US2598234A - Certain oxyalkylated derivatives of trinuclear aromatic compounds and method of making same - Google Patents

Description

Patented May 27, 1952 CERTAIN OXYALKYLATED DERIVATIVES OF TRINUCLEAR A R O M A T I C COMPOUNDS AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application November 12, 1948, Serial No. 59,766

8 Claims. (Cl. 260-613) thetic products of the formula O(RaO),.H O(Ri),.H 0 R=0 ..H

in which R is a member of the class of alkyl, aralkyl, alicyclic and aryl radicals having not over 8 carbon atoms, and R1 and R2 are members of the class of alkyl, aralkyl, alicyclic and aryl hydrocarbon radicals having not over 18 carbon atoms, and R3 is a member of the class of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20, with the proviso that at least two moles of alkylene oxide be introduced for each phenolic nucleus.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This specific application is described and claimed in our co-pending application Serial No. 59,765, filed November 12, 1948, now Patent Number 2,543,489. The new products are also useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; ,as wetting agents and detergents in the acid washing of fruit; in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; ,as germicides, insecticides, emulsifying agents, as, for example, for cosmetics,

spray oils, water-repellent textile finishes; as

lubricants, etc. 7 7

Attention also is directed to the fact that the herein described compounds may be employed as intermediates for the manufacture of more complex derivatives, for instance, they may be used as polyhydric alcohols combined with polycarboxy acids or their anhydrides, such as phthalic anhydride, with or without drying oil fatty acids, such as linseed oil, fatty acid, to give resins or materials suitable for use in paints and varnishes. Furthermore, this is true even though the average value of n in the previously described formula is less than 2, for instance, a trinuclear compound is treated with two to five moles of an alkylene oxide, such as ethylene oxide, and particularly if it is treated with 3 moles, so as to yield a product of the following composition:

own m O(C2H40)H ounruom u 2 R1 Such particular product is of distinct value for combination with such reactants, such as phthalic anhydride or linseed oil fatty acid, to produce desirable paint and varnish constituents.

If desired, one may consider the new materials or substances herein described as hydrophile oxyalkylated phenol-aldehyde resins obtained from oxyalkylation-susceptible, Water-insoluble, organic solvent-soluble, fusible, phenol-aldehyde resins derived from certain monofunctional and difunctional phenols in the ratio of two moles of a monofunctional and one mole of a difunctional phenol.

This application is a continuation-in-part of a number of our co-pending applications all of which were filed February 16, 1948, to wit: Serial No. 8,722, now Patent Number 2,499,365; Serial No. 8,723, now Patent Number 2,499,366; Serial No. 8,724, now Patent Number 2,499,367; Serial No. 8,725, now Patent Number 2,581,367; Serial No. 8,726, now Patent Number 2,499,368; Serial No. 8,727, now abandoned; Serial No. 8,728, now abandoned; Serial No. 8,729, now abandoned; Serial No. 8,730, now abandoned; Serial No. 8,731, now abandoned; Serial 'No. 8,732, now abandoned; Serial No. 8,733, now abandoned, and Serial No. 8,734, now Patent Number 2,501,015, which describe hydrophile oxyalkylated products obtained.

by oxyalkylation of oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenolic resins including particularly products derived from such phenol-aldehyde resins, and their use for various purposes, particularly demulsification.

It will be noted that in all of the foregoing co-pending applications we have not attempted,

'for reasons which are perfectly obvious, to refer to a single specific compound derived from a difunctional phenol and an aldehyde, such as formaldehyde. .The reason or reasons are obvious, to wit, the resinification may involve resin molecules having 3 to 7 or 10, or even more structural units. Numerous variations can take place, depending upon whether ortho or para-phenols are used, and depending upon the particular'aldehyde selected, on the particular catalyst selected, whether or not vacuum distillation isused as an after-step, etc.

In connection with the instant application, we are doing two things which differentiate said invention from the various inventions previously described, and they are as follows:

(1) We are concerned with the product of a definite chemical composition, and thus, claims are not concerned with describing the product in terms of method of manufacture, but the demulsifyingagent is described in terms of structure only; and

(2) Instead of being derived solely, or substantially solely, from difunctional phenols, the herein described products are resin molecules derived from monofunctional phenols and difunctional phenols, jointly, the ratio being two of monofunctional to one of difunctional. In all our various aforementioned co-pending applications there is either no use of a monofunctional phenol at all, or, if employed, it is only employed to modify, i. e., prevent cross-linking in the instance of large-size resin molecules, and particularly those derived totally or in part from trifunctional phenols. In brief, then, the present invention is concerned with the breaking of petroleumemulsions by means of oxyalkylated tri-nuclear'resins of the kind hereinafter described.

The preparation of tri-nuclear phenolic resins of known composition which can be stated with specifity appears to be limited to formaldehyde derivatives. Such resin molecules are tri-nuclear condensation products, are well known, and have been described in the literature.

These compounds are those which may be represented by the formula on 011 OH H H R oo- .R

R1 R: R1

in which R is'a member of the class of alkyl, aralkyl, alicyclic and aryl radicals having not over 8 carbon atoms, and R1 and R2 are members of the class of alkyl, aralkyl, alicyclic and aryl materials.

OH H OH H C C )3 H A B C D E l methyl.-. methyl... methyl.-. methyl... methyl. 2 tei-t-amyl tert-amyi tert-amyl tert-amyl tert- 1 amy. 3 tert- .do. tertnonyl.... mcnthyl.

butyl. octyl. 4 tert-amyl .do tert-amyl tert-amyl tert- 1 amy. '5 methyl-.. methyl..- methyl..- methyl... methyl.

M01. Vt. 530 54 i 586 G00 612. ofCmpd.

F G H I I l tert-amyl tcrt-zunyl tcrt-amyl tert-amyl tert- I army 2 terttert terttcrttertbutyl. butyi. butyl. butyi. butyl. do tert-amy tertnohyl. mcuthyl.

octyl. do tertterttcrttertbutyl. but-yl. butyl. utyl. tert-amyl 'tcrt-amyl tert-amyl tert-amyl tert- 1 amy. Moi. Wt. 614 628 670 G84 696.

of Cmpd.

K L l\[ N O phenyl.-. phenyl... phenyl.-- phenyl. tertterttertte 5 phenylln phenyl... phenyl... phenyl... phenyl Moi. W t. 738 752 794 S 820.

P Q R S T cyclocyclocyclocyc1ocyclohexyl hexyl. hexyl. hexyl hexyl. octyl octyl. octyl..- ctyl-.. octyl.

terttertnonyl. menthyl. butyl. amyl. octyl. rttert- ..do tcrttertoctyl. octyl. octyl octyl. cyclocyclocyclocyclocyciohexyl. hexyi. hexyl hexyi hexyl. 726 4 80G 820 73 2.

U V W X Y terttertterttertrtbutyl. butyl. butyl. butyl butyl nonyl. 'nonyl. nonyl. nonyl. nonyi. tertterttertl do mcnth'yl.

butyl. amyl. octyi. nonyl nonyL... nony1 .do ncnyl. tertterttertterttertbutyl. butyl. butyi. butyl. butyl. .Mol. Wt. 6 740 782 796 of Cmpd.

Having obtained a tri-nuclear'phenolic molecule or resin of the kind described by the formula:

on OH on -oxyalkylation, particularly oxyethyl'ation. The

procedure employed is substantially' -the same as described in-various oftheprecedlng-cm-pending 5 applications, particularly Serial No. 8,730 and Serial No. 8,731, filed February 16, 1948.

Briefly stated, the process is essentially as follows: The trinuclear compound or resin is mixed with a suitable amount of solvent, for instance, about one-third or one-fourth its weight of xylene. Some other solvent, such, as .cymene, or the like, can be employed. An alkaline catalyst, such as caustic potash, caustic soda, sodium carbonate, sodium methylate, or the like, is added. Our preference is to use approximately 2.0% to 2.5% of sodium. methylate, based on the weight of the solvent-free compound. The mixture of compound, solvent, and alkaline catalyst (sodium methylate) is placed in a stirring autoclave and ethylene oxide or any other selected alkylene oxide added, either continuously or batchwise. For various reasons, our preferred alkylene oxide is ethylene oxide. It will be noted that the present compounds are characterized by the addition of two to four moles of the alkylene oxide per phenolic nucleus. Thus, assuming uniform distribution, the previous formula can be rewritten as follows:

H R C- in which the various characters have their previous significance and R3 is a member selected from the class of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene H C R H radicals, and'hydroxybutylene radicals, and n is Example 1 530 grams of a tri-nuclear compound of the kind characterized by the formula A preceding, is mixed with 135 grams of xylene and 12 grams of sodium methylate. The mixture is placed in an autoclave and 132 grams of ethylene oxide added. The temperature is raised to 150 to 160 C. The autoclave is stirred rapidly during this period and the maximum pressure usually remains between 155 to 185 pounds per square inch. At the end of approximately 2 /2. to 4 hours the pressure is dropped to almost zero, particularly when the autoclave is cooled to room temperature. At the end of this period, the ethylene oxide is reacted completely so as to give a product having incipient hydrophile properties characterized by the introduction of one mole of ethylene oxide per phenolic nucleus, based on average distribution. The reaction mass is subjected to a second treatment of ethylene oxide in substantially the same manner so as to introduce an additional 132 grams of ethylene oxide. The procedure and conditions of operation, i. e., temperature, pressure, etc., are substantially the same as before. The final product obtained is a light amber-colored fluid, having distinctly emulsifiable properties and having an average ratio of two for the character 1:. previously noted.

Example 2 The same procedure is followed as in Example 1, preceding, except that 4 additions of ethylene oxide are made under substantially the same op-' crating conditions so as to introduce a total of 528 grams of ethylene oxide. The final product contains proportionately less xylene and is somewhat lighter in colon-and is readily dispersible. In this instance, the value of n is 4.

Example 3 The same procedure is repeated as in the two.

preceding examples, except that the total amount of ethylene oxide added is 792 grams in sixproportions of 132 grams each. If the addition of ethylene oxide tends to slow down during the final phase when the fifth and sixth additions are made, we have found it desirable to-cool the reaction vessel, add another five to six grams of sodium methylate, and then start up again, go-v The same procedure is followed as in Example 1, preceding, except that the trinuclear compound employed is C, preceding, and the amount employed is 586 instead of 530 grams.

Example 5 The same procedure is followed as in Example 1, preceding, except that the trinuclear com pound employed is F, preceding, and the amount employed is 614 grams instead of 530 rams.

' Example 6 The same procedure is followed as in Example 1, preceding, except that the trinuclear compound employed is G, preceding, and the amount employed is 628 grams instead of 530 grams.

Example 7 The same procedure is followed as in Example 1, preceding, except that the trinuclear compound employed is H, preceding, and the amount employed is 670 grams instead of 530 grams.

Example 8 The same procedure is followed as in Example 1, preceding, except that the trinuclear compound employed is H, preceding, and the amount employed is 794 grams instead of 530 grams.

Example 9 The same reactants and the same procedures were employed as in Examples 1 to 8, preceding, except that propylene oxide was used instead of ethylene oxide in the same molar proportions, i. e., so the values of n still represented 2, 4, and 6, based on average distribution. The resultants, even on addition of the same molar amount'of propylene oxide, have diminished hydrophile properties, in comparison with the resultants obtained with ethylene oxide. This illustrates the point that propylene oxide and butylene oxide give products of lower levels of hydrophile properties than does ethylene oxide.

Example 10 The same reactants and the same procedures were employed as in Examples 1 to 8, preced- 7 mg, except athat sglycide was used :insteadzof ethylene oxide. :This :particular :reaction was conducted with extreme :care and the glycide added in only small :amounts representing :a fraction rof a imole. The ;reaction was stopped when two moles of :glycidewereaddedper mole of phenolic nucleus. We are extremely hesitant to suggest even the experimental use of glycide and methylglycide, for the reason that 'disastrous --resultscan be obtained, even in experimentation with laboratory'quantities. -WeJhave found nd-"advantage to be obtained, particularly from lthe -economic 'standpoint, in any of the oxides other than ethylene oxide, and propylene oxide. We have found no genuine advantage Tfrom "the use of propylene oxide over and above ethylene oxide. Ethylene :oxide is definitely our preferred and the most "advantageous oxyalkylating agent.

Jf desired. oxyalkylati'on,particularly oxyethylation, can be conducted without theuse of a -solvent. All that is required is that the phenoliccompound be a liquid at the'temperatureOf-"OXyethylation, for instance, between l-fill to 200 C. If -a-:solvent is employed, there isno objection iJ-to the solvent being presentin the final product for many uses, and Particularly for demulsification. If desired, of course, products exemplified .by previous examples to wit, Examples .l to 10, inclusive, maybe-sum jected to distillation, particularly vacuum .distillation, to remove the-solvent, such as xylene; for instance, we have found that raising the temperature to 150 C. under a vacuum in 25 mm. of mercury removes-the xylene readily.

The instant application is concerned with certainaoxyalkylated derivatives of trinuclear compounds. it is obvious that the :alicycl-ic analogues derived by nuclear hydrogenation are equally serviceable for this purpose, and particularly, as intermediates for the manufacture of'more complex compounds for use as demulsifying agents. In a general way, conversion of the aromatic'material to an'alicyclic material follows either one of two procedures; one can hydrogenate the resin in a conventional manner, followed by oxyalkylation of the hydrogenated resin in substantially the same manner 'as is employed in .the case of the nonhydrogenated resin. The second procedure is to hydrogenate the oxyalkylated derivative, rather than the resin itself. As an example of such procedure, .referenceis -made to our copending application Serial No. 726,201, .filed February 3,1947, now abandoned.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

in A which is a member of the class 'of alkyl,

aralkyl, i'alicyclic and aryl radicals .having .not over 8 carbon atoms, and-R1 -and R2 sare-zmembers of the class of alkyl, aaral'kyl, al-icyclic -and aryllhydrccarbon radicals :having not .over 118 carbon: atoms, and .TRs is a member :of Et'he :class of ethylene :radicals, propylene radicals, abutylene :radicals, lhydroxyp'ropylene :radicals, :and hydroxybutylene radicals, and is ca :numeral varying. from .1 to :20, with the :proviso that-lat least :2 moles of .alkylene :oxide :be iintroduced for each phenolic nucleus.

-2. Hydrophile synthetic formula:

in which.2R:is azmemberiof the-.classmfaalhyl, ara'lkyl, 'alicyclic and .aryl radicals z'having :not over 8 :carbon: atoms,..and R1 and 1R2 :are-rmembers of the class of alkyl, aralkyl, alicyclici-and aryl hydrocarbon radicals having not over 18 carbon atoms, and n is a numeral varyingfrom l to 20, with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus.

3. The'product of claim 2, wherein .n is not greater than 6.

4. .-The product ofcla-im'2, wherein m'isinot greaterthan' 6 and all nuclear substituentlhydrocarbonura-dicals are a'llryl.

,5. The product of claim .2, wherein-n -is-.not greater than 1 Sand all nuclear substituent. hydrocarbon radicals are alkyl radicals having at least 4 and:not morethan's carbonatoms.

.6. ,The'product'of claimi2, wherein '12. is not greater I than '6 and all nuclear substituent hydrocarbon radicals are alkyl. radicalsrhaving 4 products of :the

to 8 carbon atoms, with the added proviso that there is at least one occurrence of a butyl radical.

'7. The product of claim 2, wherein n is not greater than 6 and all nuclear substituent hydrocarbon radicals are alkylradicalszhaving 4 to 18 carbonatoms. with the added :proviso that there is :at least one occurrenceof :an -amyl radical.

8. The product of claim 2, wherein n is not greater than 6 and all'nuclear substituent hydrocarbon radicals l are alkyl radicals having :4 to 8 carbon atoms, with :the i added proviso that there is: at least one occurrence of a butyl radical.

MELVIN DE l GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are (if-recordintho file of this patent:

UNITED. STATES PATENTS Number Name :JDate 72,430,002 :De .Groote .et1al. Nov.-'?4,:194.=7 12,454,541 .Bockxet' al. l Nov. 23,1948 2,450,272 Doelling :et'al. Sept;- 28, -1948 2,501,015 Wirtel Mar. .21, 11-950

Claims (1)

1. HYDROPHILE SYNTHETIC PRODUCTS OF THE FORMULA