US2072068A - Resinous products or compositions and process of making same - Google Patents

Description

Patented Feb. 23, 1937 This invention relates to resinous products or compositions and to the process of making same and relates especially to resinous compositions maleic, fumaric, mucic, succinic acids and the like may be utilized; also non-crystalline acids such as lactic acid; likewise aromatic acids such as phthalic, diphenic or other polybasicacids, or benzoic, salicylic or similar monobasic acids. The anhydrides of these acids may be used to advantage in some cases. The employment of substances yielding these acids during the reaction is not precluded. Mixtures of such crystalline acids likewise may be employed.

The oily material includes the fatty acids of various drying oils such as linseed, tung and the like, fish and whale fatty acids and those of rape, perilla, soya bean, sunflower, corn and others of a similar character; in some cases including fatty acids of cottonseed oil such as those obtained by Or a mixture of fatty glycerides and free fatty acids may be utilized. Blownoils are especially desirable when a light color is not required and I prefer to employ blown rape or corn oil or similar blown oils preferablyco'ntaining some free fatty acid. In the case of the blown'oils the oxygen which is combined with the oil through the operation of blowing apparently serves as a locus of reaction to enable a deep seated resiniiication to take place.

The union with the foregoing of resin acids such as those of ordinary rosin is notprecluded.

In the illustrations which follow I have employed phthalic anhydride as a typical acid for carrying out the present invention but it should be understood of course that various other crystalline acids, or acids recognized as having deflnite crystallizing properties, may be used in admixture with, or to supplant phthalic anhydride or phthalic acid set forth illustratively herein.

The following examples are illustrative of the polymerization which takes place when a fatty oil is used. The point of polymerization is that temperature at which the mixture in the reacting flask almost instantaneously becomes solid forming an, infusible and insoluble-product and assoumrao STATES PATENT, OFFICE RESINOUS PRODUCTS OR COMPOSITIONS AND PROCESS OF MAKING SAME Carleton Ellis, Montclair, N. 1., assignor to Ellis- Foster Company, a corporation of New Jersey No Drawing. Application October I0, 1925, Serial No. 61,839. Renewed October 2d, 1936 (on. ace-s) eiated with a certain amount of free uncombined oil.

Note.--In all the examples given below the glycerol used was a C. P. glycerol of 98 per cent strength.

Example 1.1l1 parts by weight of phthalic anhydride, 47 parts of-glycerol and 50 parts of raw linseed oil were gradually heated in a flask fitted with an air condenser and a mechanical agitator. The oil did not appear to enter into reaction with the phthalic anhydride and glycerol since a non-homogeneous mixture remained in the flask continuously .during the heating and the mixture polymerized at 270 C. forming an infusible and insoluble product with separation of a considerable quantity of oil.

Example 2.-- -94 parts of glycerol, 160 parts of phthalic anhydride and 80 parts of soya bean oil containing 3 per cent free fatty acids were heated in the same apparatus as above for one hour and fifteen minutes raisingthe temperature gradually. At the end of one hour and ten minutes a considerable frothing took place accompanied by thickening of the mixture and when temperature reached thepoint of 235 C. the

whole contents of the flask polymerized into a solid spongy infusible body containing free oil.

Example 3.94 parts of glycerol, 160 parts of phthalic anhydride, 80 parts of China-wood oil were placed in the apparatus as above and gradually heated on an oil bath with agitation. The

temperature was gradually brought up to 235 C.

in one hour and twenty minutes. Beginning at 222 C. the contents of the flask gradually became thicker. The productwas not heated above 235 C. and was taken from the flask and v cooled. A dark yellow, hard brittle resin containing a small amount of unreacted oil was obtained. This resin had a melting point of 73 (3., acid number 56. It was soluble in organic solvents such as an equal part butyl acetate-butanol mixture and mixture of equal parts of benzol and'alcohol. When dissolved in proper solvent it can be blended with nitrocellulose forming a uniform solution. v

Example 4.94 parts of glycerol, 160 parts phthalic anhydride and parts of cocoanut oil containing 12 per cent of free fatty acids were heated in the apparatus as above for one hour and ten minutes. When the temperature reached 260 C; the contents of the flask became almost solid forming a dark yellow brittle opaque resin containing a great excess of uncombined oil. This product has a melting point of C. and anacid number of 34.

In the foregoing examples the product in every case was either infusible and insoluble with separation of oil or contained a. quantityof uncombined oil. Resins prepared from the fatty acids of the drying and semi-drying oils with organic do Example 2 Example 7 Example 8 Per cent of fatty acids in total weight of oil and fatty acids. 3% 13% 267 Tamperature of polymeriza- 235 C. 246 C. Atove 275 on. i

acids and polyhydrie alcohols are clear homogeneous soluble masses and show no indication of any free oily material and in most cases have a comparatively low acid number. In the following examples illustrations of resin prepared from the free fatty acids are given.

Example 5.--23 parts of glycerol, 46 /2 parts of phthalic anhydride and 40 parts of linseed oil fatty acids were heated in the apparatus described above for half an hour bringing temperature up to 290 C. I The product obtained was a soft sticky resinous material soluble in butyl acetate and miscible -.with nitrocellulose.

Example 6.94 parts of glycerol, 160 parts of phthalic anhydride and parts of soya been 011 fatty acids were heated in a round bottom glass flask with a reflux condenser with mechanical agitation for one and one-half hours up to 265 C. The product obtained was a dark, glossy, brittle, very slightly tacky' resin. This resin has a melting point of 71 C. and a low acid number, namely 17.2. The resin was easily soluble in the usual organic solvents and was blendable with nitrocellulose.

Mixtures of oils and fatty acids instead of the fatty acids alone also produce a satisfactory resinous mass'for some purposes but greater care must be exercised in the preparation of such resins. In general, the resins are more susceptible to polymerization at the elevated temperatures required in their production. The greater the proportion of fatty acids to oil used in their production, the less susceptible are such compositions to polymerization and this point is clearly brought out in the following ilustrations.

Example 7.94 parts of glycerol, 160 parts of phthalic anhydride and 80 parts of a rancid soya bean oil containing 13 per cent of fatty acids were heated with agitation in a flask supplied with an air condenser for one hour and twenty minutes. The mixture did not polymerize at 235 C. but gradually became thicker on heating above this point and polymerization occurred at 246 C.

Example 8.94 parts of glycerol, 160 parts of phthalic anhydride, 60 parts of soya bean oil containing 13 per cent of fatty acids and 10 parts of additional soya bean fatty acids were placed in the same apparatus as above and gradually heated with agitation on an oil bath for two hours and forty-five minutes, bringing temperatureas high as 275 C. without any indication of polymerization. The product of this reaction was a clear dark resin resembling that preparedwith fatty acids alone (Example 6). The melting point of this resin was 89 C. and its acid number was 16.5.

Comparing the results obtained in Examples 2, 7 and 8, the relation between the relative amount of fatty acids and the temperature of polymerization was as follows:

Theuse of blown oils in the preparation of the resinous products produced by means of the present invention is not precluded, and in some cases their use is of advantage in that a superior product from some purposes is formed.

The product differs from those produced from butanol.

the oils which have not been blown in that a" homogeneous product is formed at lower temperatures whichis soluble in butyl'aeetateebutanol mixtures and benzol-alcohol, and'there is no a non-homogeneous resin is produced containing free oil, and unsuitable for use in many instances. When blown oils are substituted for the vegetable oils in the preparation of these resinous compounds polymerization also takes place at 240- 250 C., but very little, if any, free oil separates.

If the blown oil resinous compound is prepared at a'temperature below that at which the mass will polymerize, or, 235-240 0., a homogeneous translucent resin is produced, which is soluble in the above named solvents. It also has the additional .valuable property of being. much tougher than the resins produced from the free fatty acids, and in this respect differs from them.

Following are examples of methods of producing the resins from blown oils.

- Example 9.-94 parts of glycerol, 160 parts of phthalic anhydride and 80 parts of heavy blown rapeseed oil were heated in an apparatus similar to that used in the preceding examples. After heating for one hour and five minutes the ternperature was brought to 235 C., and a sample of resin drawn from the flask at that point was a hard, (rubbery while hot) resin. The heating was continued for thirty minutes more keeping the temperature of the reacting mixture, between 235 and 240 C. At the end of this time the product obtained was a dark, uniform, hard, exceptionally strong glossy resinwhich did not melt when heated on hot plate but softened at a temperature of 90 C. The resin was easily s01- uble in butyl acetate-butane] mixture, alcoholbenzol mixture and in isopropyl alcohol. It was easily blendable with nitrocellulose and had an acid number of 57.0. v

Example 10.94 parts of glycerol, parts 'phthalic anhydride and 80 parts of blown fish one hour and ten minutes the temperature final ly reached 280 C., and a dark opaque hard brittle resin having a glossy appearance and fair strength resulted. The yield was 94 per cent, the acid number 28, and the melting point about 80 C. It was found to be soluble in a mixture of benzol and alcohol, but yielded a turbid solution in the cold with a mixture of butyl acetate and This cleared on warming.

The solution to which nitrocellulose was added was somewhat more turbid, but became clear on the addition of some acetone. The resulting film was translucent.

Example 11.-Glycerol 23 parts, or 1 mol., benzoic acid 60 parts, or 2 mols, and the free fatty acids of tung oil 40 parts, or approximatehr mol., were heated in a receptacle fitted with an air condenser and provided with an agitator,

the temperature being raised gradually to 260 glycerol, or with the latter and a neutral fatty oil,

6., over a period of two hours. The resulting product on cooling was a dark soft gummy material, having an acid number of about 14. The

yield was 87 per cent. The product was easily soluble in a mixture of alcohol and benzol, also in butyl acetate, and in a mixture of the acetate Equal parts of the gum and low viscosity nitrocellulose were warmed and stirred together without any solvent. Practically a homogeneous mixture resulted, which under the microscope exhibited very few fibres.

Example 12.A product of a high acid num-' ber, namely; 62, was made by. heating glycerol 46 parts by weight, or 1 mol., phthalic anhydride 92 parts, or 1 "mols,.and the distilled free fatty acids of corn oil 80 parts, or mol. After twenty minutes heating the temperature was 240 0., and the forming resin was soft and turbid. At the end of one hour, the temperature being 270 C., the resin was clear. After a total heating of one hour and fifteen minutes, with a final temperature of 290 0., at which pointsome frothing occurred, the resin was still soft and clear. Finally it was heated for thirty minutes longer between 280 and 290 C., fumes of acrolein being given off, and the resin darkening rapidly. The product was soluble in a mixture of benzol and alcohol, and also in a mixture of butyl acetate and butanol, giving a clear goldencolored solution with a green fluorescence. The addition of low viscosity nitrocellulose second soluble cotton) yielded a strong clear film.

Example 13.-A very soft resin or gum having a low acid number was obtained with the aid of corn oil fatty acids, as follows:

94 parts of glycerol, or 1 mol., 60 parts phthalic anhydride, oat 3 mol., 50 parts benzoic acid, or mol., and 100 parts fatty acids of corn oil, or approximately mol., were heated for twenty minutes with temperature rising to 180 C.

After an additional twenty-five minutes tem-- perature 215 0., ten minutes later 235 C.,. at which point considerable bumping occurred. In one hour the temperature was 260 0., and in one hour and fifteen minutes 295 C. There was no indication-of any coagulation due to polymerization. The product was rather dark and had a thick honey-like consistency. The acid number was 9.7. Theproduct was easily soluble in. a number of organic solvents, and blended with nitrocellulose forming a clear solution and a clear film. It had a gelatinizing action on soluble cotton in the absence of volatile solvents, having in this respect an effect somewhat. akin to camphor.

Example 14.A solidhaving the property of dissolving in water to form a turbid solution was obtained in the following manner:

94 parts of glycerol, 160 parts tartaric acid, and '60 parts of crude cottonseed oil fatty acids were mixed and heated as before, the temperature reaching 150 0., after twenty-five minutes, considerable waterbeing givenoif; 205 C;, after 45 minutes, the reaction having advanced to yield a dark brittle solid, and at the 'end of fifty minutes the temperaturebeing 210 0.1 theheat- .ing was discontinued. The yield was 81 per cent, and the product was a hard dark fusible resinous appearing material, having-an acid polymerization usually takes place at atemperature between 170 0., and. 180 0., the 1'01- mation'of an insoluble material. It should be noted that in the above example'the temperature was carried past this polymerization point due to the presenceof the cottonseed oil fatty acids. The resin was difilcultly soluble in a mixture of benzol and alcohol, but was easfly soluble in a,

mixturepf butyl acetate andbutanol, forming a clear solution andyielding a clear film with soluble cotton. When the resin is boiledwith water it goes into solution, forming a turbidliquid of light yellow color. On evaporation a resin is obtained which is hard and brittle when cold, and is not as easily soluble in a mixture of butyl acetate 1 The employment of ricinol'eic acid to prevent polymerization and thereby enable'the temperature and period of heating to be adequate to substantially reduce the acid number of the product has been set forth in my co-pending application Serial No. 22,882, filed April 13, 1925.

The present application is concerned with resinification reaction by the aid of fatty acids of mineral or vegetable oils (e. g., those with 16 to 20 or 22 carbon atoms) containing siccative components such as linoleic, linolenic, clupanodonic acids and'the like, likewise preventing polymerization of the desired resin during a period of heating sufiicient to reduce the acid number greatly 'and bring about the desired resiniflcation reactions without the formation of insoluble products preventing utilization in paints, varnishes and lacquers.

on the other hand the soluble product may be baked, with or without fillers, eventually to yield infusibie and insoluble bodies or masses, which may be used as insulating material or otherwise in the field of plastic molding.

A specific form of the invention involves a lacquer solution of the aforesaid type of resln with nitrocellulose, especially low viscosity soluble cotton, employing various proportions, say equal parts in a solvent mixture such as benzol-anhy-r drous ethyl alcohol for the alcohol-soluble type of nitrocellulose or butyl acetate-butanol for nitrocellulose generally. Other solvents such as ethyl carbonate, furfuraLtoluol, xylol, amyl acetate, acetone, methyl alcohol and the like may be employed according to requirements. Coatings of this character have shown a very great resistance on exposure tests.

The softer forms of the resins require no softeners or plasticizers but with the harder resins the employment of diethyl phthalate, diamyl phthalate, tricresyl phosphate, acetin, castor oil and the like is sometimes advantageous, when a very flexible nitrocellulose film'is required.

Mixtures of any of the foregoing resins may be made for incorporation'with nitrocellulose and other synthetic or natural resins may be added in appropriate and compatible proportion.

Pigments such as prussian blue or titanox should be ground with the vehicle in a ball or tube mill for a considerable period to attain a very fine suspension perhaps partly colloidal or dispersed.

Instead of using natural fatty oils consisting of or containing oily fatty acids more unsaturated than oleic acid, mixtures of fatty oils or fatty acids may be made, for example by mixing linoleic i v 4- A v acid'with oleic acid to have present a substantial or influential proportion of the former. Or the fatty acids of cocoanut oil may be mixed with those of linseed oil or with linseed oil itself. Such mixtures of these water-insoluble oily fatty acids or fats may be utilized to make the resin in conjunction with the water-soluble or crystallizable acidsaforesaid and glycerol, glycol or similar polyhydric alcohol.

In general I prefer to employ in the latter class acids of ten carbon atoms or less, these being 12 carbon atoms and preferably 16 or 18 carbon atoms and upwards. This may include cyclic acids such as naphthenic acids in some cases.

The oily component conferring such water-resistance preferably should contain a siccative constituent, e. g., the fatty acids of a drying or semi-drying oil, specifically acids with two or more double bonds, or a higher degree of unsaturation than oleic acid. The latter acid may however be present. Stearic acid in'large proportion is likely to give a greasy product and in the case of nitrocellulose, films containing such product greasy exudations frequently will be observed.

A specific and desirable form of the invention is the employment of a blown fatty oil, especially -a blown drying or semi-drying oil, blown rapeseed oil being preferred. A heavy blown rapeseed oil yields a very tough water-resistant resin.

- What I claim is: Y

l. The herein-described resinous reaction product of polyglycerols, phthalic anhydride and a monobasic fatty acid.

2. The herein described resinous reaction product of polyglycerols, phthalic anhydride and a monobasic unsaturated fatty acid.

3. The herein-described resinous reaction product of polyglycerol, phthalic anhydride, and oleic acid.

4. A reaction product of a polymerized polyhydric alcohol, a resinifying crystalline organic carboxylic acid, a monobasic fatty acid, and natural resin.

5. A reaction product of: a polymerized polyhydric alcohol, a resinifying crystalline organic carboxylic acid, an oily material containing the acid radicals of glyceride oils, and a natural resi acid. 6. A reaction product of a polymerized polyhydric alcohol, a crystalline organic carboxylic acid, drying oil acids, and a natural resin.

7. A reaction product of a polymerized polyhydric alcohol, a crystalline organic carboxyl acid, a drying oil, and a natural resin.

8. A resinous reaction productof: a polyhydric alcohol, a resinifying organic carboxylic acid, fatty acids of a semi-drying oil, and a natural resin.

9. A resinous reaction product of: a polyhydric alcohol, a resinifying organic carboxylic acid, a semi-drying oil, and a natural resin acid.

10. A resinous reaction product which on saponiilcation yields a polyhydric alcohol, a resinifying carboxylic organic acid, a natural resin acid,

and acids of a semi-drying oil.

11. A resinous reaction product of solely: a polyhydric alcohol, a resinifying organic carboxylic acid, a blown oil, and a natural resin acid.

12. A resinous reaction product of a polyglycerol, an organic carboxylic acid selected from the group consisting of phthalic acid, maleic acid, succinic acid, fumaric acid, and malic acid, and anoily material containing acid radicals of glyceride oils. r

13. A resinous reaction product of a polymerized polyhydric alcohol, an organic carboxylic acid selected from the group consisting of phthalic acid, maleic acid, succinic acid, fumaric acid and malic acid, and oily material containing acid radicals of glyceride oils and a natural resin acid.

14. A resinous product comprising a polyhydric alcohol mixed ester of acids of a semi-drying oil, natural resin acid, and an organic carboxylic acid selected from the group consisting of phthalic acid, maleic acid, succinic acid,.fumaric acid and malic acid.

15. A process of producing a synthetic resin which comprises heating to a reaction temperature, a reaction mass containing a polyhydric alcohol, an oil material containing acid radicals of semi-drying glyceride oils, an organic carboxylic acid selected from the group consisting of phthalic acid, maleic acid, succinic acid, fumaric acid and malic acid, and a natural resin acid.

CARLE'HION ELL-Is.