CA1237960A - Stable substituted succinic anhydride/emulsifier composition and methods for its use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A stable hydrocarbyl-substituted succinic anhydride/polyethyleneoxy-containing emulsifier composi-tion. There is also disclosed a method for imparting water repellency to surfaces containing groups reactive to anhydrides and a method for the sizing of paper using said composition.

Description

~L23~7~0 STUFFILY SUBSTITUTED SIOUX NIX ANYWHERE DE/EMULSI FIX EN
COMPOSITION AND METHODS FOR ITS USE

13ACKGRC)UND Of THE I NVE~TI ON

This invention relates to a stable hydrocarbyl-substituted succinic anhydride/emulsifier composition.
This invention also relates to an improved method for imparting water repellency to surfaces containing groups reactive to androids. A further aspect of this invent lion relates to an improved method for the sizing of paper and paper board products.
It is well known in the art that hydrocarbyl-substituted succinic androids are good for treating planer, fabric, or other surfaces to impart water repellency. As indicated in U.S. Patent Nos. 3,102,064, 3,821,069, 3,968,005, and 4,040,900 ORE 29,960), these compositions are particularly useful for sizing paper.
It is also known that these succinic androids are best applied for such purposes in a highly dispersed form, such as an aqueous emulsion. See, for example, U.S.
Patent No. 4,040,900 ORE 29,960), which describes paper sizing emulsions made from mixtures comprising a subset-tuned cyclic dicarboxylic acid android and polyoxy-alkaline alkyd or alkylaryl ether or the corresponding moo- or divester.
Loony chain divester emulsifiers, as well as moo-esters, alkyd phenol ethoxylates and alcohol ethoxylates,are disclosed in U.S. Patent No. 4~040/900 ORE 29,960) as useful emulsifiers for substituted succinic androids.
A major drawback of these prior art emulsifiers is the fact that, once formed, the succinic android-emulsifier mixtures are unstable and must be promptly used. There therefore exists a need in the art for sub-stituted succinic anhydride-emulsifier mixtures which demonstrate enhanced stability upon eying or storage.

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SUMMARY OF TOE INVENTION
The present invention provides a stable hydra-05 carbyl-substituted succinic anhydride/emulsifier - composition comprising:
(A) 70 to 99.5% of a normally liquid hydrocarbyl-substituted succinic android containing from 6 to 50 carbon atoms in the substituent; and (s) 0.5 to 30~ of an emulsifier of the formula:
R-W-Y
wherein R is a hydrophobic alkyd, alkylaryl, aureole-alkyd or azalea group containing from 8 to 30 carbon atoms;
W is a water-soluble polyethyleneoxy-containing group having from 3 to ethylene oxide units which is indepen-deftly connected to R and Y through oxygen, sulfur or nitrogen linkages;
Y is an azalea capping group for the oxygen, sulfur or nitrogen linkages on W not connected to R, wherein Y
contains from 2 to 8 carbon atoms, provided that no more than 7 carbon atoms are ethylene carbons; and further provided that Y may not contain a free carboxyl group;
n is 1/3, 1/2, 1, 2, or 3;
and the hydrophile-lipophile balance (HUB) is between about 9 and I
The resent invention further provides a method of imparting water repellency to surfaces containing groups reactive to androids which comprises impregnating said surfaces with an aqueous emulsion of the substituted succinic anhydride/emulsifier composition of the invention.
The present invention is also concerned with a method of sizing paper which comprises intimately disk porcine within the wet paper pulp, prior to the ultimate conversion of said pulp into a dry web, an aqueous Emil-soon of the substituted succinic anhydride/emulsifier composition of the invention.
Among other factors, the present invention is based on my discovery that certain derivatives of polyp I ethyleneoxy-containing or "polyethylene glycol-based") ~23~9~

emulsifiers, wherein the free hydroxyl groups are capped with small carbon-containing groups, are surprisingly effective emulsifiers upon aging in substituted succinic android. These emulsifiers provide stable mixtures with substituted succinic android and do not react with the android under storage conditions.
Advantageously, the substituted succinic ashy-dride-emulsifier mixtures of the present invention are highly effective in treating various surfaces to impart water-repellency. These compositions are particularly useful as superior paper sizing agents.
DETAILED Description OF THE INVENTION
The hydrocarbyl-substituted succinic android useful for preparing the anhydride/emulsifier composition of the present invention is a hydrophobic molecule. Us-ally it will have one substituent in the 3-position, but it may have substituents in both the 3- and possessions.
In general, the substituent will be an alkyd, alkenyl or aralkyl group. Other elements may be present in a minor amount, such as a sulfur or ether linkage. The total number of carbon atoms in the substituent is between 6 and 50. A preferred substituent size is between 10 and 30.
More preferred is between 12 and US. A preferred embody-mint of the contemplated androids is the alkenyl Sioux-nix android made by allowing an olefin to react with malefic android by the well-known "Eye" reaction. Also suitable is the "Diels-Alder" product derived from malefic android and a conjugated dine. For the present pun-poses, I shall refer to the androids contemplated as "AS".
The emulsifier of the present composition posy senses three essential properties. First it is soluble in AS at ambient temperatures. Secondly, it is stable Jo storage when dissolved in AS. Thirdly, it has surfactant power to emulsify AS in water. To satisfy these requirements, the present emulsifier contains no free -OH, OH or -NH groups which could react with AS and it has a I hydrophile-lipophile balance (HUB) between about 9 and 18.

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Of -4- 1936-1645 Generally, to achieve the desired HO the Emil-sifters will contain between about 3 and 80 average moles 05 of ethylene oxide, depending on the size of the lipophilic and other hydrophilic groups present. More commonly, the suitable range of moles of ethylene oxide employed will be from about 5 to 40.
The present emulsifier can be prepared from lo commercially available polyethylene glycol-derived emulsi-liens which contain free hydroxyl groups. These common-Shelley available emulsifiers are themselves soluble in AS
and are effective for emulsifying the android in water.
However, they are not stable in AS on storage due to the presence of the hydroxyl groups. examples of this class of hydroxyl-containing compounds are described in U.S.
Patent No. ~,040,900 ORE 29,960) and include the polyp ethylene glycol derivatives of long-chain alcohols, alkyd-phenols and carboxylic acids, which are commonly used to emulsify oils in water. In general, these compounds will contain one free hydroxyl group and can be represented by the following formulae:

CXH2X+l C-(OC~2CH2)z / I\
x ox (OCH2CH2)z OH, CXH2 +1 ( 0CH2CH2 ) Z

wherein x is an integer from 8 to 24 and z is an integer from 5 to 20. Typical commercial examples of these hydroxyl-containing emulsifiers include Igepal C0-630 (GAY), Briton X-100 (Room and Hays), Tergitol TMN-6 and Tergitol 15-S-9 (Union Carbide), and PEG 400 moo and dilaurate (Steepen).
In addition to the above monohydroxy-containing surfactants, suitable surfactants may contain various * Trade Mark Jo ~Z3~

hydrophilic moieties familiar to the art. In addition to polyethyleneoxy groups, they may contain glycerol, polyp 05 glycerol, anhydrosorbityl or pentaerythrityl groups, and the like. With these compounds more than one hydroxyl group is present which must be capped to form the surface tents of the present invention. Small amounts of pro-pyleneoxy groups may also be present. It is not desirable to employ surfactants which possess more than about four hydroxyl groups because of the excessive amount of capping required.
lo contemplated are surfactants in which sulk fur or nitrogen linkages are involved, between the hydra-Philip group and either the hydrophobic or the capping group For example, ethoxylated mercaptans or ethoxylated fatty acid asides can be used. Ethoxylated sulfonamides can also be used.
The hydrophobic moiety may be straight chain, branched or cyclic. It may be alkyd, alkylaryl or aureole-alkyd. It may also include an azalea attachment.
The above-described compounds are converted to the emulsifiers of the present invention by reacting the free hydroxyls with a small carbon-containing reagent which caps, or covers up, the hydroxyls. Generally, the capping group will have the effect of modestly lowering the hydrophile-lipophile balance HO of the emulsifier because the capping group adds a small hydrophobic moiety to the molecule. One must select the surfactant and capping group to ensure that the capped emulsifier is within the desired HUB range. Enough capping reagent is used to cover up all the reactive -SO, -OH and -NH groups in the surfactant employed In general the capping reagent can be any reagent which will form a derivative of the emulsifier's -OH, -SO, or -NH groups, as long as the derivative provides a stable emulsion when dissolved in AS.
Surprisingly, I have found that certain common derivatives do not give stable emulsions. Thus, sill ethers and sulfonate esters do not form stable emulsions upon aging.

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However, carboxylic esters, carbamate esters and veto esters have been found to provide stable emulsions in AS.
ox Therefore, capping reagents suitable for use in preparing the compositions of the present invention are those which add an azalea cap to the starting emulsifier.
Contemplated capping reagents are those that form a carboxyl derivative linkage, such as ester, aside, carbamate, urea, and the like, to the hydrophilic moiety.
Suitable reagents are carboxylic androids, acid halides, isocyanates, kitten divers, and the like. Examples of suitable reagents include acetic android, kitten, Dakotan, acutely chloride, acutely bromide, propionyl android, bitterly chloride, pivaloyl chloride, hexanoyl chloride, bouncily chloride, toluyl chloride, ethyl isocyanate, ethyl isothiocyanate, Huxley isocyanate, and the like.
While the capping reagents are normally moo-functional, they can also be difunctional or even in-functional, as long as the structural requirements are met proportionately for each functional group. examples of suitable difunctional reagents include sectional chloride, molehill chloride, adipoyl chloride, decant dicarboxylic acid chloride, Tulane diisocyanate, diphenyl methane-4,4'-diisocyanate, and the like.
The following illustrates the range of suitable carbon-containing groups and reactive functions which may be combined to make suitable reagents. Carbon-containing groups include methyl, ethyl, propyl,butyl, ponytail, Huxley, hotly (all branched or straight chain), cyclopentyl, cyclohexyl, phenol, bouncily and toll. Reactive functions include androids, acid halides, isocyanate, and isothiocyanate.
Capping reagents are preferred which require no catalyst or coreactant and which form no byproducts.
Consequently, no additional processing steps are required. Examples of suitable reagents include ethyl isocyanate, Tulane diisocyanate, kitten and kitten diver.
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The azalea capping group on the emulsifier, design noted Y in the formula above, will generally contain from 05 2 to 8 carbon atoms, provided that no more than 7 carbon atoms are ethylene carbon atoms. The capping group, Y, also may not contain a free carboxyl group. By "ethylene" I mean any carbon atom which has at least three bonds attached to hydrogen or to another carbon atom. Therefore, methyl and some methane groups are included in this definition. The capping group, having relatively few ethylene carbon atoms which are lip-Philip, will not strongly alter the hydrophile-lipophile balance (HUB) of the emulsifier. Carbon atoms taking part in carbon-carbon double bonds are also counted, but as equal to 2/3 of a ethylene carbon. Preferably, Y will contain from to 6 carbon atoms. With a difunctional capping reagent, these numbers of carbon atoms may be doubled. Inert groups, such as an ether or trio linkage, may also be present. In addition, inert aside linkages, such as in carbamates derived from isocyanates, may be present. Inert carbonyl groups, such as those seen in veto esters obtained from reaction with Dakotan, may be present. Inert halides may also be present.
If the capping group contains a reactive lung-lion such as the double bond in a molehill divester, react lions known to the art may be performed with this function as long as the product conforms to the composition of this invention. For example, isomerization of a molehill divester to a fumaryl divester yields a suitable emulsifier.
.
Examples of suitable capping groups on the Emil-sifter of the present composition include the following:
Jo O

35~ -C-R' and -C-NH-R' wherein R' is an~n-alkyl, isoalkyl, cycloalkyl or ; aureole group containing from l to 7 carbon atoms;

:: :
::

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O O
,. ..
C-CH-C-CH2R'' R'' wherein R'' is hydrogen, methyl or ethyl; and O O O O
1, , -CROOK- and -C-NH-RI''-NH-C-wherein R' " is an n-alkylene, isoalkylene, cycloalkylene or Arlene group containing from 2 to 14 lo carbon atoms.
pacific examples of contemplated capping groups include:

O () O
,. .. ..
C~13C-~ CH3(CH2)4C , (C~3)3C-C-, O O O
,. .. ..
CH3C~CH2-C-, CH3CH2-NH-C- I

O O
i- -SCHICK-SCHICK
., .
O
; " SHEA O
C- I .-; : / NH-C
I:: 35 (Shelley and NH-C-O ..
O

40~
, :

" ~237~6~3 Another example of a capped emulsifier conforming to the composition of the present invention is the product made by heating at 150C to 230C for 1 to 500 hours an emulsifier capped with a cyclic android, such as succinic android.
The heat treatment which removes the pendant carboxyl group leading to a capped emulsifier according to the composition of the present invention is also described elsewhere.
The hydrophobicthydrophilic balance of the capped emulsifiers is in the normal emulsifier-detergent range. One way of defining this balance is by the use of the HUB scale (Hydrophile-Lipophile Balance). See P. Becker, Chapter 18, in "Non ionic Surfactants", MY Schick, Editor, Marcel Decker (1967). The hydrofoil lipophi].e balance is an indication of the size and strength of the hydrophiLic (water-loving or polar) groups, and the lipophilic (oil-loving or non-polar) groups in a surEactant material expressed by a numerical value designated the HUB number. On what scale, for my oil-in-water carped emulsifiers, the HUB should be about 9 to I preferably 11 to 16.
The HUB may be estimated by comparison of various properties, such as water volubility, with emulsifiers of known HUB. Alternatively, the HUB may be calculated by several procedures known in the art. See, for example, JUT. Davies, Second Proceedings International Congress on Surface Activity, page 426 (1957). A simple approach with polyethyleneoxy-containing non ionic compounds is to divide the weight percent polyethylene oxide by five. X have estimated the HUB this way AS
for several emulsifiers of the present composition. Very good , , to `'`

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emulsions in water are obtained when the estimated HO is in the 11 to 16 range.
05 The emulsifier of the present composition is prepared by reacting the unstable hydroxyl-containing emulsifier described above with the capping reagent until the hydroxyl groups have reacted. Generally, from a few minutes to several hours are required for this reaction at 10 temperatures from about 80C to kiwi With catalysts, lower temperatures and shorter times may be employed. The ester derivatives, which would normally be made from carboxylic android or acid halide reagents, could alternatively be prepared from a carboxylic acid or ester by other esterification reactions well known to the art, such as acid-catalyzed esterification or base-cataly~ed ester interchange. Before making the ASA/emulsifier composition of the present invention, it is preferable to remove an byproducts which may have been formed, such as water, acetic acid or hydrogen chloride. The capped emulsifier is then blended into the AS, yielding the ASA/emulsifier composition of the invention.
Alternatively, when the capping reagent is sufficiently reactive, the hydroxyl-containing emulsifier may be first dissolved in the AS and then reacted with the capping reagent.
The ASA/emulsifier compositions of the present invention comprise 70 to 99.5 parts by weight, preferably 80 to 98 parts, of the substituted succinic android and 0.5 to 30 parts by weight, preferably 2 to 20 parts, of the capped emulsifier. These ASA/emulsifier combinations are easy to make at a central location and can be stored ; and shipped to the location where the AS emulsions will be made The two components are miscible and the mixture is liquid at ambient temperatures.
This ASA/emulsifier composition readily emulsi-lies into water of various hardness and pi with simple mixing in the absence of high shear. Fine droplets are formed and the emulsion is stable until it is used for treating a surface which contains groups reactive to the ~;~37~;0 android. The time between formation and use could range from a few seconds to several hours. Longer times are generally not preferred because the android groups will gradually be hydrolyzed by the water present.
The water used can be relatively pure or can contain the usual impurities in domestic water. It can have a pi above or below 7, generally in the range of 3 to 11. Calcium and magnesium hardness ions may be present.
The amount of AS suspended in the water can vary widely, from a few parts per million to 10% or more depending on the use and method of application. For wood or fabric treatment, concentrations around 1% may be used, whereas for internal paper sizing, the concentration in the pump slurry is normally below about 10~ parts per million. Thereby about 0.] to I of AS is finally absorbed on the paper.
Surfaces to be treated with the ASA/emulsifier compositions of the invention to gain water repellency will contain integral groups which are reactive to the AS
android group. This normally will involve reaction with groups such as hydroxyl, amino or Marquette. A preferred type of material which may be treated with emulsions of the compositions of the invention contains carbohydrate molecules, such as cellulose or starch, at the surface of the material. These materials contain many hydroxyl groups which can react with the AS.
As stated above, the ASA/emulsifier compositions of the present invention may be used to impart water repellency to cellulosic materials. The water-repellent compositions described above are preferably applied to the material in aqueous emulsions. The emulsion may be sprayed onto the material or the material may be dipped into the emulsion in order to distribute the derivative evenly throughout the material. The impregnated material is then withdrawn from the solution and air dried. After air drying, the material is then heated, preferably to a temperature in excess of 100C, to effect a curing of the I impregnated agent within the material It has been found .

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that one may conveniently use a temperature of about pharaoh a period of 15 to 20 minutes. At lower temperatures, 05 longer periods of time are required to effect the curing process. Lower temperatures and shorter times may be used if an acylation catalyst is present. To be commercially practical, the curing time should be as short as possible and generally less than one hour. At higher temperatures, the heat curing may be accomplished in shorter periods of time. The upper limit of temperature at which the heat curing process may be carried out is limited to the them-portrays at which the cellulosic material begins to decompose. Using the composition of the present invent lion, it is preferred to impregnate the material with from about 0.5 to 3% by weight of the material of the ASA/emul-sifter composition.
The ASA/emulsifier compositions of the present invention may additionally be used as paper sizing agents.
These novel sizing agents display all of the features and advantages of prior art sizing agents. Moreover, the novel sizing agents of this invention impart Jo paper sized therewith a particularly good resistance to acidic liquids such as acid inks, citric acid, lactic acid etch as compared to paper sized with the sizing agents of the prior art. In addition to the properties already men-toned, these sizing agents may also be used in combine-lion with alum as well as with any of the pigments, fillers and other ingredients which may be added to paper.
The sizing agents of the present invention may also be used in conjunction with other sizing agents so as to obtain additive sizing effects. A still further advantage is that they do not detract from the strength of the paper and when used with certain adjuncts will, in fact, increase the strength of the finished sheets. Only mild drying or curing conditions are required to develop full sizing value.
The actual use of these sizing agents in the manufacture of paper is subject to a number of variations in technique, any of which may be further modified in ~Z3~9$0 Of -13-light of the specific requirements of the practitioner It is important to emphasize, however, that with all of 05 these procedures, it is most essential to achieve a unit form dispersal of the sizing agent throughout the fiber slurry, in the form of minute droplets which can come in intimate contact with the fiber surface. Uniform disk perusal may be obtained by adding the sizing agent to the pulp or by adding a previously formed, fully dispersed emulsion. Chemical dispersing agents may also be added to the fiber slurry.
Another important factor in the effective utile-ration of the sizing agents of this invention involves their use in conjunction with a material which is either cat ionic in nature or is, on the other hand, capable of ionizing or dissociating in such a manner as to produce one or more cations or other positively charged moieties.
These cat ionic agents, as they will be hereinafter referred to, have been found useful as a means for aiding in the retention of sizing agents herein as well as for bringing the latter into close proximity to the pulp fibers. among the materials which may be employed as cat ionic agents in the sizing process, one may list alum, aluminum chloride, long chain fatty amine, sodium alum-Nate substituted polyacrylamide, chronic sulfate, animal glue, cat ionic thermosetting resins and polyamide polyp mews. Of particular interest for use as cat ionic agents are various cat ionic starch derivatives including primary, secondary, tertiary or qua ternary amine starch derivatives and other cat ionic nitrogen substituted starch derive-lives, as well as cat ionic sulfonium and phosphonium starch derivatives. Such derivatives may be prepared from all types of starches including corn, tapioca, potato, waxy maize, wheat and rice. Moreover, they may be in their original granule form or they may be converted to pregelatinized, cold water soluble products.
Any of the above noted cat ionic agents may be added to the stock, lye., the pulp slurry, either prior to, along with, or aster the addition ox the sizing agent.
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However, in order to achieve maximum distribution, it is preferable that the cat ionic agent be added either subset ox quint to or in direct combination with the sizing agent The actual addition to the stock of either the cat ionic agent or the sizing agent may take place at any point in the paper making process prior to the ultimate conversion of the wet pulp into a dry web or sheet. Thus, for exam-pie, these sizing agents may be added to the pulp wealth latter is in the head box, beater, hydropulper or stock chest.
further improvements in the water resistance of the paper prepared with these novel sizing agents may be obtained by curing the resulting webs, sheets, or molded products. This curing process involves heating the paper at temperatures in the range of from 80 to 15~C for periods of from 1 to 60 minutes. However, it should again be noted that post curing is not essential to the success-us operation of this invention.
The sizing agents of this invention may, of course, be successfully utilized for the sizing of paper prepared from all types of both cellulosic and combine-lions of cellulosic with non-cellulosic fibers. The cellulosic fibers which may be used include bleached and unbleached sulfate croft), bleached and unbleached sulk file, bleached and unbleached soda, neutral sulfite, semi-chemical chemiground wood, ground wood, and any combine-lion of these fibers. These designations refer to wood pulp fibers which have been prepared by means of a variety of processes which are used in the pulp and paper incus-try. In addition, synthetic fibers of the viscose rayon or regenerated cellulose type can also be used.
; All types of pigments and fillers may be added to the paper which is to be sized with the novel sizing agents of this invention. Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulk ; fate, and diatomaceous earths. Other additives, including alum, as well as other sizing agents, can also be used with these sizing agents.
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With respect to proportions, the sizing agents may be employed in amounts ranging from about 0.05 to 05 about 3.0~ of the dry weight of the pulp in the finished sheet or web. While amounts in excess of 3% may be used, the benefits of increased sizing properties are usually not economically justified. Within the mentioned range the precise amount of size which is to be used will depend for the most part upon the type of pulp which is being utilized, the specific operating conditions, as well as the particular end use for which the paper is destined.
; Thus, for example, paper which will require good water resistance or ink holdout will necessitate the use of a lo higher concentration of sizing agent than paper which does not.
The following examples are provided to thus-irate the invention in accordance with the principles of this invention but are not to be construed as limiting the invention in any way except as indicated by the appended claims.
EXAMPLES
Example 1 The alkenyl succinic android (AS) employed in this example was a commercial type of liquid C15_20 AS
prepared by the "Eye" reaction of malefic android with C15_20 olefins. The olefins consisted ox a 50/50 mixture of straight chain internal olefins and branched chain propylene oliyomer, both of which covered the C15-C20 range, inclusive.
A 10% solution of Igepal C0-630, a commercial non ionic oil-in-water emulsifier, was made in the above AS. This was a clear homogeneous solution at room them-portray. One drop (0.026 y) of this mixture was shaken with 25 ml of water for 15 seconds in a stopper Ed graduate. A stable white emulsion was formed. This Emil-sifter, which has an HUB of 13.0, is therefore an excellent emulsifier for AS when freshly mixed.
The 10% emulsifier in AS mixture was allowed to 40 stand at room temperature. After one week it would no :: :

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longer form a stable emulsion. similarly, when aging was accelerated by heating for 3 hours at 80C, the mixture 05 would not form a stable emulsion.
Similar results were obtained with six other commercial emulsifiers, namely, Tergitol TM~-6, Tergitol sly Briton X-114, Briton X-100, Igepal C0-620, and Igepal C0-720. After heating for three hours at 80C, the 10% mixtures in AS had lost their self-emulsifying power. The HUB of these emulsifiers ranged from 11.7 to 14.5.
This example shows that commercial emulsifiers, which form excellent emulsions when freshly mixed with AS, do not form stable emulsions with AS after aging the mixture.
Example 2 Igepal C~-630 was mixed in a 1/1 mole ratio hit acetic android and heated at 80C for sixteen hours.
Infrared analysis of the mixture indicated that the acetic ; android had been consumed, as ester had formed, and by-product acetic acid was present. An intense ester carbonyl absorption at 1735 cm 1 had replaced the android peats at 1750 and 1820 cm 1. The acetic acid showed absorption at 1710 and 3150 cm 1. The hydroxyl absorption at 3430 cm 1 of the alkylphenol ethoxylate had disappeared. The by-product acetic acid was removed by heating in a vacuum oven at 80C overnight.
The HUB of this capped emulsifier is estimated at 12.2, assuming that Igepal C0-630 is an ethoxylated nonyl phenol containing 9.3 ethylene oxide units.
Example 3 The capped emulsifier of Example 2 was mixed into the AS of Example 1 at the 10~ level A homogeneous solution at room temperature was obtained.
When this mixture was tested for emulsifying power by the procedure described in Example 1, it formed a good emulsion in water. However, in this case, the mixture was stable to storage. After accelerated aging, 3 O hours at 80C, it still gave a good emulsion.

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Therefore, this ASA/emulsifier composition, which is stable to storage, exemplifies the present 05 invention.
Example 4 Igepal C0-630 was mixed in a 1/1 mole ratio with ethyl isocyanate and heated at 80C for sixteen hours.
Infrared examination of the product showed that the hydroxyl absorption at 3480 cm 1 had disappeared, an N-H
band was present at 3350 cm 1, and a large carbamate carbonyl band was present at 1725 cm 1.
The HO of this capped emulsifier is estimated at 11.7. The ethyl isocyanate reagent is advantageous in that no by-product is formed in the capping step.

The capped emulsifier of Example 4 was mixed into the AS of Example 1 at the I level. A homogeneous solution at room temperature was obtained.
When this mixture was tested for emulsifying power by the procedure described in Example 1, it formed a good emulsion in water. However, in this case, the mixture was stable to storage. After accelerated aging, 3 hours at 80C, it still gave a good emulsion.
Therefore, this ASA/emulsifier composition, which is stable to storage, exemplifies the present nventlon.
Example 6 The same procedures and tests as in Examples 2 and 3 were carried out starting with Igepal C0-630 and capping with, in one case, methane sulfonyl chloride, and in another case, chlorotrimethyl Solon. In both cases, the capped emulsifier was dissolved in ALA. When freshly mixed, good to excellent emulsions were formed in water After aging for 3 hours at 80~C, neither formed a stable emulsion.
This example shows that some common hydroxyl reagents are not satisfactory capping reagents for use in the present invention.
I

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The same negative result was obtained with Igepal C0-720 capped with methane sulfonyl chloride.
05 Example 7 The same procedures and tests as in Examples 2 and 3 were carried out starting with Igepal C~-630 and capping with one equivalent (one-half mole) of sectional chloride. In this case, the final ASA/emulsifier mixture was stable to storage, producing a good emulsion in water after heating at 80C for 3 hours.
This capping procedure with a difunctional reagent provides a composition exemplifying the present invention. The capped emulsifier HUB is estimated at 12,2.
Example 8 The same experiments as in Example 7 were carried out with sectional chloride as the difunctional capping event hut with Igepal C0-720 as the starting ; 20 emulsifier. In this case, an excellent emulsion was produced before and after accelerated aging. The HUB is estimated at 13.4, assuming that Igepal C0-72~ is an ethoxylated nonyl phenol containing 12 ethylene oxide units.
Example The same procedures as in Examples 2 and 3 were carried out starting with Igepal C0-630 and capping separately with Dakotan and Tulane diisocyanate. In each case the A~A/capped emulsifier formed a stable emulsion in water after accelerated aging.
These reagents are advantageous in that no by-product is formed in the capping step. The HUB for the Dakotan capped emulsifier is estimated at 11.5 and the HUB for the Tulane diisocyanate capped emulsifier is estimated at 11.4.
Example 10 The same procedures as in Examples 2 and 3 were carried out starting with Igepal C~-720 and capping separately with Dakotan and the acid chlorides of 1, 10 I decant dicarboxylic acid, benzoic acid, pivalic acid, and ~237~6(~

n-hexanoic acid. In each case, the A~A/capped emulsifier formed a stable emulsion in water after accelerated aging.
05 The HUB of these capped emulsifiers is estimated to range from 12.4 to 12.7.

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A stable hydrocarbyl-substituted succinic anhy-dride/emulsifier composition comprising:
(A) 70 to 99.5% of a normally liquid hydrocar-byl-substituted succinic anhydride containing from 6 to 50 carbon atoms in the substituent; and (B) 0.5 to 30% of an emulsifier of the formula:
R-W -Y
wherein R is a hydrophobic alkyl, alkylaryl, arylalkyl or acyl group containing from 8 to 30 carbon atoms;
W is a water-soluble polyethyleneoxy-containing group having from 3 to 80 ethylene oxide units which is indepen-dently connected to R and Y through oxygen, sulfur or nitrogen linkages;
Y is an acyl capping group for the oxygen, sulfur or nitrogen linkages on W not connected to R, wherein Y
contains from 2 to 8 carbon atoms, provided that no more than 7 carbon atoms are methylene carbons; and further provided that Y may not contain a free carboxyl group;
n is 1/3, 1/2, 1, 2, or 3;
and the hydrophile-lipophile balance is between about 9 and 18 on the HLB scale.

2. The composition according to Claim 1, wherein the hydrocarbyl substituent of component (A) is selected from the group consisting of alkyl, alkenyl and aralkyl.

3. The composition according to Claim 2, wherein the hydrocarbyl substituent of component (A) is alkenyl.

4. The composition according to Claim 1, wherein the hydrocarbyl substituent of component (A) contains from 10 to 30 carbon atoms.

5. The composition according to Claim 4, wherein the hydrocarbyl substituent of component (A) contains from 12 to 25 carbon atoms.

6. The composition according to Claim 1, wherein W
has from 5 to 40 ethylene oxide units.

7. The composition according to Claim 1, wherein W
is connected to R and Y through oxygen linkages.

8. The composition according to Claim 1, wherein Y
contains from 2 to 6 carbon atoms.

9. The composition according to Claim 1, wherein R-W- is derived from hydroxyl-containing compounds selected from the group consisting of:

wherein x is an integer from 8 to 24 and z is an integer from 5 to 20.

10. The composition according to Claim 1, wherein Y
is selected from the group consisting of:

wherein R' is an n-alkyl; isoalkyl, cycloalkyl or aryl group containing from 1 to 7 carbon atoms;

wherein R'' is hydrogen, methyl or ethyl; and wherein R''' is an n-alkylene, isoalkylene, cycloalkylene or arylene group containing from 2 to 14 carbon atoms.

11. The composition according to Claim 10, wherein Y
is selected from the group consisting of:

12. The composition according to Claim 1, wherein the emulsifier of component (B) has a hydrophile-lipophile balance of about 11 to 16 on the HLB scale.

13. The composition according to Claim 1, wherein the composition is in the form of an aqueous emulsion.

14. A method of imparting water repellency to sur-faces containing groups reactive to anhydrides which com-prises impregnating said surfaces with an aqueous emulsion of the composition of Claim 1.

15. The method of Claim 14, wherein said surfaces are cellulosic materials.

16. A method of sizing paper which comprises the step of intimately dispersing within the wet pulp, prior to the ultimate conversion of said pulp into a dry web, an aqueous emulsion of the composition of Claim 1.