US2542005A - Process for breaking petroleum emulsions - Google Patents

Description

l 'atented Feb. 20, 1951 UNITED STATES PATENT OFFICE PROCESSES FOR BR EAKING PETROLEUM EMULSIONS Melvin DeiGroote, University City, and Bernhard Keiser, Webster Groves, Mm, assignors to'P'etro lite= Corporation, Ltd Wilmington, DeL, a cor pox-ation of Delaware No Drawing. Application December 13', 1948,

Serial No. 65,090

11 Claims. (Cl. 252-341) ruary 16, 1-948 mow abandonedi, and also serial No; 82,704; filed *Ma'r'chZl, 1949, nowissued as Patent No; 2,499,370; dated March 7, 1950. Attention is also directed to our co-pending' application Serial- No'. 65,688, filed December 13, 19481 Complementary to the above aspect of the incvention', is our companion invention concerned with the new chemical roducts or compounds used as the demulsifying agents in said aforementioned processes or" procedures, as well as the application of such chemicai compounds; products, and the like, in various other" arts and industrie's, alongwith the methods for manufacturing' said n'ew'ch'emical products or compounds 1 which are of outstanding value in demulsification. See our co-p'endi'ng application Serial No. 65,09l-, filed December 13, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water in-oiLtype, that are commonly referred to as cut oil, roily oil, emulsified oil, etc, and which comprises fine droplets of naturally-occurring waters-or brines dispersedin a more or less permanent state throughout theoil which constitutes the continuous phase of the emulsion.

"It also provides an economical and rapid 'process for separating emulsions which have been prepared under controlled conditions from min- I eral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions. just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil. v I

Demulsification as contemplated: in the present application, includes the preventive step of commingling the demulsifler with the aqueous component which would or might subsequently become either phase of the emulsion, in'theabsence of such precautionary measure. Simi1arly,

I ated' derivatives of certain resins hereinafter specified.

Thus, the present process is concernedwith breaking: petroleum emulsions of the water-inoil type, characterized by subjecting the emulsion to the hydrophile quaternary ammonium compounds hereinafter described. Said hydro-' phile quaternary ammonium compounds are obtained by reaction between a dimethylated higher aliphatic amine, in which the aliphatic radical has at least 10 and not more than 22 carbon atoms, and the ester of an alpha-halogen monocarboxylic acid having not over 6 carbon atoms and hydrophile hyd'roxylated synthetic products; said hydrophile synthetic products being oxyalkylationproducts oi (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected: from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and m'ethylglycide; and (B) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional' monohydric phenol and an aldehyde having not over 8- carbon atoms and reactive towards said phenol; said resin being formed in the substan tial absence of trifunctionalphenols; said phenol being of the formula:

in which R is ahydrocarbonradical having at divalent-radicals having the formula (R-iOh in a which R1 is a member selected from the class consisting 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 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as well as the oxyalkylated resin in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For convenience, what is said hereinafter may be divided into five parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with chloroacetic acid, or the like; Part 4 will be concerned with a reaction between such esters containing a labile halogen and the dimethylated higher aliphatic amines of the kind previously described; and Part 5 will be concerned with the use of such quaternary ammonium compounds, as hereinafter described.

PART 1 .As to the preparation of the phenol-aldehyde resins reference is made to our co-pendingapplications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948, both now abandoned. In such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymerof the formula the'resin is fusible and organic solvent-soluble.

R is a hydrocarbon radical having at least 4 and 4 expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higheraldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phen'olic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and, tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural .for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexana1, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal.

is tetrafunctional. been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction; The inability of the other aldehydic out theuseof any catalyst at all. Among theuse ful alkaline catalysts areammonia, amines, and

quaternary ammonium bases. It is generally accepted that when ammonia and amines are emnot over 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as in the case ofa resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latterrequire a more elaborate description.

The alkylene oxides which may be used are the ployed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. Thef compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difiicult to present any formula which would depict thestructure of the various alpha-beta oxides having not more than 4 carbon V atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable offorming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so lon as it does not possess some other functional group or structure which will-conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in

its cheapest form of an aqueous solution, for the production of the resins is particularly advanta geo'us. Solid polymers of formaldehyde-are more resins prior to oxyalkylation. More will besaid subsequently as to the difference between the-use of an alkaline catalyst and anacid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are" not identical where different basic materials are weak acids such as'sodium acetate, etc.

Suitable phenolic'reactants include the following: Para tertiarybutylphenol; para-secondarybutylphenol; para-t'ertiary-amylphenol;' parasecondary amylphenol'; pa'ra-tertiaryhexylphenol; para -isooctylphenol;

It would appear that the use of j glyoxal should be avoided due'to the fact that it However, our experience has 1 ortho-phenylphenol;

amaoce Mra-phenylphenol; ortho benzylphenol; parabenzylphenol; and para-cyclohexylphenol, and the. corresponding ortho-para substituted meta-- cresols and 3,5-xylenolsi Similarly, one may usepara-roe ortho=nonylphenol or amixture, paraor ortho decylphenol' or a mixture; men-thylpheno or para or ortho-dodecylphenol.

For convenience, the! phenol has previously been referred to as monocyclio in order to (iii-- ferentiate from fused nucleus polycyclic phenols, such. as substituted naphthols; Specifically, iiionocyclic limited to the nucleus in which the hydroxyl radical is attached. Broadly speak ing}, wherea substituent iecyclic', particularly aryl, obviously in the usual sense such phenol is: actually polycyclic although the: phenolic by droxyl is not attached to a. fused. polycyclic nucleus; Stated another phenols in which the hydroxyl group is directly attached to a com denseu o'i' fus'e'd polycyclic structure, are excluded. This matter, how'ev'er is clarified by the followirig consideration. The phenols herein contemplated for reaction may be'indicated by the following formula:

in which R. is selected fromthe class consisting of hydrogen atomsand hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of: the 3 and 5 positions may be methyl substituted.

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

The manufacture of thermoplastic phenol-aldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted: by a hydrocarbon roup, and particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

Thermoplastic or fusible phenol aldehyde resins are usually manufactured for the varnish trade and oil solubility is of prime importance. For this reason, the common reactants employed are but-ylated henols. amylated phenols, phenylphenols,.etc.- ,The methods employed manufacturing such resins are similar to: those em ployed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difii-culty, while when a waterinsoluble phenol is employed some modification is usually adopted to increase the interiacial surface and thus cause reaction to take place. A common solvent issometimes employ iil Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist. in hastening the reaction. We" have found it'd'esirable to employ a small proportion of an or= gahic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydroclilori'c acid. For example, alkylated aromatic sulfo'nic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkaliv salt plus a small. quantity of strong mineral acid, as shown. in the. examples below. If desired, such organic sulfo-acids may be prepared in situ. in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In suchcases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent. such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, inthe form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too. marked a change in conditions of reaction and ultimate product. There is usually little,- if any; advantage, however, in using an' excess over and above the stoichiometric propor tions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1. with 1.05 as the preferred ratio, or sufficient, at least theoretically, to con"- vert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimeswhn high aldehydes. are used an excess of ald hydic reactant can be distilled off and thus re: covered from" the reaction mass. This same pro-- cedure: maybe used with formaldehyde and ex": cess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiomet'ric ratio of one-to-one or thereabouts. With the use of al k'aline catalyst it has been recognized that considerably increased amounts of formaldehyde may" be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more; with the result that only a small part of such aldehyde remains unco'mbined or is subsequently li-beratedduri-ng resinification. structures Which have been advanced to explain such increased use of aldehydes are the following:

OE OH Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or' converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split off water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the 7 amount of formaldehyde used may and does usuallyafiect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is speventional resinification procedure will yield products usually having definitely in excess of 8 nuclei. In other words, a'resin having an average of 4, or 5 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average 7 to units. Sometimes the expression low-stage resin or low-stage intermediate is employed to mean a stage having 6 or 7 units or even less. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight.

- The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for" instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Any suit-' Chem. Soc. 43, 2309 and 2314 (1921)). able method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenyl-; amine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947) Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no cata.yst. As far as resin manufacture per se is concerned, We prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, ashereinafter illustrated in detail. However, we have obtained products from resins obtained 'by ;use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as high-" stage resins, are conveniently obtained by subjecting lower molecular Weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it it a.most certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approxi mately 4 phenolic units or thereabouts may bei subjected to such treatment, with the result that one obtains a resin having approximately The usual prodouble this molecular weight. cedure is to use a secondary step, heating the resin in the presence or absence of an inert gas,

limit specified herein, there may be some tend-' ency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly de-H sirable to use the procedures described else-.

substituted conveniently in the oxyalkylation stage.

where herein, and employing a combination of an organic sulfo-acid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in any suitable manner.

Oxyalkyation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example. be carried out by melting the thermoplastic resin and subjecting it to treatmentwith ethylene oxide or the like, or by treating a, suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or s s ensi n of thermonlastic resin in an inert solvent such as ylene. Under such circ mstan es the resin obtained in the usual manner is dissolved by heating in xylene und r a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is pre ent or may be present during oxyalky -ation, it is obvious there is no obiection to having a sol ent present during the resinifyin stage if, in addition to being inert towards the resin, it is 'also inert towards the reactants and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphtha ene),

ethylene glycol diethylether, diethylene glycol 'ing, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of

course, with the ordinary product of commerce containing about 37 /275 to 40% formaldehyde, is the preferred reactant. When such solvent is used it is advantageously added at the beginning of the resinification procedure or before the re action has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a Lfinal higher temperature can be employed to.

"complete reaction if desired. In many instances it is most desirable to permit part of the solvent,

particularly when itis inexpensive, e. g., xylene, to remain behind in a predetermined amount so to have a resin which can be handled more If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ react-ants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzen'e. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amountpresent is considerably less than 1% and not infrequently in the neighborhood of 1% of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or met-acresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be sufficient to cause insolubility at the completion of the resinification stage or the lack of 'hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such tri'functional phenols as hydroxybenzene or metacresol i not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a .phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is ob vious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is pro- .duced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in difierentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly 'if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any apother words, the presence of such reactant may 'cause cross-linkin in a conventional resinification procedure, or in the oxyalkylation procedure,

or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2

moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example 1a of our Patent 2,499,370 granted March '7, 1950. If the resin so obtained is solvent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected l65, C. with addition of at least 2 and advanta eously up to 5 moles of ethylene oxide per phenolic hydrox-yl. .tageously conducted so as to require from a few two or less reactive hydrogen atoms. what appears inthese most recent and most up-to-date investigation is pertinent to the pres- The oxyethylation is advanminutes up to to hours. If the product so "obtained is solven-soluble and self-dispersin or ;vent may be removed prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence ofja small amount of trireactive phenol, as previously mentioned, or for some other reason,.it

may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. ,Increasing the size of the aldehydic nucleus, .for

instance using heptaldehyde instead of formaldehyde, increases tolerance. for trifunctional phenol.

.The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so,

especially if the proportion is small. Resinifica- 'tion involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of What is someiitimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to be contradictory to what one might expect in 'light of the theory of functionality in resinifica- "tion. "stances, or rather under the circumstances of conventional resin, manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent-soluble. fusible resins. However, when conventional procedures are employed in connection with resins "for varnish manufacture or the like, there is I involved the matter of color, solubility in oil, etc.

When resins of the same type are manufactured It is true that under ordinary circumfor the herein contemplated purpose, i. e., as a.

'raw material to be subjected to oxyalkylation,

such criteria of selection are no longer pertinent.

conditions of resinification than those ordinarily with the minor react.ons of ordinary resin manufacture which are'of importance in the present invention for the freason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and

they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now understood A or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zlnke and his co-workers, Hultzsch and his associates, and to von Eulen and his co-workers, and others. As to a bibliography of such investigations, see Carswell, Phenoplasts,

' chapter 2. These investigators limited much of their work to reactions involving phenols having Much of oxyalkylation stage. This situation may be related ent invention insofar that much of it is referring to resinification involving difunctional phenols.

For the moment, it may be simpler to consider a mo-st typical type of fusible resin andforget for the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text. it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insoluble must be avoided in order to obtain the products herein contemplated for use as reactants.

The typical type of fusible resin obtained .from a para-blocked or ortho-blocked phenol is of the difunctional phenol-aldehyde type resin;

but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for examplethe use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

The intermediates herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or the subsequent stage of resinmanufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the rationale of resinification involving formaldehyde, forexample, and a difunc- 'tional phenol would not be expected to form crosslinks. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowl edge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and fro-m various reactants, and by means of different catalyst by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufacture there may be a potential crosslinking combination formed but actual crosslinking may not take place until the subsequent stage is reached, i. e., heat and vacuum stage, or

or explained in terms of a, theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolublcs may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these re ins.

All that has been said previously herein as regards resinification has avoided the specific reference to'activity of a methylene hydrogen atom. Actually th re is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom. Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to, both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 119 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heatin may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufiiciently fusible to permit processing to produce our oxyall zylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

'The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number or" procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature.

The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-suscpetible, water-insoluble, organic solventsoluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. la through 103a of our Patent 2,499,370, granted March 7, 1950, and reference is made to that patcut for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabutylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or para-butylphenol and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producin simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish on with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reaction alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes amaooe the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene ox de molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, thesetwo reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylen oxide is much more eifective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more eifective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactite, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the o .1 hand, glycide react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins oi the kind from which the initial reac d. 5 used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysis include. soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. lhe amount of alkaline catalyst usually is between (1.2% to 2%. The temperature employed may vary'from room temperature to as high as 206 C. The reaction may-be conducted with or without pressure, i. e., from zero pressure to approximately 206 or even. 3% pounds gauge pressur (pounds per square inch). In a general way, the method employed is substantially the same procedure used for o-xyalkylation oi other organic materials having reactive phenolic groups.

It'may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in Oxyalkylation. For instance, if a nonvolatilestrong acid such as sulfuric acid sumably after being converted into a sulfonid acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorlly without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent 'to'z-al pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of tWo Ways: After the introduction of approximately 2 or 3 moles of ethylene oxide,

for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be elLminated by distillation (vacuum distillation if desired) .and the subsequent intermediate, being comparatively soft and solvent-iree, can be reacted further in the usual manner with ethylene oxide'or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactantin the earlier stages along with ethylene oxide,.'for instance, by dissolving the powdered resin in' propylene oxide even though oxyalkylation. is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in ay suitable manner.

1 Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solis used to catalyze the rcsinification reaction, pre- 15 vents are alcohols and alcohol-others. However,

17 where a resin is; soluble in an organic solvent, there are usually available other organic solvents which arenot susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100v to 200 mesh, and

a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. Thefact that the resin is soluble in an organic solvent orthe fact that it is fusible means that it consists of separate molecules. of the type herein specified posse s reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with ability to vary the hydrophile properties ofthe hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in turn, of course, are effected subsequently by the acid employed for esterification and the quantitative nature of the esterification itself, i. e., whether it, is total or partial, and also by the dimethylated higher aliphatic amine used to obtain. the final product for use in the process of the present invention. It may be well, however, to point out what has been said elsewhere in regard to the hydroxylated intermediate reactants. See, for example, our co-pending ap lications, Serial Nos. 8,730, and 8.731, both filed February 16, 1948, and Serial No. 42,133, filed August 2, 1948, and Serial No. 42,134, filed Augustv 2, 1948 (all four cases now abandoned). The reason is that, the reactions. depending on the acid and the, dimethylated higher aliphatic amine selected, may vary the hydrophile-hydrophobebalance in one direction or the other, and also. invariably causes the development of some property which makes it, inherently different from the, reactants from which the derivative is obtained.

Referring to the hydrophile hydroxylated intermediates, even more, remarkable and equally difficult to ex lain, are the versatility and the utility of these compounds cons dered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the po nt where two ethyleneoxy r dicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at. least emulsify-. ing properties or self-dispersion in cold or even in warm dist lled water to 40 C.) in concentrations of 0.5% to. 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling Water. Moderately high temperatures aid in reducing the v scosity of the solute under ex-.. amination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mix,- ture cools. Such self-dispersion. tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufficient to give a. sol as described immediately preceding, then, and in that event hydrophile properties are ind cated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solu- Phenol-aldehyde resins.

ates-.095.

18 I tion within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxya-lkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not suflicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such $01 or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.) Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oXyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as polyhydric reactants, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are selfemuls fying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most eflicacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibllity.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be meas ured by determining the surface tension and the 19 interfacial tension against paraflln oil or the like. At the initial and lower stages of oxyal kylatlon, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oilin-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with l-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is read'ly disp1rsible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of dist lled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and furs ther dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of Xylene, will serve to illustrate the above emulsification test.

In a few instances, the res n may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the pres ence or absence of hydrophile or surface-active characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surfaceactive property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are.

useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self -emulsification begins, then it is better to eliminate the xylene or equivalent 20 from a. small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It'is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient seif-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

E1sewhere,it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immateral whether a xyene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the efiectfveness of various alkylene oxides, and most particularly of all ethyene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, aslong as it is atleast 2 moles per phenolc nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size or the resin chain resulting from reaction between the difunctional phenol and the aldehyde'such as formaldehyde. It is we'l known that the size and nature or structure of the resin polymer obtained varies somewhat withthe condtionsof reaction, the. proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or '7 phenolic nuclei with approximately 4 or 5 nuclei as an average.

More drastic conditions of resinfication yield.

resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired.v Molecular weight, of course, is measuredby any suitable procedure, particularly by cryoscopic methods;

but us ng the same reactants and using morestance, an alkaline catalyst is sometimes em,-

ployed in a first stage, followedby neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the

number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of'an acid catalyst.' It is possible that such groups may appear in the finished prepared by ourselves. Our preference, however,

is, to use. an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to;1.20 and, as far as;.we have been able todeterminep'i. such resins are free from methylol groups; amatter of'fact, it isprobable that in, acid-catalyzed: resini'fications, the methylol structure, may appear only momentarily at the very beginning of the reaction and in all probability is converted at once intoa more complex structure during the intermediate stage.

= 3 One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparationof compounds employed in ;the present invention, is to determine the hydroxyl value, by the Verley-Biilsing method or its equivalent. 7 The resin as, such, or in the'form ofj'a, solutionas described isthen treated with ethylene oxide in. presence of 0.5% to 2% of sodium methylate as a catalyst instep-wise fashon. II'heconditions of, reaction, as far as time or pencent are concerned, are Within the range soft or pitch-like resin at ordinar temperatures. such resins becom comparatively fluid at 110 to-165i C. as a rule, and thus can be readily oxyalklated, preferably oxyethylated, without the use of asolvent. I V

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and

particularly oxyethylation. What has been said previously, is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum "to an ultimate maximum. One should not underestimate the utilit of any of these polyhydric alcohols in a surface-active or subsurfaceactive rangewithout examining them by reaction with a number of the typical acids and dimethylated higher aliphatic amines herein described and subsequently examining the resultant for utility, either in demulsi-fication or in some other art or industry as referred to elsewhere, or as a replicyiol'lslyindicated. With suitable agitation the thyleneoxide, it addedin molecular proportion, combineswithina comparatively short time, for instance .a flfe'wminutes to 2 .to 6 hours, but in some instances requires as muchasS to 24 hours.

Afuscful temperaturerange is from'1-25? to 225 ,ufllhefcompletion of.v the reaction or? each additionjf ethylne .oxide in step-wise fashion usuallylindicatedj bythe' reduction or elimination of, pressure; An amount conveniently used for j each addition is generally equivalent to a molep f liwomolesof ethylene oxide per hydroxyl radical. Whenjithe. amount ofethylene oxide added is equ valent to approximately 50% by weight of the original resin, .a.'sample is testedfor incipient hydrophile, properties by simply shaking up in Watenasi is,,or.after theeliminatio n of thesolvent ifa solvent is present. .fI'heamount is ethylene oxide used to obtaina .useful demulsifying agent as a rule variesjrom 7.0% by Weight of the original resin to .as much as five or six times the Weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as50 by weight of ethylene oxide "may give suitable solubility. With-pro? pylene oxide; 'even'a greater molecular proper; tio'n is required and sometimes a resultantjof only limit'ed hydrophile properties is obtainable.

The" same is true td'even a greater extent with butylene "oxide. The "hydroxylated ,alxlene oxides are more effective in' solubilizingproper tiesthan the comparable compounds in which noihydroxyl is present.

,Attention' directed to the fact that in the subsequent examples reference is made to the, stepwise additionof the alkylene aside-gush as ethylene oxide. It understood, of course, there v is no-objiection' to the continuous addition of alkyieneoxide. until the desired stage-of reaction is reached. In? 'fact,1ther may-' b less of a haz ard ainvolved and-it isoften advantageous to add the alkylene oxide slowly in a continuous stream and. such. amountlas to avoid! exceeding the higher. pressureslnoted in the various examples or. elsewhere...

It may bewellto emphasize the fact that when resinsxare produced from difunctional phenols actant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted ina routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and. being organic solvent-soluble, Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2-to 1; 6' to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. It the 2 t0 ,1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test showsthe required minimum hydrophile property, repetition using 2 /2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is'indicated by the fact that the $01 in distilled water within the previously mentioned concentration range isa permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio testin that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a, product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5%.1' 9. 5.0% aqueous solution is shaken,

' is anexcellenttest for surface activity. Previous referenc has been made to the fact that otheroxyalkylating agents may require the use of' increased' amounts of alkylene oxide. Howeverpif one does not even; care to go to the troubleof calculating molecular weights one can using approximately 200% to 300% by Weight,

and some of the higher-aliphatic aldehydesfsuch;

as acetaldehyde, the resultant isa comparativelyf and a third example using about 500% to 750% by weight, to explore the range of hydrophilehydrophobe balance.

pacity of about to gallons as hereii'iafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that is required to ive a suitable variety covering the hydrophile- U 'hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation,-how

tolprepare in a perfectly. arbitrary manner, a

series of compounds illustrating the hydrophilehydrophobe range. 1 I

If one purchases a thermoplastic or fusible resin on the open market selected from a suit- "able number which are available, one might have to make certain determinations in order tomake the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyl, amyl, or phenyl. With such information one is. in substant ally the same posit on as if one had per 'sonally made the resin prior to oxyethylation. For instance, the molecular weight of the. in.- ternal structural units of the resin of the follow-' ing over-simplified formula:

(n=1 to 13, or even more) is given approximately by the formula: (M01. wt. of phenol 2) plus mol. Wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (n plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in errormby several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more thansatisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene, oxide or product of minimal hydrophile character.

from resins which are producing the quaternary ammonium compounds 24 useful as intermediates for used in accordancewith the present application, such examplesgiving exact'and complete details for carrying out the oxyalkylation procedure."

The resins, prior-to oxyalkylation; vary'from tacky, viscousiliquids to hard, 1 high-melting sol ids. Their ,color varies from 'alight yellow through amber, -to .a deep .red or even almost black. In the-manufacture of resins, particu-- larly hard resins, as the reaction-progresses the eaction mass frequently goes through -a liquid state to a sub-resinous or semi-resinous state, often characterized byi-being tacky or sticky, to a final complete resin; As the resin is subjected to oxyalkylation these "same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxy'alkylated it decr'eases'in viscosity, that is, becomes more liquid orchanges from a solid to a liquid, particularly when it is converted to the water-dispersi ble or water-soluble stage. The color of the oxyalkylated derivative is usually considerably light; er than the original product from which it is made, varying from a pale straw color to an aim:

her or reddish amber. The viscosity usuallyvar-i ies from that of an oil, like castor oil, to that'o'f a thick viscous sirup. Some products are waxy.

Thepresence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and ther oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of the type described herein, we have found no instance where the use of less than 2-moles of ethylene oxide per phenolic nucleus gave desirable products.

Examples lb through 1812, and the tables which appear in columns 51 through '56 of our said Patent 2,499,370 illustrate oxyalkylation products also reduces the color in dilution. No undue significance need be attached to the color for they reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture, i. e.' aprocedure that excludes the presence of oxygen during the re inifica'tion and subsequent cooling of the resin, then of course the initial resinis much lighter incolor. We have employed some resins which initially are almost water-White and also yield a lighter colored final; product. r q Actually. in considering the ratio of alkylene-' oxide to add, and we have previously pointed;outthat this can be predetermined using laboratory tests, it is our actral preference from a practical-- standpoint to ,make tests on asmall pilot plant scale. Our reason for so doing is that we make one run, and only one, a n d that we have a-complete series which shows the-progressive effect of introducing the oxyalkylating agent, for instance, the ethyleneoxy radicals. Our preferred 'proced'a ure is .as follows: We prepare a suitable resin, or

for that matter, purchase it intheopen'market; We employ 8 pounds of resin and 4 pounds ofxy lene and place the resin and Xylene in suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete.

'We have pointed out that soft resins which arefluid or semi-fluid can be readily. prepared in variv ous ways, such as the use of ortho-tertiary amylphenol, ortho-hydroxydiphenyl, orthoedecylphe- J nol, or by the use of higher molecular weight aldehydes than formaldehyde. If such resinsare used,

a solvent'need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2%

. 25 l usethe equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature ,of about 150 C. to 175 C. We also take samples at intermediate points as indicated in the following table:

Pounds of Ethylene Percentages Oxide Added per 8-pound Batch lution may be suflicient to indicate hydrophile character or surface activity, i. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a Du Nouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description.- Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a'greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention,

Another reason why we prefer to use a pilot planttest of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydr0xy-" benzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will, yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surfaceactive, upon oxyethylation, particularly extensive oxyethylatiomf It is also obvious that one may have a solvent-soluble resin derived from a mix-'- ture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of-2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant which is perfectly. sati'sfac tory, while more extensive oxyethylation yields an ating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not-appear in a normally conducted reaction. Reference'has been made to cross-linking and its eifect on solubility and also the fact that,if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a. semi-rubbery or. rubbery stage. Incipient stringiness, .or even pronounced stringiness, or even the tendency towarda rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which'we want to make here,- however, is this: Stringiness or rubberization at this stage may possiblybe the result-of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain crosslinking in the same general way that one would obtain cross-linking'in other resinification reactions; Ordinarily there is little or no tendency toward etherification during" the oxyalkylation step, If "it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of; ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or'5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringines's' or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note-one peculiar reaction sometimes noted in the course of oxyalkyiation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presencepf some accompanying water-insoluble sol vent such as 10% to'15% of xylene. Further oxyalkylation, particularly oxyethylation, may then yielda product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change hasjtaken place. One explanation of the above change is that the structural unit indicated in ,theyfolloWing way where 8n'is a fairly large number, for instance, 10 to 20, decomposes and an oxyalkylatecl resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no dimculty for the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for products for use as polyhydric reactants in the practice of this invention, this is not necessary and, in fact, may be undesirable, i.-e., reduce the efliciency of the product.

We do not know to what exent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethy.ene oxide per phenolic nucleus are added, this would mean an addition of moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would containB ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units; there might be some having, for

example, 4 and 6 units, or for that matter 3 or 7' units. Nor is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to solvents used in cryoscopic determinations for ob vious reasons. Attenton is directed to the fact that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility tests merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylation. For solu- O H Ommmomn Gownnomn vtiori of the oxyalkylated compounds, or their de-- rivatives a great variety 'of'solvents may be employed, such as alcohols, ether alcohols, CIGSOlSy;

Reference to cryoscopic measurement is concerned with the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight I determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should bechecked so as to insure that it gives consistent values on. such conventional resins as. a control. make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical combination of two moles "of 'the same phenol and one mole of the same aldehyde under conditions to insure dimerization. Asto the preparation offsuch dimers from substituted phenols, isee Carswell, Phenoplasts, page31." The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently areall that is required to establish that the resin contains 3 or more structural units per molecule.

Ordinarily the oxyalkylation is carried out in autoclaves provided with agitators or stirring devices. We have foundthat the speed of the agitation markedly influences the reaction time. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of 60 to 200 R. P. M., to highspeed agitation, with the stirrer operating at 250 to 350 R. P. M.,'re-

' duces' the time required foroxyalkylation by when produced by similar procedure'but 'with' high speedagitation, as "a'result, we'believe, of

the .reduction'inthe time required with conse-' quent elimination or curtailment of opportunity Frequently all that is necessary to" 29 for curing or etherization. Even if ,theformation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale opera.- tions, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation. 7

Previous reference has been made to the fact that in preparing compounds of the kind herein described, particularly adapted for demulsification of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the 'most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously.

From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene oxide is one to one, 1 to 5, l to 10, 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufficiently great to pass into the autoclave, or

else we have used an arrangement which, in essence, was the equivalent of an ethylen oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically." Such procedure and arrangement for injecting liquids is, of course, conventional. The following .data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five different variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously if reaction is not started at the beginning of the reaction period. Since theaddition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (b) amount of cool ing water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience We have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We have also indicated the maximum pressure that we obtained or the'pressure'range." Likewise, we'have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one periodends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the mannerdescribed in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to l5-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their Bulletin No. 2087 issued in 1947, with specific reference to Specification No. 7l3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, to one gallon, one can proceed through the entire molal stage of l to 1, to l to 20, without remaking at any intermediate stage. This is illustrated by Example 10%. In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result it was necessary in such instances to start with a new resin sample in order to prepare suflicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables Where, obviously, it shows that the starting mix was not removed from a previous sample.

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Formaldehyde Date, June 22, 1948 v [Resin made in pilot plant size batch, approximately pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 1040.]

- Mix Which is Mix Which Restarting Mix at of Removed for mains as Next eac 0 Sample Starter Max. Max. Time Pressure Temperahrs Solubility 7 lbs. sq. in. ture, C. lbis. gbs. Lbs kbs. Lbs abs. Lbs abs. Lbs 0 eso eso eso esvent in Eto vent in Eto vent in vent in Eto First Stage Resin to EtO. Molal Ratio 1:1 14. 25 15. 75 0 14. 25 15. 75 4. 0 3. 3. 1. 0 10. 9 12. 1 3. 0 80 150 $4 I Ex. No. 104b Second Stage Resin to EtO v Molal Ratio 1:5. 10 9 12. 1 3. 0 10. 9 12. 1 15. 25 3. 77 4. 17 5. 31 7. 13 7. 93 9. 94 158 l ST Ex. No. 105b 1 Third Stage Resin to Et0. Molal Ratio 1:10 7 13 7. 93 9. 94 7. 13 7. 93 19. 69 3. 29 3. 68 9. 04 3. 84 4. 25 10. 65 60 173 55 PS EX. No. 106b Fourth Stage Resin to EtO Molal Ratio 1:15- 3 84 4. 25 10. 65 3. 84 4. 25 16. 15 2. 04 2. 21 8. 55 1. 2. 04 7. 60 220 160 16 RS Ex. No. 107D.

Fifth Stage Resin to EtO. Molal Ratio 1:20- 1 80 2. 04 7. 60 1. 80 2. 04 10. 2 Ma QS Ex. No. 108b.

I=Insoluble. ST=Slight tendency toward becoming soluble. FS=Fairly soluble. RS=Readily soluble. QS=Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date, June 18, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 70a of Patent 2,499.370 but this batch designated 10911.]

. Mix Which is Mix Which Re- Starting Mix fi 3 3 2 33 or Removed for mains as Next Sample Starter Max Max 1tljressu e 'iemp egx- 1 2 Solubility Lbs. Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs Lbs Lbs. Lbs Lbs Sol- Res- Sol- Res- Sol- Res Sol- Resvent in Eto vent in ELO vent in Eto vent in Eto First Stage Resin to EtO Molal Ratio 1:1 15 0 15.0 0 15.0 15.0 3 5.0 5.0 1.0 10.0 10.0 2.0 50 150 1% ST Ex. No. 109l) Second Stage Resin to Et0 Molal Ratio 1:5 10 10 2. 0 10 10 9. 4 2. 72 2. 72 2. 56 7. 27 7. 27 6.86 100 147 2 DT Ex. No. 1l0b Third Stage Resin to EtO I Molal Ratio 1:10. 7 27 7. 27 0. 86 7. 27 7. 27 13. 7 4. 16 4. 16 7.68 3. 15 3. 15 5. 95 125 1% S Ex. N0. 1110.--" V Fourth Stage Resin to EtO Molal Ratio 1:15. 3 15 3.15 5. 95 3. 15 3.15 8.95 1.05 1.05 2.95 2.10 2.10 6.00 220 174 2% S Ex. No. 112b Fifth Stage Resin to EtO. 1 Molal Ratio 1:20. 2 10 2. 10 6.00 2. 10 2.10 8. 00 v 220 183 34; VS EX.No.113b

S=Soluble. ST =Slight tendency toward solubility. DT=Deflnite tendency toward solubility. VS=Vei y soluble.

. 1 j 1Phenolforgresin: Para-octylphen-ol Date, June 23, 24, 1948 [Resin made inpiiot plant size batch, approximately pounds, corresponding to So of Patent 2,499,370 but this batch designated 1140.]

Aldehyde for resin: Formaldehyde Mix Which is Mix Which Restarting Mix fig figg of Removed for mains as Next Sample Starter Max Max Time Pressure Tempsrahrs Solubility gbls. abs. Lbs gbls. Ifibs. Lbs r b s. I bs. Lbs l b s. Ifibs. Lbs

o eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to Et0 Moiai Ratio 14.2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.75 11.1 12.4 2.6 150 1342 NS Ex. No. 114b.

Second Stage Resin to EtO. Molal Ratio 15... 11.1 12.4 2.5 11.1 12.4 12.5 7.0 7.82 7.88 4.1 4. 58 4.62 171 )6 SS Ex. No. 5b

Third Stage Resin to EtO Molal, Ratio 1:10. 6.64 7.36 0 6.64 7.36 15.0 190 1% 8 Ex. No. 116b.

Fourth Stage Resin to 13110.... M0121 Ratio 1:15. 4.40 4.9 0 4.4 4.9 14.8 400 160 )4 VS Ex. No. 117b.

Fifth Stage Resin to Et O Molai Ratio 1; 20. 4.1 4.58 4.62 4.1 4.5a 13.52 260 172 $4. vs Ex. No. 118b S=So1uble. NS=Not soluble. SS =Somew1 at soluble. VS=Very soluble.

Plieml'fe aresi en y p 7 Date, July 8-13, 1948 [Resin made in pilot piant size pat'chfapproxiniately 25 pounds, corresponding to 69a of Patent 2,499,370 but this batch designated 119a.]

Aldehyde for resin: Formaldehyde Mix Which is Mix Which Restarting Mix figg ggg of Removed for mains as Next Sample Starter Max. Max. Time v Pressure 'lempgrahrs Solubility Lbs. Lbs. Lbs; Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- Res- Sol- Res-, Sol- Res- 1 .....ym. .Y e in First Stage Resin to EtO.

Moial Ratio 1:1 13.65 16.35 0 13 65 16.35 3.0 9.55 11.45 2.1 4. 1 4.9 0.9 60 150 156 NS Ex. No. 119b Second Stage Resin to EtO"-. i 3 Molal Ratio 10 12 0 12 10.75 4.52 5.42 4.81 5.48 6. 58 5.94 160 1952 8 Ex. No. 1200--- Third Stage 1 Resin to Et0 g I Molal Ratio 1:10. 5.48 6. 58 5.94 5.48 6. 58 10.85 90 160 H 5 Ex. No. 121b- Fourth. Stage Resinto-EtO Molal Ratio 1:15 4. 1 4.9 0. 9 4. 9 13.15 180 171 1542 VS Ex. No. 1220..." Fifth Stage Molal Ratio 1:20- 3.10 3. 72 0.68 3.10 3.72 13.43 320 VS Ex. No. 123b S-Soluble. NS-Not soluble. VS=Very soluble.

Phenolfof resin: Para-secondury butylphenpl" A ld'efiyde'fbrresih: Fbrmaldehyde Date, July 14-15, 1948 [Resin made in pilot plant size batch. approximately 25-pounds; correspondingte2iroivPatenii 2449937013115thisbatch designated 12411.]

- 3 Mix Whiehis 1- Mix Which Re- Starting Mix g figg RemovedTor mains as.Next

6 Sample Starter Max Max Time nlj'ressuge fimpgighrs Solubility 's.sq..n. e ei- .1221 .2:ezzu e ;ase ee-ezae vent in vent in v vent in vent in:

First Stage Resinto F120-.-" I r Molai Ratio 1 14; 15. 0 14. 45 15.55 4. 25 5.97 6. 38 1. 8. 48 9. 17 2.50 60 150* 5f: NB Ex. N0. 124!) Second Stage Resin m EtO I Molal-Ratio 1:5..- 8548 9.17 2.50 8.48 9.17 16.0" 5. 83 6. 32 11.05 2.65 2.85 4.95 95 188' M SE Ex. N 0. 125b V 1 Third Stage 1 Resin to EtO a Molal Ratio 1:10. 4.82 5.18 0 4. 82 5:18- l4-.25 400 1831 $6 S Ex. N0. 12Gb Fourth Stage I Resin to EtO v V I Molal Ratio 1:15- 3. 85 4.15 0 3.?85 4.15 17.0" 120 180 $6 V5 Ex. No. 12712---. I

Fifth Stage l Resin to EtO Molal Ratio 1:20 2.65 2. 85 4.95 2.65" 2. 85 15.45 80 7 170 fi VS Ex. No. 128b I S=So1ub1e. NS=Not soluble. SS=Somewhat soluble. VS'=Very-so1ub1e:

Date, August 12-13, 1948 Phenolfor resih: Men-thyl' Aldefiyctfbr resin: Piopionaldefiyd [Resin made. on pilot plant size batch, approximately 25 pounds, corresponding 170 81a ofjPatent 2,499,370 but this batch designated 12911.]

. Mix Which is Mix Which Re- Starting Mix if 'g figg Removed Iormains 'as N ext 7 Sample Starter. Mam M-ax I Pressure Tempera- Solubility lbs sq in tine "0 gbs. Lbs kbs. Lbs gbs. Lbs, Ifibs. I 0- es- 0- es- 1 0-- es- 0-- es-"- vent in Eto vent in vent; in E vent. in fl First Stage Resin to E110"... Molal Ratio :1 12.8 17.2. 2.75 4. 25 517 0: 8555 11. 50 12 80 150i 3% Not soluble. Ex.N0.129b I v i i 2.

Second Stage Resin to E--- f Molal Ratio 1:5 8.55 11.50 1.80 8.55 11. 50 9.3 4.78. 6.42. 522 3177 5508 4: 10 x 100 170 Somewhat Ex.N0.130b soluble:

Third Stage Resin to EtO Molai Ratio 1:10- 3. 77 5. 08 4. 10 3. 77 5. 08 13. 1 100. 182i M a 801111316: Ex. No. 1310------ Fourth Stage Resin to E tO V Molal Ratio 1:l5 5.2 7.0. 5.2 7.0 17.0 3.10 4.17 10.13 2.10. 2.83. 6. 87 200 182 Y 34- Verysolirble. Ex:N0. 132b Y 1 r- A Fifth Stage Resin to EtO V Molal Ratio 1:20 2.10 2.83 6.87 2.10 2.83 9.12 90 i Verysoluble. Ex. No. 1330:..... i i j Phenol for resin: Para-tertiary amylphenol Date, August 27-31, 1948 [Resin made on pilot plant size batch, approximately pounds, corresponding to 42a of Patent 2.499.370 but this batch designated as 13411.]

Aldehyde for resin: Furfural Mix Which is Mix Which Re- Starting Mix g ggg of Removed for mains as Next Sample Starter Max Max Pressure Tempgera- 3,2 Solubility Lbs. Lbs. Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. mm Sol- Resb' Sol- Res- Sol- Res- Sol- Resb' vent in vent in vent in vent in First Stage Resin to Eton--- Molal Ratio 1:1-.- 11.2 18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 120 135 Not soluble. Ex. No. 1340------ Second Stage Resin to EtO Mola1Ratio1:5-- 84513.6 2.65 8.45 13.6 12.65 5.03 8.12 7.55 3.42 5.48 5.10 150 )4 Somewhat Ex. N 0. 135b soluble.

Third Stage Resin to EtO.. Molal Ratio1:10-- 4.5 8.0 4.5 8.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 180 163 V1 Soluble. Ex.No.136b

Fourth Stage Resin to EtO MolalRatio1:15- 3.42 5.48 5.10 3.42 5.48 15.10 180 188 so Verysoluble. Ex. Nov 137b Fifth Stage Resin to EtO MolalRati01:20 2.05 3.65 6.60 2.05 3.651335 $5 Verysoluble. Ex.N0.138b

Date, Sept. 23-24. 1948 Phenol for resin: Menthyl Aldehyde for resin. Furfural [Resin made on pilot size batch, approximately 25 pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 13911.]

. Mix Which is Mix Which Re- Starting Mix fi g figg of Removed for mains as Next Sample Starter Max. Max. Time 1tli'ressure 'emp ege- Solubility 5. sq. m. ure, 52%: 22: ggg sBf: 322: 5 s: 23: s'lif: 322: $3 vent in vent in vent in vent in First Stage Resin to EtO. MoialRatioLL- 10.25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 46 Not soluble. Ex No. 13911 Second Stage Resin to EtO. MolalRatio1:5.-- 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 Somewhat :Ex.No.140b soluble.

Third Stage Resin to EtO.--" Molal Ratio 1:10 4.22 6.98 4.22 6.98 10.0 90 16:. 44 Soluble. Ex.No.141b

Fourth Stage Resin to 'EtO-.- Mo1alRatio1:15 3.76 6.24 3.76 6.24 13.25 100 171 94 Verysoluble. Ex. No.142b

Fifth Stage Resin to EtO Mola1Rati01:20 2.4 4.15 2.95 2.4 4.15 11.70 90 150 $4 Verysoluble Ex. No.143b--- Resin to EtO [Resin made on pilot plant size batcl1, appr0ximate1y pounds,porres ponding to 420 of Patent 2,499 370 wit 206 parts by weight of commercial =1 1 Mix whihis' Mixwm h Re- Starting Mix 12011151701101" 1 11121115 5511510 E Sample Starter M ax Max 1 I Time I lgresssure' '{emgeaahrs Solubility w 1. s-. q.in. ure' Lbs. Lbs. Lbs Lbs. .Lps. L, lib-S: L135. g Sol- Res- Eto Soi- Res- Etc 301- 1 vent in vent in in 'vent m First Stage:

11 51110012001... v MolaLL-Ratid 1:1" 12:1 18. 6 12. 1' I18. 6' 3.0 i 5. 38 8. 28 i 1.34 6. 72 10.32 7 1: 66 80 150 M2 :Insolubiec- Ex. No. 1440..-

Second Stage i t; m9- Resin to E00 U p M r j e n c y' 00; MblaLRatid 1:5 9.125 14. 25 2..-... 9.25 14. 25 11.0 1 3. 73 5 5.73 4.44 5. 52 8352 6556 100 177 912' $75101 be- Ex. N0.- 1450... coming soluble. Third Stage 5 5 Y Resin m 1310;". MolalSRatifi 1:10. 16.72 10.32 1.66 6. 72 '10. 32 14. 91 I 1. 97 r 7. 62 11.01 a 1.75 2; 5 3.90 '5 85 182 1 M I Fairly s0]!!- Ex. No. 14Gb l ble:

Fourth Stape Resin to EtOI 1 f V Molzih-Ratib' 1:15 55:52 8.52 6. 56 5. 52 8. 52 19. 81 2 1 100 '1 176 'Readily SD1- Ex. No. 14712;... ub

Fifth Stagk Resinto EtOI... Iv'ipiPBatiD 1:20. 12 2.70 3.90 1.75 2.70 8.4 I 160 $4 Quite Soil!- Ex. N0. 148b bl;

Phenol for resin: Para-phenyl Aldehyde for resin: Furfur'al Date; October 11-13, 1948 [Resin'madeon pilot'plant'size'batch; approxim ate]wfipoundsycorrespondipgto 4200f Patent2;499,37(1 with170'p'arts by weight"ot'con1mercial para'phenyiphenol replacing 164'parts by weight of para-ternary amylphenol but this batch designated as 14911.]

Mum End'of Mix W1ii011is" Mix Which Re- S'tartin'Mix: Reaemm Rersrgggllifor' maiisigfigext' b r i ax.'=; Tem era- Solubility m .1 hrs. 1 1 v 5 1bs.sq. in. ture C.

vent in vent in 1 vent in 1 vent First Stade 11 10101110110 13.9 10.7 13.0 10.? 3.0 3.50 4325 0.80 10.35 12.45 2.20 100 Ex. No. 149b i Second Stdge I Re's'ifitEtO v A I} k M0121 Ratio 10.35 12. 45 2.20 10.35 12.45 12.20 5.15 0.19 0.00 5.20 0:20 0.14 so 153 25 .watgsolu- Ex. N0. 150b. bility';

Third Stage V V V E J 7 3; Resin to EtO ii'a'irli 06111- Moial Ratio 78.90 10.7 8.90 10.70 19.0 5.30 6.38 11.32 3.00 4.32 7.68 90 193 an. 010. Ex.No. 1510 M0121 Ratio Ex. N0. 152b Resin to EtO Molal Ratio. I 3.60 4.32: 7. 68 3.60 4 -12 .15. 68 .samplesdmewhzit.rubiiermandgelat- 230 i 2' Ex. No. 153b inous but fairly soluble 12Eadiiy's6l- 100 171- 0015.

Claims (1)

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WAER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFLER INCLUDING A HYDROPHILE QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN A DIMETHYLATED HIGHER ALIPHATIC AMINE IN WHICH THE HIGH MOLAL RADICAL HAS AT LEAST 10 AND NOT MORE THAN 22 CARBON ATOMS, AND AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF AN ALPHA-HALOGEN MONOCARBOXYLIC ACID HAVING NOT OVER 6 CARBON ATOMS AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID PHYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE PHENOL-ALDEHYDE RESIN, SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARDS SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; PHENOL BEING OF THE FORMULA: