl acrylate, acrylonitrile, methacrylonitrile, allyl acetate, vinyl acetate, chloroallyl caproate, allyl alcohol, isobutylene, allyl glycidyl ether, vinyl methyl ether, allyl giycolate, methyl allyloxy-acetate, vinyl pyridine, glycidyl methacrylate, hydroxyethyl methacrylate, octyl acryiatd, Yinyl pyrollidone, allyl dimethyl eyanurate, allyl butyl phthalate, dialkyl maleates, and the like. In preparing copolymers of theunsaturated aldehydes with these dissimilar monomers it is preferred to employ thedissimilar riionomer in amounts varying from I% to 70 % by weight of the total monomer mixture. The polymerization may be accomplished by treqting the monomer composition contaii3ing the unsaturated gldehyde and, if desired, adissimilar monomer, with an iinitiator which generates free radicals, such as peroxide and azo-type initiators. Specific peroxides which can be used include dialkyl peroxides, e. g., di-t-amyl peroxide; alkyl hydro peroxides, e. g., t-butyl hydroperoxide; and diacyl peroxides, c. g', benzoyl peroxide, Acetyl peroxide and acetyl benzoyl peroxide. Specific azo compounds which can be used include alpha,alpha'-azodiisobutyramide, 1,1'-azodicyclohexanecarbonitrile and alpha, alpha'-azobis(alpha,gamma-dimethylvaleronitrile). These catalysts are preferably employed in amounts varying from about 0.1% to 10% by wei.-ht of the material being polymerized and more preferably from 1% to 5% by weight. The polymerization may be effected over a wide range oftemperatures depending upon the catalyst selected and the desired molecular weight of the polymer. If one desires very low molecular weight products, one should select a higher reaction temperature, such as of the order of 100' C. to 250' C., and select a catalyst that has a satisfactory decomposition rate within that range of temperature. If the highe r molecular weig,ht products are desired, one may select the lower range of temperature, such as, for example, 50' C. to 100' C., and select a catalyst having a decomposition rate within that range. In general, it is preferred to employ temperatures within the range of 80' C to 200' C., and catalysts that will be effective within that range. The polymerization may be conducted in bulk, solvent solution or aqueous emulsion or system. The polymerization i8 preferably conducted, however, in bulk or in the presence or absence of solvents, such as ethanol, hL 21809,186 4 butanol, dioxane, acetonitrile, isopropyl ether, and the like, and mixtures thereof. After the polymerization has been accomplished, the polymeric polyaldehydes may be recovered from the reaction mixture by any suitable means, such as distillation, filtration, extraction and the like. The new polyols are obtained by condensing one or more of the abovedescribed polyaldehydes with formaldehyde and then hydrogenating the resultin.- product. 10 The formaldehyde used in this reaction may be employed as such or one may emp oy materials that liberate formaldehyde, slich as trioxane (trimer of formaldehyde), paraformaldehyde, and the like. The formaldehyde may also be used in admixture with other monoaldehydes, 7.5 such as acetaidehyde, propionaldehyd-. and the like. The polyaldehyde and formaldehyde should be combined in a mole ratio of at least 1:2. For best results, however, there should be employed at least one mole of formaldehyde for every aldehyde group present on the 20 polyaldehyde molecule and for every hydrogen attached to the carbon atoms adjacent to the aldehyde -roups. Thus, in the reaction with dialdehydes, such as glutaraldehyde, one should, for best results, employ at least 6 moles of formaldehyde for every mole of the dialde25 hyde, and with substituted dialdehydes, stich as alphahyd,roxyaldipaldehyde, one should employ at least 5 moles of formaldehyde for every mole of the dialdehyde. Alkaline catalysts are preferably utilized to effect the desired condensation. Such materials include the alkali 30 metal hydroxide, stich as sodiurfi and potassium hydroxide, the alkaline earth metal hydroxides and oxides, such as calcitim oxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, organic amines, such as triethyl amine, pyridine, and the like. The amount of the catalyst 35 employed will vary preferably from about .1 mole to .8 mole per mole of the polyaldehyde, and more preferably from .5 mole to .75 mole per mole of the polyaldehyde. The temperature employed in the condensation reaction may vary over a considerable range. In general, 40 the temperature will range from about 10' C. to 150' C. Preferred temperatures range from about 40' C. to 100' C. The reaction is preferably conducted at atmospheric pressure, but s uperatmospheric or subatmospheric pressures may be employed as desired or necessary. 45 The condensation may be conducted with or without the use of solvent or diluents. Preferred solvents include Water and various organic materials in which the polyaldehydes may be soluble, such as ethanol, methanol, dioxane, butan(il, methyl butyl ether, dimethyl ether 5o of ethylene glycol, benzyl alcohol, chloroform, and the like. After the condensation reaction has been completed, the reaction mixture is then treated to remove the catalyst and rdcover the condensation product. The catalyst 55 may be removed by any suitable means, such as by precipitation with an acid as oxalic or sulfuric acid. The condensation product may then be recovered by distillation, precipitation, and the like. The condensation products produced by the above proc60 ess are viscous liquids to solids at room temperature. The products have a relatively high hydroxyl value and, if desired, may be used as polyol of low functionality. The desired, superior polyols having high functionaiity ate obtained from these pro4ucts, however, only by subsequent hydrogenation. 65 The hydrogenation is accomplished by treftting the condensation product with hydrogen at a temperature between 1301 C. and 3001 C., and an elevated pressure in the presence of certain hydrogenation catalysts. The 70 process may be executed in the presence or absence of diluents and solvents, but for best restilts it is usually de-sirable to employ inert diluents, such as ethanol isopropanol, ethylene glycol, dioxane, and the like an@ mixtures thereof. 75 Hydrogenation catalysts that may be used include,
[3]among others, the heavy metals of groups I,, 11 and IV to VIII of the periodic table of elements, mixtures of these metals, their alloys and derivatives as their sulfides, oxides and chromites, such as si@lver, copper, iron manganese,- molybdenum, nickel, palladium, pl.atinum, chromium, cobalt, rhodium, tungsten, mixtures of the metals, such as copper-silver mixtures, copper-chromium mixtures, nickelcobalt mixtures and their derivatives 8uch as copper oxide, copper chromite, nickel sulfide, silver sulfide, and the like. Particularly preferred catalysts are the niembers of the group consisting of nickel, copper, cobalt, iron chromium, silver and platinum, and their oxides, sulfides and chromites. These catalysts may be@ employed in a finely-divided form and dispersed in aiad throughout the reaction mixtures, or they may be employed in a more massive state, either in essenti-.tlly the pure state or supporied upon or carried by an in-,rt carrier material, such as pumice, kieselguhr, diatomaceous earth, clay,,alumina, charcoal, carbon or the,like, and the reaction mixture contacted therewith as by flowing the rlixture over or throu.-h a bed of the catalyst or according to other methods known in the art. The amount of the catalyst employed may vary over a considerable range. In general, the amount of the catalyst will vary from 1% to 30% by weight of the reactants. Preferred amounts of catalyst range from 1 % to 25 % by weight. The abovedescribed preferred catalysts are generally employed in amounts varying from 1% to 20% by weight. ,Temperatures used during the hydrogenation will generally vary from above 130' C. to about 300' C. Particu ' larly preferred temperatures range from 100' C. to 250' C. Hydrogen pressure of 250 potinds per square itch are edective, but higher pressures of the order of about 500 to 8000 p. s. i. are generally more preferred. Particularly preferred hydrogen pressures range from about 1000 p. s. i. to 5000 p. s. i. At the conclusion of the hydrogenation treatment, the polyols may be recovered directly from the reaction mixture by any suitable manner. For example, the hydro_ genation catalyst, if dispersed in the reaction mixture, may be removed by filtration or centrifugation and the polyols recovered , by distillation, solvent extraction, cryst@,llization or other known methods. The polyols prepared by the above process are viscous liquids to solids at room temperature, If solid, they have loW melting points and can@be converted to liqu,:ds at tempetatures generally below Eibout 100' C. All of the polyols have a high degree of functionality and preferably have at least four to six hydroxyl groups. The polyols are valuable as humectants, as softening agents for casein and other protein plastics, as textile lubricants, as lubricatiiag pil additives and as blending . agents for dyes, 'inks and paints. They are also useful as valuable intermediates in the preparation of emulsifying agents, surface active agents, adhesives, herbicides, fungicides, insecticides aiad tackifying -and softening a.-ents for natural and synthetic rubbers. The polyols are particularly valuable, however, in the preparation of modified alkyd resins. The polyols impart faster dryijig and baking characteristics and pr I oduce films having grcater hardness and flexibility. I The polycarboxylic acids which may be reacted with the novel polyols to prepare the above-described alkyd resins iii@y be of any suitable type. They may be saturated, unsaturated, cyclic, aromatic and may possess two, three or more carboxyl groups. Examples of these acids include, among others, phthalic acid, isophthahc acid, terephthalic acid, t6trachlorophthalic acid, glutaric acid, adipic acid, diglycolic acid, suceinic acid, pimelic acid, suberic acid, cyclohex anedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, 1,8-naphthalenic acid, and the like. Preferred polyearboxylic acids t - o-be u,sed in producing the alkyds comprise the unsubstituted dicarboxylic acids containing no more than par@bon 'atbms., such as, for ex6 aniple, the alkanedioic, cycloalkanedioic acid, alkenedioic, cycloalkenedioic acid, aromatic hydrocarbon dicarboxylic acids and the alkyl-substituted aromatic hydrocarbon dicarboxylic acids. 5 The modifying age@nts employed in producing the above-described alkyds comprising monohydric alcohols, as allyl alcohol, butyl alcohol, and octyl alcohol, monocarboxylic acids, such as, for example, butyric acid, capric acid, cyclohexanecarboxylic acid, chlorobutyric acid, lo benzoic acid, p-tertbutylbenzoic acid, 3,5-di-tert-butylbenzoic acid, chlorobenzoic acid, fatty acids derived from natural oils, as drying oils, semi-drying oils and non-drying oils, such as linseed, soybean, perilia, tung, walnut, pineseed, olive, oiticica, corn cottonseed, cocoanut, hemp 15 seed, herring, poppy seed, mustard, peanut, rapeseed, salmon, dehydrated castor oil, rubber seed, safflower, and the like, and mixtures thereof@ Particularly modifiers comprise the non-drying oil, semi-drying oil and drying oil fatty acids, and particularly those derived from dehy20 drated castor oil, soybean oil, linseed oil, cocoanut oil, safflower oil and oiticica oil. The alkyd resins are preferably prepared by heating the polyol with the polycarboxylic acid (or its anhydride) alid the modifiers together, preferably in an inert atmos25 phere. Ordinarily, no catalyst need be employed to effect this reaction, but, if desired, substances as p-toluenesulfonic acid, zinc chloride, stannic chloride, calcium acetate, barium acetate, and the like, in amounts varying from about 0.1% to 5% by weight of reactants may be 30 employed. The proportions of reactants to be used in preparing the alkyds may vary depending upon the properties desired in the finished product. Ordinarily, the polyearboxylic acid or anhydride will be reacted with at least 35 a chemical equivalent amount of the polyol and satisfactory results are obtained when up to 50% excess of the polyol is employed. A "chemical equivalent amount" as used herein in this regard refers to that amount of alcohol needed to furnish one OH group for every car40 boxyl group. In order to obtain superior alkyds, one preferably reacts the acid or anhydride with an excess up to 40% excess of the polyol. The amount of the modifier to be combined with the polyearboxylic acid or anhydride and polyol will vary 45 over a wide range depending on the type selected and the product desired. Generally, the amount of the modifier will vary from 20% to 80% by weight of the resinous product, with a preferred range of proportions varying from 30% to 70% by weight of the resin. ,3 0 The temperature employed during the resin-forming reaction may vary over a considerable range depending upon the type of reactants, catalyst, etc. In most cases, the temperature will ran.-e between about 100' C. and 250' C., with a preferred range of between 200' C. to 55 23 0'- C. 6 The alkyd formation may be accomplished in the presence. or absence of dillients. If solvents a-ud diluents are employed, it is desirable to utilize inert organic compounds, such as benzene, toluene, xylene, cyclohexane, 0and the like, and mixtures thereof. It is preferred to accomplish the preparation of the alkyd resins under a blanket of an inert gas, at least during the initial stages of the reaction. By an inert gas is meant one substantially devoid of moleculai: oxygen, such 65 as nitrogen, carbon dioxide, helium, methane, and the like. When the reaction is substantially complete, the inert solvents or diluents, remaining water and uncombined reactants are preferably removed from the reaction mix70 ture. Removal is conveniently accomplished by vacuum distillation, although fractional distillation, precipitation, may also be utilized. The alkyds prepared from the new polyols are particularly valuable in the preparation of air-drying or bak75 ing coating compositions. For this . applica on t ev ti
[4]-7 may l@e co -mbin@d with various coating s6lvents or oils or may be added to compositions containing film-forming components such as vinyl polymers, aminoplast resins@ cellulose ethers and esters and the like. The oil-modified alkyds- are particularly useful in the preparation of baking lacquers and enamels. In this case they are preferably combined with urea-formaldehyde or m elamineformaldehyde resins and other desired components, such as pigments, plasticizers, stabilizers, and the like, and the mixture then diluted with solvents or diluents to provide a composition having the desired viscosity. The composition may then be applied to the desired surface and baked at temperatures generally varying from 100' C. to 175' C. The resulting baked films are very hard and have good flexibility. The new polyols of the present invention may also be used to produce valuable monomeric esters and ethers. The esters of the polyols and monocarboxylic acids or acid esters of polycarboxylic acids are especially,useful as plasticizers for vinyl polymers, and particularly the vinyl halide polymers, as they are compatible therewith and form very hard flexible films. The monocarboxylic acids used in producing such esters may be exemplified by butyric acid, hexanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, palmitic acid, stearic acid, arachidic acid, sorbic acid, acrylic acid, methacrylic acid, crotonic acid, alphachloroacrylic acid, cyclohexanecarboxylic acid, toluic acid, methylbenzoic acid, nonylbenzoic acid, oleic acid, and the like and mixtures thereof. Mixed esters wherein one of the monocarboxylic acids is in aromatic acid and the other acid or acids is an aliphatic open-chain fatty acid are particularly good plasticizers for the vinyl halide polymers. The esters of the polyols and the unsaturated acids, such as acrylic acid and methacrylic acid, or the esters of the polyols and acid esters of polycarboxylic acids and unsaturated alcohols, such as allyl hydrogen maleate, are valuable as polymerizable plasticizers for the vinyl halide polymers as they may be mixed with vinyl halide polymers and a free radical yielding catalyst, such as a peroxide catalyst, and the combination then heated to effect polymerizafion. The product prepared in this monomer are very hard and tough but still highly flexible. The products plasticized in this monomer are useful in preparation of floor tile, seat covers, draperies and the like. The new polyols may also be used to produce polyepoxy ethers which are valuable in the formation of pottings and castings. This may be accomplished by reacting the polyol with an epoxy-halo-substituted alkane or dihalohydr oxy-substituted alkane to form a polyether halohydrogen and then treating that product with a dehydrohalogenating agent, such as sodium aluminate, to form the corresponding polyepoxy ether. To Rlustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and the invention is not to be regarded as limited to any of the specific compounds or conditions recited therein. Unless otherwise specified, parts disclosed in the following examples are parts by weight. E,cample I This example illustrates the preparation and properties of a polyol from alphahydroxyadipaldehyde and formaldehyde. 56 parts of acrolein dimer (.5 mole) was added to 1000 parts of water and .3 part concentrated sulfiiric acid. This mixture was stirred at room temperature for 30 minutes. To this solution of alphahydroxyadipaldehyde was added without further treatment, 147 parts (2.35 mole) of paraformaldehyde. Calcium oxide 33.5 parts (0.59 mole) was added portionwise over a 20 minute period. The solution was then warmed to 40' C., and stirred for 2 hours at this temperature and thenheated to, 2,809,186 8 and maintained at 50' C., for 2 hours. The calciuni' formate was removed by filtration and a slight excess of sulfuric acid was added to complete removal of calcium as calcium sulfate. Filtered and filtrate passed over basic ion-exchange resin to remove excess acid. The filtrate was then treated with charcoal. Solvents were removed by distillation at reduced pressure finally at 80' C. (I mm.). The residue 120 parts of a light colored syrup was viscous at 100' C., but solid at lower temperatures. 10 The solid had the following analysis: Ester value=0.34 eq./100 g. Carbonyl (free and combined) =0.125 eq./100 g. C=46.07 H=7.41 15 OH@ 1.45 eq./100 g. 60 parts of the solid produced above was mixed with 175 parts of water and exposed to hydrogen under 3000 p. s. i. at 200' C., in the presence of Raney nickel. In 6 hours .75 mole of hydrogen was absorbed. The nickel 20 was removed by filtration and the filtrate concentrated under reduced pressure to yield a water white syrup. This product had a 2.47 eq./100 g. OH value. The polyol produced by the above process can be used to produce valuable modified alkyd as shown by 25 the following experiment. 148 parts of phthalic anhydride, 300 parts of the polyol and 225 parts of dehydrated castor oil are placed in a reaction flask equipped with a stainless steel stirrer, nitrogen bubbler, thermometer and phase separating condenser. Xylene is used to 30 remove the formed water azeotropically. The charge is brought to a cooking temperature of 230' C., and held at that temperature for several hours. The resulting product is a light brown resin having an acid number 35 below 10. A white baking enamel is prepared by combining 100, parts of titanium dioxide, 75 parts of the alkyd prepared above and 25 parts of a urea-formaldehyde resin (Beetle 227-8) and adding xylene to obtain the desired viscosity. -10 This enamel is then sprayed on steel panels to form a film having thickness of 1 to 1.5 mils. These panels are then baked for 12 minutes at 165' C. The resulting films are very hard and flexible. A polyol having related properties is obtained by replacing the hydroxyadipaldehyde in the above prepara45 tion process with equivalent amounts of a hydroxypolyaldehyde obtained by condensing methacrolein in the presence of 4% aqueous NAOH as described in J. Am. Chem. Soc. 60, 1737 (1938). 50 Example II This example illustrates the preparation and properties of a polyol from glutaraldehyde and formaldehyde. 114 parts of 2-(3,4-dihydro-1,2-pyranyl) methyl ether was combined with 114 parts of water and the mix placed 5,5 in a reaction vesse equipped with a water-cooled reflux condenser. The mixture was then heated to boiling (about 95' C.) with total reflux condensation for about 8 hours. To the resulting solution of glutaraldehyde was added without further treatment 180 parts of para6o formaldehyde. Calcium oxide 33.5 parts was added portionwise over a 20 minute period. This solution was warmed to 40' C., and stirred for 2 hours at this temperature and then heated to and maintained at 500 C. for 2 hours. The calcium formate was removed by fil65 tration and sulfuric acid added to assist in removing calcium as calcium sulfate. Filtered and filtrate passed over ion-exchange resin. The filtrate was then treated with charcoal and distilled under reduced pressure. The resulting product was a light brown viscous syrup having 70 the following analysis:. C-41.96 H-6.85 OH-1.66eq./lOOg. Ester, 0.41 eq./ 100 g. 75 Carboriyl (free and combfned), 0.03
[5]9 50 parts of'the brown syrup was mixed with 175 parts of water and exposed @to hydrogen under 3000 p. s. i. at 200' C., in the presence of Raney nickel. 'In 6 hours .9 mole of hydrogen was absorbed. The nickel was removed by fiitration and the filtrate concentrated under 5 reduced pressure to yield a water white syrup. TEs prodiict had an OH value 'of 1.76@ eq./lOO 9. The polyol produced by the above process can also be used to produce valuable modified alkyd resins as shown by the following experiment. 148 parts of phthalic 10 anhydride, 300 parts of the polyol produced above and 230 parts of cocoanut oil fatty acids are placed in the reaction flask shown in Example I with toluene as the azeotrope former. The charge is brought to a cooking temperature of 230' C., and held at that temperature 15 for several hours. The resulting product is a light resinous solid. A clear coating lacquer is prepared by combining 40 parts of the alkyd produced above with 60 parts of benzoquananiine-formaldehyde resin (Uformite MX-61) and 20 adding toluene to obtain the desired viscosity. The restilting lacquer is then flowed out on tin plate panels to form a fflm of I to 1.5 thickness. These panels are then baked for 30 minutes at 150' C. The resulting films are placing the glutaraldehyd6 in the above-described preparation prbcess by equivalent amounts of each of the following: 1,6-hexanedial, 1,8-octanedial and 2 methoxy-1,8- octanedial. 30 Example III This example illustrates the preparation of a polyol from alpha,ganima-dimethylalpha-allyloxymethylglutaraldehyde and formaldehyde and some of the properties of 35 the-resultiiig' POIYOI.' A solution 43 paits (1.07 m6les) 6f sodium hydr6xide in 200 parts of water was added dropwise with stirirng to a solution of 86 parts -(0.435 mole) of alpha,gammadimet hyl - alpha - allyloxytnethylglutaraldehyd,6 and 144 40 parts (33.5%, .11.695 moles) '.for' fbrmalin in 300 ml., of metha nol at 15' C. The temperature was allowed to increa se to. room temp@rature during the addition of the latter 'of the 'sodiuhi hydroxide after which the mixture was heated to 45' C:, for one hotir. The addition 45 of carbon dioxide to the reaction mixture caused the separ ation of a large amount of salt which was removed by filtration. The filtrate was concentrated to a viscous mass from which more water was removed by - azeotroping with benzene. When no more water distilled, the 50 benze ne solution in the kettle was separated from the salt by filtration. The benzene was removed from the filtrate under reduced pressure and the residue was evacuated finally at 1001 C. (0.5 mm.), for one hour. The residu e was 50 parts of a light brown viscous syrilp. 55 The brown syrup produced as shown above is mixed with 175 parts of water and exposed to hydrogen under 3000 p. s. i. at 200' C., in the presence of Raney nickel. After .7 mole of hydrogen is absorbed, the nickel is remove d by filtration and the filtrate concentrated under (;0 reduc ed pressure to yield a water white syrup which had a high hydroxyl value. The polyol produced above can be used to produce a modifi ed alkyd resin as shown by the following. 148 parts of phthalic anhydride, 310 parts of the polyol and 65 225 parts of castor oil fatty acids are placed in a reaction flask described in Example 1. Xylene is used to remove the formed water azeotropically. The char.@e is broug ht to a cooking teinperature of 230' C., and held atthatt emperatureforseveralhours. The resultingprod- 70 uct is a light brown resin having an acid nuinber below 10. A clear lacquer composition is prepared by combining 60 parts of the alkyd produced above and 40 parts of a urea-formaldehyde resin (Beetle 227-8) and adding toluen e to obtain the desired viscosity. This lacquer is 75 10 then flowed out on tin pariels to form a film having ness of I mil. These panels are then baked for 30 minutes at 150' C. The resulting films are hard and have good flexibility. P61yols having related properties are obtained by repldcing th6 alpha,g@mmadimethyl-alpha-allyloxymethylglutaraldehyde in flie above preparation process with equivalent amounts of each of the following: alpha, gamma-dimethyl - alpha - hydroxyethoxymethylglutaraldehyde, alpha,gamma-dimethyl - alpha - dodecyloxymethylglutaraldehyde and alpha,gamma - dimethyl-alphacyclohexyloxymethylgliitaraldehyde. Example IV This example iflustrates the preparation of a polyol from an acrolein-alphamethylstyrene copolymer and formaldehyde. . 1 A solution of 69 parts of alpha-methylstyrene, 30 parts of acrolein and I part of ditertiary-butyl peroxide was. heated at reflux temperature for 24 hours. Removal of the unreacted materials by reduced pressure distillation gave 21 parts of solid copolymer resin having carbonyl value of 0.55 equivalents per 100 grams and a moleclular weight of 765. and then reacted with 6 parts of paraformaldehyde in the presence of 0.5 part, of sodium hydroxide. The reaction was carried out with stirring at 70-85' C., for 2 hours. The formed resin was precipitated from the reaction solution by pouring the solution into water and futering the resin tberefrom. The dried resin was a solid having a hydroxyl value of 0.23 eq./100 g. 50 parts of the above resin is mixed with 175 parts of: water and alcohol and exposed to hydrogen under 3000 p. s. i. at 200' C., in the presence of Raney nickel. The nickel'is rbmoved by filtration and the filtrate concentrated under reduced pressure to yield a solid polyol having,a very high OH content. This polyol is re@acted with phthalic anhydride and castor ofl fatty acids by the method shown in the preceding example to produce a modified alkyd resin which is useful in the preparation of baking enamels. We
