US2388583A - Chemical process and product - Google Patents

Description

Patented Nov. 6, 1945 CHEMICAL PROCESS AND PRODUUE Alger L. Ward, Bala-Cynwyd, Pa.,' assignor to The United Gas Improvement Company, a corporation of Pennsylvania No Drawing. Application June d, 1943, Serial No. 489,693

7 Claims.

This application is a continuation-in-part of my copending application Serial Number 264,591, filed March 23, 1939.

The present invention relates to the production of aryl substituted phenols.- More particularly, it relates to the production of aryl substituted phenols by reacting phenols with unsaturated aromatic hydrocarbons including unsaturated aromatic hydrocarbons boiling in the range of from 150 to 167 C. and obtained from light oil from the pyrolysis of petroleum oil.

The lower boiling condensate and the distillate from the tar produced in the manufacture of carburetted water gas, oil gas, and the like, which involve the pyrolysis of petroleum, is termed light oil. The higher boiling portion of the light oil contains a variety of unsaturated aromatichydrocarbons mixed with saturated aromatic hydrocarbons of neighboring boiling points.

For instance, the higher boilingportion of a light oil produced in'the manufacture of oil gas may contain styrene, ortho, para, and meta methyl styrene, indene, and other unsaturated aromatic hydrocarbons in admixture with the xylenes, cumene, pseudo-cumene, durene, and possibly other saturated aromatic hydrocarbons. These unsaturated hydrocarbons may be concentrated by further fractionation of the higher boiling portion of the light oil. For instance, alight oil produced in the manufacture of oil gas has been fractionated as follows to concentrate the following unsaturated aromatic hydrocarbons:

' Cut points, *0. styrene forerunnings 135 to 140 Styrene 140 to 15-0 Unsaturates A1 150 to 160 Unsaturates A: 160 to 167 Methyl styrene group 1 167 to 172 Methyl styrene group 2 1'72 to 175 ,Indene group 175 to 183 Unsaturates 3B1 183 to 190 Unsaturates B: 190 to 200 The letters A1, A1, B1, and B2 refer to unsaturated aromatic unsaturated hydrocarbons and including unsaturated aromatic hydrocarbons boiling in the range from 150 to 167 C., may be reacted with phenols to give mixed aryl substituted phenols corresponding to the various aromatic unsaturates contained therein, or preferably the ing in the range from 150 to 167 C. The con:

rately reacted with a phenol.

centration may be such as to yield a fraction having its 10% and boiling points within the recited range or the concentration may be such as to yield a fraction boiling substantially completely within the recited range.

The unsaturation contained in the light oil and boiling within the range from to 167 C. may be subdivided, if desired, and the divisions sepamay be advantageous to react with a phenol a light oil fraction having the preponderant part of its unsaturation in the form of unsaturated aromatic hydrocarbon material boiling in the range from 150 to C. The concentration may be such, that the 10% and 90% boiling points of the fraction fall between 150 and 160 C.. or substantially the entire fraction may boil between 150 and 160 C. Likewise a phenol may be reacted with a light oil fraction having the preponderant portion of its unsaturation in the form of unsaturated aromatic hydrocarbon material boiling in the range from 160 to 167 0., or having its 10% and 90% boiling points within that range, or boiling substantially completely within that range.

It may be desirable in the case of highly concentrated individual unsaturates or groups, to add an inert solvent such as a saturated hydrocarbon prior to reaction with the phenol.

By phenols, I intend to mean the monoand polyhydroxy derivatives of benzene and its homologues, such as for instance, phenol, cresol, resorcinol, pyrogallol, hydroquinone, pyrocatechol, naphthols, and the like, and substitution products of such compounds. As examples of acids suitable as catalysts for the reaction, sulphuric acid and phosphoric acidmay be mentioned,

For example, it

I have found that the aryl substituted phenols produced in the performance of my invention may be reacted with aldehydes to form resins which are soluble in drying oils, such as linseed oil and tung oil. This characteristic gives them great value for use in varnishes and lacquers in which the usual phenol aldehyde condensation products cannot be used due to their incompatibility with linseed oil and tung oil.

By aldehydes, it is intended to mean the aldehydes customarily employed in the production of phenol aldehyde condensation products of which, for example, formaldehyde and furfural may be preferred because of their relative cheapnesa.

I have found that in the performance of my invention, in addition to producing valuable aryl unsaturated aromatic hydrocarbons contained in.

such light oil fractions, the proportion of the mono substituted aryl phenols with respect to diand tri-substituted phenols may be controlled, increasing excesses of phenol giving higher pro- 7 portions of mono substituted products.

The invention will be further understood by reference to the following illustrative examples:

Exsuru 1 Twelve mols of phenol (1128 grams) were weighed into a 3 necked flask equipped with a stirring device, a'dropping funnel and a thermometer. To this was added 1.2 cc. of 96% H2804. To this were added 1684 grams of a light oil hydrocarbon fraction obtained during a fractional distillation of light oil produced in the manufacture of oil gas by taking a cut over the temperature range 150-160. C. This hydrocarbon fraction contained 28.0% of unsaturated materials by bromine analysis (the unsaturatedmaterial being arbitrarily calculated as monooleiine and having an average molecular weight of 118) and the weight used contained 4 mols of reactive hydrocarbon material. This addition was performed dropwise with vigorous agitation. To facilitate agitation at the start of the reaction, the phenol was melted by heating it on a water bath to about 42 C.

By variation of the rate of addition of the hydrocarbon fraction, the temperature was maintained at approximately 45 C. during the entire time the hydrocarbon was being added to the phenol catalyst mixture. The time required for this addition ofhydrocarbon material was 3-4 hours.

When addition of the hydrocarbon fraction had 2 hours.

ing about 2263 grams of unreacted phenol and saturated hydrocarbons, a fraction was taken distilling over in the range 140-200 C. at 2-5 mm. absolute pressure, which weighed 494 grams (58.7%) of theory. This fraction was a viscous. oily liquid, phenolic in nature as shown by subsequent tests. A solid residue remained in the distillation flask, amounting to 95.5 grams.

Color (Gardner Holt) 64 Sp. gr. D 20/4 1.0798 N 20/D 1.5860 Mol. weight"; 178.6 Zerewitinofl value"... per cent 90.8

This phenolic material evidently comprises a mixture 01' aryl substituted phenols produced by reaction of the phenol with the aromatic unsaturates contained in this light oil cut.

Exam 2 6.6 mols of phenol (620, grams) were weighed into a 8 necked flask equipped with a stirring device, a dropping tunnel and a thermometer. To this was added 0.66 cc. H2804. To this were then added dropwise 880 grams of a light oil hydrocarbon fraction obtained during a fractional distillation of light oil produced in the manufacture of oil gas by taking a cut over the temperature range 160-167 C. This hydrocarbon fraction contained 29.8% by weight of unsaturated materials according to bromine analysis (the unsaturated material being arbitrarily calculated as monoolefine and having an average molecular weight of 118) and the weight used therefor contained about 2.2 mols of reactive hydrocarbon material. To facilitate agitation at the start of the reaction, the phenolwas melted by heating it on a water bath to about 42 C.

By variation of the rate of addition of the hydrocarbon fraction, the temperature was maintained at approximately 45 C. during the entire time the hydrocarbon was being added to the phenol-catalyst mixture. The time required for this addition of hydrocarbon material was about 3 hours.

When addition of the hydrocarbon fraction had been completed heat was applied. The material was kept at a. temperature of l30-l60 C. for 2 After cooling to C., the H2504 in the mixture was neutralized by adding the calculated quantity of NarCOa dissolved in a few cc. of water.

The purification oi the desired condensation product and the recovery of the excess phenol and saturated hydrocarbon was accomplished as follows Without washing or other treatment the reaction mixture was distilled. After collecting about 979 grams of unreacted phenol and saturated hydrocarbons, a fraction was taken distilling ,over in the range -l96 C. at 2-3 mm. absolute pressure, which weighed 360 grams (about 77% theory). This fraction was a viscous, oily liquid, light amber in color and phenolic in nature as shown by subsequent tests. A solid residue remained in the distillation flask amounting to 84 grams. This solid residue need not be addition.

considered a waste as it has interesting properties indicative of industrial value.

The hydrocarbon and the unused phenol can each be recovered in a relatively pure state by simply conducting the distillation under a fractionating column.

The material distilling in the range l40-196 C. at 23 mm. absolute, pressure, had the following physical properties:

Color (Gardner Holt) 5 Sp. gr. D 20/4, 1.0901 N 20/ 1.5915 M01. w i 194.5 Zerewitinoif value percent 86.5

The phenolic material evidently comprises a mixture of aryl substituted phenols, produced by reaction of the phenol with the aromatic unsaturates contained in the light oil out.

' Referring to Examples 1 and 2, the following table gives properties of the distillation residues produced therein.

Distillation of these residues gives very viscous semi-solid liquids of deep amber color constituting di-substituted phenols.

As before stated, the proportion of mono-substituted phenols to til-substituted and tri-substituted phenols produced in the reaction'may be 40 controlled by controlling the proportion of phenol to the unsaturated aromatic hydrocarbons, a

molar excess of phenol having been found desirable when the desired products are mono substituted phenols. However, the excess of phenol may be limited by practical considerations and it may be desirable to employ proportions resulting in the production of considerable proportions of both mono and di-substituted products.

For example, a molar ratio of phenol to fractlon unsaturation (considered arbitrarily for purposes of calculation as monoolefinic material of Exlmru: 3 To two mols of phenol containing 0.2% by weight of H2804 are added slowly a quantity of a cut takenfrom 150 to 160 C. of a light oil obtained, in the manufacture of oil gas. said quantity containing 1 mol. of unsaturation (arbitrarily calculated as monooleflnic and having a molecular weight of 118). The temperature is kept below50p C. by regulation of the rate of When the light oil out is all added the mass is heated to 120-150 C. for 2 hours with agitation. After neutralization of the H2804 with the calculated amount of NazCOz solution, the product is fractionally distilled. The fraction distilling above 200 C. at 2-5 mm. will be found to be. principally the disubstituted product;

Exsmru: 4

Following the same procedure as in Example 3, but employing a light oil out taken from 160 to 167 C. in sufllcient quantity to provide 1 mol of unsaturation (arbitrarily calculated as mono- 'oleflnic and having an average molecular weight of 118), the distillation of the product will yield a fraction boiling above 196 C. at 2-5 mm. and containing principally the disubstituted product.

Itwill be seen from the examples given above, that the process of the invention provides a simple and inexpensive separation of the products of the reaction.

After, neutralization of the small quantity of acid, it is only necessary' to distill the products to recover separately the unreacted hydrocarbons,

and water, the unreacted phenol, and to separate the mono aryl phenol from di-aryl phenols and any higher substitution products, which are less valuable products. It is not necessary to wash out the acid catalyst prior to distillation because of the small quantity employed.

The procedure permits the recovery of the saturated aromatic hydrocarbons of the light oil fractions boiling in the range from 150 to 167 C. and obtained in the pyrolysis of petroleum, which contain considerable concentrations of aromatic unsaturates without the large wash losses incident to washing out the aromatic unsaturates and further provides for recovering the aromatic unsaturates as valuable aryl phenols.

For example, in the production of substituted phenols from the light oil unsaturation in the boiling range of from 150 to 167 C., recoveries of saturated aromatic hydrocarbons containing little olefinic contamination are possible by frac: tional distillation of the product. The yield of saturated hydrocarbons may be as high as 75% or more of the light oil fraction employed.

As stated before, the aryl phenol produced in accordance with the present invention may be reacted with aldehydes to produce substituted phenol-aldehyde resins which are compatible with drying oils, such as linseed oil and tung oil.

EXAMPLE 5 Approximately 318 grams of the mono-substituted product of Example 1 (corresponding to 1% mols of the mono-substituted phenol on the basis of the assumed average molecular weight of 118 for the'o'riginal unsaturates) are used in a specific preparation of a varnish resin. A wide boiling cut made from about 140 to 200 C. at approximately 2-5 mm. pressure is used. The above quantity is reacted with three mols grams) of formaldehyde in the form of an approximately 37% solution and three grams of oxalic acid with agitation on a steam bath for 24 hours. The reaction is carried out in a flask provided with a refluxcondenser. In order to compensate for the loss of formaldehyde by vaporization during the long heating period, the formaldehyde solution is added stepwise: 50% being added initially, 25% after 8 hours and 25% after 16 hours. After the heating period, the reflux condenser is changed to a take-oil condenser, the temperature is raised to about 200 (2., the system is evacuated to about 50 mm. pressure and the resin issteamed for two hours. The flask is cooled somewhat and the resin is poured out while still molten.

The hardened resin is crushed and sieved. It will be found compatible with linseed and tung oil and may be cooked with these oils tofiorm varnishes. 1

The compatibility of these resins with the usually employed drying oils, linseed oil and tuna oil, is an extremely valuable characteristic. It opens the door to the employment 01' phenol aldehyde condensation products in coating compositions, such as drying oil varnishes, and aflords a new utilization oi the unsaturated aromatic hydrocarbons contained in light oil from petroleum pyrolysis, of which there i an extremely large potential supply.

The process herein described also 'aifords a more economical method of recovering the saturated aromatic hydrocarbons accompanyinl the unsaturated aromatic hydrocarbons in such light oil.

It is to be understood that the above particular description is by way of illustration and that changes, omissions, additions, substitutions. and/or modifications may be made withinv the scope of the claims without departing from the spirit of the invention which is intended to be limited only as required by the prior art.

. I claim:

1. A proces comprising reacting a phenol with a light oil traction containing unsaturated hydrocarbon material boiling within the range from 150 to 167 C., said reaction taking placein the presence of a condensation catalyst, and said light oil having been obtained from products of pyrolysis of petroleum oil.

2. A process comprising condensing a phenol in the presence of a mineral acid catalyst with a light oil fraction containing unsaturated aro-- matic hydrocarbon material which boils in the range from 150 to 167 C., said light oil having been obtained from products of pyrolysis produced inthe. manufacture of combustible gas by a process involving the thermal decomposition of petroleum oil.

3.A process for producing aryl substituted phenol material comprising reacting a phenol in the presence of a mineral acid catalyst with a light oil traction boiling preponderantly in the range from 150 to 167' C. and containing unsaturated aromatic hydrocarbon material boiling within said range, said light oil having been separated from Products of pyrolysis obtained in comlight oil traction having 10% and boiling 1 points within the range from to 167' C. and

containing aromatic unsaturation boiling within said range, said light oil having been recovered from petroleum pyrolysis products.

5. A process for producing aryl phenol material comprising condensing a phenol in the presence of a mineral acid catalyst with a light oil fraction boiling preponderantly within the range from 150" to C. and containing aromatic unsaturation boiling in said range, said light oil having been obtained from products of petroleum oil pyrolysis.

6. A process for producing aryl phenol material comprising condensing a phenol with a light oil traction the preponderant part of which boils in the range 160 to 187 C. and which contains aromatic unsaturation which boils within said range, said light oil having been obtained from products of pyrolysis of petroleum oil.

7. A process tor producing and phenol material comprising condensing phenol in the presence of sulfuric acid as a cataLyst with a fraction oi a light oil obtained from petroleum oil pymlisis products, said fraction containing unsaturated aromatic hydrocarbon material which boils with- 40 in the range from 150 to 167- C., said condensa-