Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~L23~7~0
01 -1-
STUFFILY SUBSTITUTED SIOUX NIX ANYWHERE DE/EMULSI FIX EN
COMPOSITION AND METHODS FOR ITS USE
05
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.
"t' 1`".
~2379~
01 -2-
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~
I -3-
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.
~Z37~
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~
01 I
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.
;~37~
01 I
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.
:
~2~7~
01 -7-
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;
:: :
::
~2~'7~6~
01 -8-
O O
,. ..
C-CH-C-CH2R''
05
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
- 9 - 1936-1645
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 `'`
~L23~
01 -10-
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
01 -11-
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
.
ISLES
01 -12-
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.
:
lZ3'~
01 -14-
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.
:
1;~37~
01 -15-
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
:: :
3 237~
I -16-
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.
~ll23~
01 -17-
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
lZ3'~1'3`~
01 -18-
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(~
0 1
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.
