Note: Descriptions are shown in the official language in which they were submitted.
~L~798~
--1--
01
STABLE EMULSIFIER AND SUBSTITUTED
SUCCINIC ANHYDRIDE COMPOSITIONS THEREWITH
05 ACKGROUND OF THE INVE~TION
This invention relates to a stable polyethylene-
; oxy-containing emulsifier and an improved hydrocarbyl-
substituted succinic anhydride/emulsifier composition.
This invention also relates to an improved method for
imparting water repellency to surfaces containing groups
reactive to anhydrides. A further aspect of this inven-
tion relates to an improved method for the sizing of paper
and paperboard products.
It is well known in the art that hydrocarbyl-
substituted succinic anhydrides are good for treating
paper, 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 (RE 29,960)l these
2 compositions are particularly useful for sizing paper.
It is also known that these succinic anhydrides
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 (RE 29,960), which describes paper
siæing emulsions made from mixtures comprising a substi-
tuted cyclic dicarboxylic acid anhydride and polyoxy-
alkylene alkyl or alkylaryl ether or the corresponding
mono- or di-ester.
Long-chain diester emulsifiers, as well as mono-
esters, alkyl phenol ethoxylates and alcohol ethoxylates,
are disclosed in U.S. Patent No. 4,040,900 (RE 29,960) as
useful emulsifiers for substituted succinic anhydrides.
A major drawback of these prior art emulsifiers
is the fact that, once formed, the succinic anhydride-
emulsifier mixtures are unstable and must be promptly
used. There therefore exists a need in the art for sub-
stituted succinic anhydride-emulslfier mixtures which
demonstrate enhanced stability upon aging or storage.
:
1~7~7~
0l -2-
SUMMAR~ OF THE_INVENTION
The present invention provides a novel emulsi-
S fier of the formula:
R-W t Y-(COOH)mln
wherein R is a hydrophobic alkyl, alkylaryl, aryl-
alkyl or acyl group containing from 8 to 30 carbon atoms;
W is a water-soluble polyethyleneoxy-containing group
1~ having from 3 to ~0 ethylene oxide units which is indepen-
dently connected to R and Y through o~ygen, sulfur or
nitrogen linkages;
tY-(COOH)m]n is a capping group for the oxygen,
sulfur or nitrogen linkages on W not connected to R,
wherein Y contains from l to 9 carbon atoms, provided that
no more than 7 carbon atoms are methylene carbons;
m is l or 2;
n is l/3, l/2, l, 2, or 3;
and the hydrophile-lipophile balance (HLB) is between
about 9 and 18.
The present invention additionally provides a
stable hydrocarbyl-substituted succinic anhydride/emulsi-
fier composition comprising:
(A) 70 to 99.5% of a normally liquid hydrocarbyl-
substituted succinic anhydride containing from 6 to 50carbon atoms in the substitu0nt; and
(B) 0.5 to 30% of the emulsifier described above.
The present invention further provides a method
of imparting water repellency to surfaces containing
groups reactive to anhydrides which comprises impregnating
said surfaces with an aqueous emulsion of the substituted
succinic anhydride/emu~sifier composition of the
invention.
The present invention is also concerned with a
method of sizing paper which comprises intimately dis-
persing within the wet paper pulp, prior to the ultimate
conversion of said pulp into a dry web, an aqueous emul-
sion of the substituted succinic anhydride/emulsifier
composition of the invention~
~z79a7~
01 -3-
Among other factors, the present invention is
based on my discovery that certain derivatives of poly-
05 ethyleneoxy-containing (or "polyethylene glycol-based")
emulsifiers, wherein the free hydro~yl groups are capped
with small carbon-containing groups, are surprisingly
effective emulsifiers upon aging in substituted succinic
anhydride. These emulsifiers provide stable mixtures with
substituted succinic anhydride and do not react with the
anhydride under storage conditions.
Advantageously, the substituted succinic anhy-
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 anhydride
useful for preparing the anhydride/emulsifier composition
of the present invention i5 a hydrophobic molecule, Usu-
ally it will have one substituent in the 3-position, but
it may have substituents in both the 3- and 4-positions.
In general, the substituent will be an alkyl, alkenyl or
aralkyl group. Other elements may be present in a minor
~5 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 25. A preferred embodi-
ment of the contemplated anhydrides is the alkenyl succi-
nic anhydride made by allowing an olefin to react with
maleic anhydride by the well-known "Ene" reaction. Also
suitable i5 the "Diels-Alder" product derived from maleic
anhydride and a conjugated diene. For the present pur-
poses, I shall refer to the anhydrides contemplated as
"ASA".
The emulsifier of the present invention pos-
sesses three essential properties. First, it is soluble
in ASA at ambient temperatures. Secondly, it is stable to
storage when dissolved in ASA. Thirdly, it has surfactant
~ power to emulsify ASA in water. To satisfy these
~.2'79~37~
01 -4-
requirements, the present emulsifier contains no free -SH,
-OH or -NH groups which could react with ~SA and it has a
05 hydrophile-lipophile balance (HLB) between about 9 and 18.
Generally, to achieve the desired HLB, the emul-
sifiers will contain between about 3 and 80 average moles
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 400
The present emulsifier can be prepared from
commercially available polyethylene glycol-derived emulsi
fiers which contain free hydroxyl groups. These commer-
cially available emulsifiers are themselves soluble in ASA
and are effective for emulsifying the anhydride in water.
However, they are not stable in ASA 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. 4,040,900 (RE 29,960) and include the poly-
ethylene glycol derivatives of long-chain alcohols, alkyl-
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-(OCH2CH2)Z OH,
CXH2 ~ __~OCH2CH2)z OH,
CXH2 1 ~0CH2CH2)z- OH,
wherein x is an integer from 8 to 24 and z is an integer
from 5 to 200 Typical commercial examples of these
hydroxyl-containing emulsifiers include Igepal C0-630
(GAF), Triton X-100 (Rohm and Haas), Te~gitol TMN-6 and
*Trade Mark
-
~ - - ~
~ z7ga7~
01 -5-
Tergitol 15-S-9 (Union Carbide), and PEG 400 mono and
dilaurate (Stepan).
05 In addition to the above monohydroxy-containing
surfactants, suitable surfactants may contain various
hydrophilic moieties familiar to the art. In addition to
polyethyleneoxy groups, they may contain glyceryl, poly-
glyceryl, anhydrosorbityl or pentaerythrityl groups, and
the like. With these compounds more than one hydroxyl
group is present which must be capped to form the surfac-
tants 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.
Also contemplated are surfactants in which sul-
fur or nitrogen linkages are involved, between the hydro-
philic group and either the hydrophobic or the capping
group. For example, ethoxylated mercaptans or ethoxylated
fatty acid amides can be used. Ethoxylated sulfonamides
can also be used.
The hydrophobic moiety may be straight chain,
branched or cyclic. It may be alkyl, alkylaryl or aryl-
alkyl. It may also include an acyl 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 adds a free carboxyl at the same time as it caps, or
covers up, the hydroxyls. Generally, the capping group
will have only a minor effect on the hydrophile-lipophile
balance (HLB) of ;he emulsifier because the free carboxyl
group counteracts the effect of the cap on the HLB. One
must select the surfactant and capping group to ensure
that the capped emulsifier is within the desired HLs
range. Enough capping reagent is used to cover up all the
reactive -SH, -OH and -NH groups in the surfactant
employed.
Suitable capping reagents either contain a free
carboxyl group which does not react during the capping
*Trade Mark
!,"~
~;~79~
0l -6-
reaction or contain a nascent carboxyl which is formed
during the capping reaction, or both. An exa~ple of the
05 former type is chloroacetic acid which, after reaction,
leaves a carboxymethyl capping group. An example of the
latter type is succinic anhydride which, after reaction,
leaves a carboxypropionyl capping group.
The carboxymethyl type of cap can be added by a
1~ process similar to that described in U.S. Patent
No. ~,623,900. This is suitable for making emulsifiers of
the present invention but suffers from the disadvantage of
forming a sodium chloride byFroductc This capping reac-
tion produces an ether linkage to the hydrophilic moiety
of the emulsifier. Other stable linkages are also contem-
plated. For example, an ester linkage could be formed byreaction of the monoacyl chloride oE a polycarboxylic
acid.
Preferred capping reagents are those that form a
carboxyl derivative linkage, such as ester, amide, and the
like, to the hydrophilic moietyO
While the capping reagents are normally mono-
~unctional, they can also be difunctional or even tri-
functional, as long as the structural requirements are met
proportionately for each functional group.
The cyclic anhydride capping reagents are parti-
cularly preferred because they require no catalyst or
coreactant and no byproducts are formed. Consequently, no
additional processing steps are required. Examples of
suitable cyclic anhydrides include maleic, succinic,
glutaricr itaconic, citraconic, glutaconic, diglycolic,
thiodiglycolic, and the like. Anhydrides from acetyl
malic acid or diacetyl tartaric acid are suitable.
Bicyclic anhydrides, such as tetrahydrophthalic and hexa-
hydrophthalic, are suitable. The adduct of maleicanhydride with cyclopentadiene is suitable. Dianhydrides
such as pyromellitic dianhydride and benzophenone tetra-
carboxylic dianhydride are suitable. In this case, both
anhydride groups each react with a separate hydroxyl
1~2~987~
01 ~7~
group, so only half the molecule is considered one capping
group.
~5 The cyclic anhydride may also contain a pendant
carboxyl group before reaction, as in tricarballylic
anhydride, aconitic anhydride or acetyl citric anhydride.
In this case, the derived emulsifier of the present inven-
tion contains two pendant carboxyl groups for each capping
reagent.
In the capping group on the emulsifier, desig-
nated ~Y-(COOH)m]n in the formula above, Y will generally
contain from 1 to 9 carbon atoms, provided that no more
than 7 carbon atoms are methylene carbon atoms. By
"methylens" I mean any carbon atom which has at least
three bonds attached to hydrogen or to another carbon
atom. Therefore, methyl and some methine groups are
included in this definition. The capping group should
have relatively few methylene carbon atoms, which are
lipophilic, so that the hydrophile-lipophile balance (HLB)
of the emulsifier is not signi~icantly altered. Carbon
atoms taking part in carbon-carbon double bonds are also
counted, but as equal to 2/3 of a methylene carbon. Pre-
ferably, Y will contain from 1 to 4 carbon atoms. The
capping groups derived from the cyclic anhydrides will
contain from 4 to 10 carbon atoms per anhydride group,
including the pendant carboxyl produced. The smallest
cyclic anhydrides contemplated, such as maleic and
succinic anhydride, contain 4 carbon atoms. Up to 6 addi-
tional carbon atoms may be present, either in theanhydride ring or attached to it. With a dianhydride
capping reagent, these numbers may be doubled. Inert
groups, such as an ether or thio linkage, may also be
present in the cyclic anhydride. For example, diglycolic
and thiodiglycolic anhydride are suitable capping
reagents. The smaller cyclic anhydrides containing four
or five carbon atoms are preferred.
If the capping group contains a reactive func-
tion such as the double bond in a maleyl monoester, reac-
4~ tions known to the art may be performed with this function
~27~387~
01 -8-
.
as long as the product conforms to the composition of this
invention. For example, isomerization of a maleyl mono-
05 ester to a fumaryl monoester yields a suitable emulsifier.
: Examples of suitable capping groups on the emul-
sifier of the invention include the following:
O O
.. ..
-CH2COOH, -CCH2CH2COOH, -C-CH _ CH--COOH,
O O
O O C=O
" - I C=O
--C~ ~COO ~C=C~ , CH3 CH3
15 H~ ~ H H COOH
.
O O O
,. r~ .. ..
--Ct~ 5 ~) , -CCH 2CH 2CH 2COOH, -CCH 2 I HCH 2COOH,
~ COOH
COOH
O O
,. ..
-CCCH 2COOH,-CCH 2OCH 2COOH,
CH 2
O O O
~ ll ll
-CCS25CH~COOH, and ~C\
OOC COOH 1/2
Preferred capping groups include:
O O O O
,. " " ~
-CCH 2CH 2COH , -C~ C C ~ CO and ~ C=C
H~ ~ H H CO~H
~279~374
01 --9--
The hydrophobic/hydrophilic balance of the
capped emuIsifiers is in the normal emulsifier-detergent
05 range. One way of defining this balance i5 by the use of
the HLB scale (Hydrophile-Lipophile Balance). See
P. Becker, Chapter 18, in "Nonionic Surfactants", M. J.
Schick, Editor, Marcel Dekker (1967). The hydrophile-
lipophile 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 surfactant material expressed by a numerical
value designated the HLB number. On that scale, for my
oil-in-water capped emulsifiers, the HLB should be about 9
to 18, preferably 11 to 16.
The HLB may be estimated by comparison of
various properties, such as water solubility, with emulsi-
fiers of known HLB. Alternatively, the HLB may be cal-
culated by several procedures known to the art. See, for
example, J. T. Davies, Second Proceedings International
Congress on Surface Activity, page 426 (1957). A simple
approach with polyethyleneoxy-containing nonionic com-
pounds is to divide the weight percent polyethyleneoxide
by five. I have estimated the HLB this way for several
emulsi~iers of the present invention by including the
weight percent of the pendant carboxyl with the poly-
ethyleneoxide~ Very good ASA emulsions in water are
obtained when the estimated HLB is in the 11 to 16 range.
The emulsifier of the present invention is pre-
pared by reacting the unstable hydroxyl-containing emulsi-
fier described above with the capping reagent until thehydro;yl groups have reacted. Generally, from a few
minutes to several hours are required for this reaction at
temperatures from about 80C to 200C. With esterifica-
tion catalysts, lower temperatures and shorter times maybe employed. Before making the ASA/emulsifier composition
of the present invention, it is preferable to remove any
byproducts which may have been formed, such as sodium
chloride or hydrogen chloride. The capped emulsiÇier is
~10
79~37~
01 -10-
- then blended into the ASA, yielding the ASA/emulsifier
composition of the invention.
Alternatively, when the capping reagent is
sufficiently reactive, the hydroxyl-containing emulsifier
may be ~irst dissolved in the ASA and then reacted with
the capping reagent.
In addition to the ability to provide stable
self-emulsifying mixtures with ASA, the emulsifiers of the
present invention possess unusual surfactant properties.
The pendant carboxyl groups can ionize at high pH and can
form complexes with metal ions.
The ASA/emulsifier compositions of the present
invention comprise 7~ to 99.5 parts by weight, preferably
80 to 98 parts, of the substituted succinic anhydride 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 ASA emulsions will
be made. The two components are miscible and the mixture
is liquid at ambient temperatures.
This A~A/emulsifier composition readily emulsi-
fies into water of various hardness and pH with simple
mixing in the absence of high shear. Fine droplets areformed and the emulsion is stable until it is used for
treating a surface which contains yroups reactive to the
anhydride. The time between formation and use could range
from a few seconds to several hours. Longer times are
generally not preferred because the anhydride 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 pH above or below 7, generally in the range of 3 to
ll. Calcium and magnesium hardness ions may be present.
The amount of ASA 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 si~ing, the concentration in
37~
-11
01
the pump slurry is normally below about 100 parts per
million. Thereby about O.l to l~ of ASA is finally
absorbed on the paper.
05 Surfaces to be treated with the ASA/emulsifier
compositions of the invention to gain w~ter repellency
will contain integral groups which are reactive to the ASA
anhydride group. This normally will involve reaction with
groups such as hydroxyl, amino or mercapto. 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, preferab:Ly to a
temperature in excess of 100C, to effect a curing of the
impregnated agent within the material. It has been found
that one may conveniently use a temperature of about 125C
for a period of 15 to 20 minutes. At lower temperatures,
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 sh,uld 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 tem-
peratures at which the cellulosic material begins to
decompose. Using the composition of the present inven-
tion, it is preferred to impregnate the material with from
~79~374~
01 -12-
about 0.5 to 3~ by weight of the material of the ASA/emul-
sifier composition.
05 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 to paper
sized therewith a particularly good resistance to acidic
liquids such as acid inks, citric acid, lactic acid etc.
as compared to paper sized with the sizing agents of the
prior art. In addition to the properties already men-
tioned, these siæing agents may also be used in combina-
tion 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
light of the specific requirements of the practitioner.
It is important to emphasize, however, that with all of
these procedures, it is most essential to achieve a uni-
form disparsal of the sizing agent throughout the fiberslurry, in the form of minute droplets -hich can come in
intimate contact with the fiber surface. Uniform dis-
persal 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 utili-
zation of the sizing agents of this invention involves
their use in conjunction with a material which is either
~X7987~
~1 -13-
cationic in nature or i5, on the other hand, capable of
ionizing or dissociating in such a manner as to produce
05 one or more cations or other positively charged moieties.
These cationic 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
cationic agents in the sizing process, one may list alum,
aluminum chloride, long chain fatty amines, sodium alumi-
nate, substituted polyacrylamide, chromic sulfate, animal
glue, cationic thermosetting resins and polyamide poly-
mers. Of particular interest for use as cationic agents
are various cationic starch derivative~ including primary,
secondary, tertiary or quaternary amine starch derivatives
and other cationic nitrogen substituted starch deriva-
tives, as well as cationic 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 cationic agents may be
added to the stock, i.e., the pulp slurry, either prior
to, along with, or after the addition of the sizing agent.
However, in order to achieve maximum distribution, it is
preferable that the cationic agent be added either subse-
quent to or in direct combination with the sizing agent.
The actual addition to the stock of either the cationicagent or the sizing agent may take place at any p,int in
the paper making process prior to the ultimate conversion
of the wet pulp into a dry web or sheet. Thusr for exam-
ple, these sizing agents may be added to the pulp whilethe latter is in the headbox, 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
~L27~8~g~4
01 -14-
products. This curing process involves heating the paper
at temperatures in the range of from 80 to 150C for
05 periods of from 1 to 60 minutes. However, it should again
be noted that post curing is not essential to the success-
ful 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 combina-
tions of cellulosic with non-cellulosic fibers. The
cellulosic fibers which may be used include bleached and
unbleached sulfate (kraft), bleached and unbleached sul-
; fite, bleached and unbleached soda, neutral sulfite, semi-
chemical chemig~ound-wood, ground wood, and any combina-
tion 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 indus-
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 addedto 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 sul- fate, and diatom~ceous earths. Other additives, including
alum, as well as other sizing agents, can also be used
with these sizing agents.
With respect to proportions, the sizing agents
may be employed in amounts ranging from about 0.05 to
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 ~art 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
~;~7~374
01 -15-
higher concentration of sizing agent than paper which does
not.
05 The following examples are provided to illus-
trate 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.
EXAHPLES
Example 1
The alken~l succinic anhydride (ASA) employed in
this example was a commercial type of liquid C15_20 ASA
prepared by the "Ene" reaction of maleic anhydride with
C15_20 olefins. The olefins consisted of a 50/50 mixture
of straight chain internal olefins and branched chain
propylene oligomer, both of which covered the C15-C20
range, inclusive.
A 10% solution of Igepal C0-630, a commercial
nonionic oil-in-water emulsifier, was made in the above
ASA. This was a clear homogeneous solution at room tem-
perature. One drop (0.026 g) of this mixture was shaken
with 25 ml of water for 15 seconds in a stoppered
graduate. A stable white emulsion was formed. This emul-
sifier, which has an HLB of 13.0, is therefore an
excellent emulsifier for ASA when freshly mixed.
The 10% emulsifier in ASA mixture was allowed to
stand at room temperature~ After one week it would no
longer form a stable emulsion. Similarly, when aging was
accelerated by heating for 3 hours at 80C, the mixture
would not form a stable emulsion.
Similar results were obtained with five other
commercial emulsifiers, namely, Tergitol TMN-6, Tergitol
15-S-12, Trtion X-114, Triton X-100 and Igepal C0-620.
After heating for three hours at 80C, the 10% mixtures in
ASA had lost their self-emulsifying power. The HLB of
these emulsifiers ranyed from 11.7 to 14.5.
This example shows that commercial emulsifiers,
which form excellent emulsions when freshly mixed with
4n
~Z~9874
01 -16-
ASA, do not from stable emulsions with ASA after aging the
mixture.
05 Exampla 2
Igepal C0-630 was mixed in a 1/1 mole ratio with
succinic anhydride and heated at 80C for four hours.
During that time the solid succinic anhydride all
dissolved. An infrared analysis of the product indicated
that a monoester had formed. An intense ester carbonyl
absorption at 1735 cm 1 and carboxyl absorption at 3150
cm 1 were present. The hydroxyl absorption at 3480 cm 1
of the alkylphenol ethoxylate had disappeared.
The HLB of this capped emulsifier is estimated
at 12.5.
Example 3
The capped emulsifier of Example 2 was mixed
into the ASA 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
an excellent emulsion in water. However, in this case,
the mixture was stable to storage. After accelerated
aging, 3 hours at 80C, it still gave an excellent emul-
sion-
Therefore, the novel emulsifier of Example 2
exemplifies the present invention. It can be used to make
ASA/emulsifier compositions which are stable to storage.
Example 4
Igepal C0-630 was capped with a series of
different anhydride reagents as in Example 2 and the reac-
tion produc a were tested as emulsifiers for ASA using the
procedures described in Example 1. The results are listed
in Table I.
- ~279~74
01
TAsLE I
Emulsifiers made from Igepal C0-630
_nd_Various Cyclic Anhydrides
05
Cyclic Product ASA Emulsion Ratinq
Anhydrlde HLB Fresh
(a) Maleic 12.5 Good Good
(b) PMDA3 12.3 Fair Fair
(c) Diglycolic13.4 Good Good
1 Based on stability and turbidity measurements.
2 ASA/emulsifier mixture aged at 80C for 3 hours.
3 Pyromellitic dianhydride, half mole/mole was used.
These results show that various cyclic
anhydrides can be used to make emulsifiers of the present
invention. The fact that emulsifier performance was the
same after aging shows that the Igepal C0-630 was success-
fully capped in each case.
Example 5
Succinic anhydride was used to cap various poly-
ethyleneoxy-containing surfactants as was done in Example
2 and the reaction products were tested as emulsifiers for
ASA using the procedures described in Example 1. The
results are listed in Table II. In Table II, the expres-
sion "E0~ represents ethylene oxide units and the expres-
sion "PEG" represents polyethylene glycol. The
ASA/emulsifier mixtures were aged at 80C for 3 hours.
~Z79~374
01 -18-
TABLE II
Emulsifiers Made by Capping Various
05Surfactants with Succinic Anhydride
Product ASA Emul
Surfactant_ _LB Fresh Aged
Alkyl Phenol Ethoxylates
(a) C8~E7.5 11.8 Fair Fair
(b) C8 EOg 5 12.8 Good Good
(c) Cg-Eol2 5 13.9 Good Good
(d) Cg-EO4 8.9 Ineffective Ineffective
(e) C9-E8 11.8 Good Good
( f ) Cg~EOlo 5 13.0 Good Good
(g) Cg-EOl2 13.5 Excellent Excellent
(h) Cg~E100 18.8 Not soluble Not soluble
at room at room
temperature temperature
Alcohol Ethoxylates
(i) Tergitol TMN-611.2 Poor Poor
(j) Tergitol 15-S-912.7 Good Good
(k) Tergitol 15-S-1213.8 Good Good
Fa ty Acid Ethoxylates
(1) PEG 300 Laurate11.2 Poor Poor
(m) PEG 400 Oleate11.2 Fair Fair
Miscellaneous
In) Ethoxylated sorbitan
monostearate - EO20 14.6 Good Good
(o) Stearyl Amine - EO15 13.3 Good Good
(p) Pentaerythritol
monolaurate 8.7 Very Poor Very Poor
(q) Lauric Amide-EO510.2 Ineffective Ineffective
The results shown in Table II demonstrate that a
variety of polyethyleneoxy-containing surfactants may be
capped to form emulsifiers of the present invention. In
each case, the capped emulsifier is stable when aged in
mixture with ASA, giving the same emulsion power before and
after aging. The results also show that, to be an effective
emulsifier, the HLB of the capped emulsifier should lie
.
~ ~7~87~
01 --1 9--
between about 9 and 18. Below about 9, the capped emulsi-
fier is ineffective. Above about 18, the emulsifier is not
05 soluble in ASA.
The emulsifier of Example 2 was mixed at the 10
level in several different types of ASA, namely:
(a) Straight chain C15_20 alkenyl ASA
~b) Isooctadecenyl ASA
(c) Isooctadecyl ASA
(d) A C20 ASA derived from a dimer of C10 straight
chain alpha olefin
(e) A branched chain ASA derived from tetrapropylene.
In each case, when tested by the procedures of
Example 1, a stable emulsion was formed from both the
freshly mixed and aged ASA/emulsifier mixtures.
Example 7
The capped emulsifier of Example 4(a) was
20 isomerized using the procedure of U.S. Patent No. 3,953,616,
Example 3. This converted the capping group from a maleyl
group to a fumaryl group. Several changes were observed in
the infrared spectrum, including a slight shift in the car-
bonyl to 1725 cm 1, the appearance of trans olefin at 975
25 cm~l, and the appearance of a band at 780 cm 1.
This product, when tested by the procedures of
Example 1, produced a stable ASA emulsion, both before and
after aging the ASA/emulsifier mixture.
Example 8
The emulsifier product of Example 2 was used in a
paper sizing experiment. The sizing agent was the ASA
described in Example 6(a~. Eight percent of the emulsifier
was dissolved in the ASA and the mixture was held for about
one month. Normal TAPPI (Technical Association of the Pulp
35 and Paper Industry) laboratory handsheet procedures were
followed using a 50/50 mixture of hardwood/softwood pulp,
0.4~ ASA, and 1~ cationic starch. A paddle stirrer was used
to make the ASA/water emulsion. The handsheets were cured
at 105C for one hour. The sizing results, measured on a
40 Hercules Size Tester, were equal to that obtained from the
~;2798~4
01 -20--
same ASA to which 7~ Igepal C0-630 had been added just
before emulsif ication.
05
.~ .
lC
~ ' 15
