Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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01 --1--
ALKENYL SUCCINIC ANHYDRIDE CO~tPOSITION
_AND METHOD FOR ITS PREPARATION
05 ' '
~ACKGROUND OF THE INVENTION
..
This invention relates to ~n improved liquid
alkenyl succinic anhydride mixture having superior paper
sizing properties and a process for its preparation.
l~ This invention also relates to an improved method for the
sizing oE paper and paperboard products. A ~urther aspec~
of this invention relates to an improved method for
imparting water-repellency to cellulosic fabrics.
It is known in the art that long strAight chain
alkanyl succinic anhydrides can be used as effective paper
sizing agents. See, for example, U.S. Paten~
Nos. 3,102,064; 3,821,069; 3,968,005; and 4,040,900
(Re. 29,960). These alkenyl succinic anhydrides have also
been used as fabric treating agents. See U.S, Patent
2~ No. 2,903,382. The useful molecular weight range of the
alkenyl group on these sizing agents has variously been
described as encompassing 8 to 35 carbon atoms.
It is also known that these prior art sizing
agents are best applied in a highly dispersed form, such
as an aqueous emulsion. However, alkenyl succinic
anhydrides made from straight chain alpha olefins are
solids at ambient temperatures and are therefore not
effective in forming these emulsions. In view of this,
commercial alkenyl succinic anhydride paper sizing agents
are made from isomerized straight chain alpha olafins
(i.e~, straight chain internal olefins) or from branched
chain olefins. See, for example, the frequent reference
to "isooctadecenyl succinic anhydride" in UOS.
Patent No. 3,102,064.
It has been taught that the molecular weight of
the alkenyl group of the more effective or preferred
alkenyl succinic anhydride sizing agents corresponds to a
carbon number in the 13 to 22 carbon atom range. Mixtures
of several carbon numbers have also been described.
S8S;2
See, for example, the reference to C15_20 alkenyl 5uccinic
anhydride in U.S. Patent No. 4,040,900 (Re. 29,~60).
SUMMARY OF THE INVENTION
The present invention provides a two-component
alkenyl succinic anhydride composition with superior paper
sizing properties which.comprises:
~ A) the reaction product o maleic anhydride and
straight chain alpha olefins in the C13 to C18 range preferably
having an average molecular weight o from about 182 to
238; and
(b) the reaction product of maleic anhydride and
straight chain internal olefins or branched chaln olefins
in th~ C14 to C22 range preferably havin~ an average molecular
weight oE ~rom about 224 to 308;
wherein component (B) has a mol~cular weight of at least 10
units higher than component (A).
~ ; Preerably the above mixture contains about 5 to
.~ 40~ o component (.A)`and, more preferably, about 10 to 35
.~ of component (Aj.
;~` :
The present invention is also concerned with a
; ~ method of sizing.- paper~by dispersing within the wet paper
~ pulp and alkenyl succinic anhydride composition as described
-.~ above.
: The inst:an~ invention is fur*her concerned with
a method o treating cellulosic abric to render the same
:
water-repellent by impregnating the fabric with the novel
alkenyl succinic anhydride compositions of the invention.
The present invention also provides.a pr~ferred
process for the~preparation of the instant alkenyl succinic
: anhydride compositlon from maleic anhydride and a mixture of
straight chain alpha olefins in the C13 to C22 range ~hich
: comprises:
- 2 -
(A) introducing -the alpha olefins in-to a distillation
zone wherein at least a por-tion of the lowest boiling alpha
olefin is vaporized and taken overhead;
(B) isomerizin~ -the remaining bottoms Erom -the distilla-tion
zone to reduce the alpha olefin content to less than 15%
of the total olefin bottoms content;
- 2a -
'~. ...
.D~
-3-
(C) recombining the alpha olefin overhead fraction
recovered from step ~A) with the isomerized olefin bottoms
05 fraction of step (s); and
~ D) reacting the recombined olefins from step (C)
with maleic anhydrida to provide the alkenyl succinic
anhydride product.
In another aspect of the process of the
invention, the unisomerized alpha olefin overhead ~raction
recovered from step (A) and the isomeri~ecl olefin Ibottoms
fraction of step (B) are each independently reactel~ with
maleic anhydride, and the resulting alkenyl suc~cinic
anhydride products are then combined to provide the
lS alkenyl succinic anhydride of the invention.
Preferably, the alpha olefin content in step (B)
is reduced to less than 10~, and more preferably, less
than 5%1 of the total olefin bottoms content.
Among other factors, the present invention is
based on my surprising discovery that certain s~raight
chain alpha olefin-derived alkenyl succinic anhydrldes,
heretofore considered not useful, can be combined in
specific mixtures with other alkenyl succinic anhydrides
to provide a superior paper sizing product.
An additional advantaga of the present invention
is the fact that, when straight chain alpha olefins are
being used as the starting feedstock for making liquid
alkenyl succinic anhydrides, less olefin processing is
required prior to forming the alkenyl succinic anhydride.
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention may be
prepared by simply combining the described alkenyl suc-
cinic anhydride components or, alternatively, by combining
the precursor olefins and then making the desired alkenyl
succinic anhydride. For example, a broad range straight
chain alpha olefin mixture, which may be obtained from wax
cracking, Fischer-Tropsch synthesis or ethylene oligomeri-
zation, could be distilled to yield light and heavv frac-
tions. The heavy fraction is then isomerized to move the
4~ double bond to internal positions and recombined with the
01 ~4-
light fraction before makin~ the alkenyl succinic
anhydride composition of the present invention.
Q5 The olefin feed for component (A) of the present
composition should be predominantly ~traight chain
l-olefin.- Minor amounts of chain branching or internal
olefin, such as is found in commercial "alpha olefins,"
may also be present.
The olefin feed Eor either component (A~ or (B)
may consist of a single carbon number, a mixture o con-
tiguous carbon numbers or may consist of any combination
of carbon numbers within that range.
The olefin feed for component (~) may b~
IS stralght chain or branchecl. Branched chain olefin may be
obtained from various sources such a~ by oligomerization
of lower olefins in the C3 to Cll range. IE straight
chain, the olefin should be substantially free of alpha
olefin. These straight chain olefins may be obtained from
2~ n-paraffins by processes well known in the art, such as
dehydrogenation and chlorination-dehydrochlorination.
Alternatively, the straight chain olefins may be made by
isomerizing alpha olefins using acidic or basic catalysts,
in accordance with the preferred process of the invention.
According to the process of this invention, the
olefin feed for component (B) is a straight chain internal
olefin obtained by isomerizing straight chain alpha
olefins in the C14 to C22 range. This isomerization may
be accomplished using acidic or basic catalysts. The
isomerization should be sufficient to leave no more than
about 15% alpha olefin remaining, preferably less than
10~, and more preferably, less than 5~ alpha olefin.
These olefins may be augmented by the inclusion of
branched chain olefins or internal straight chain olefins
obtained from other sources, as dascribed above. In
general, the olefin feed for component ~s) should be sub-
stantially free of straight chain alpha olefin.
The novel sizing agents display all oF the
features and advantages of the cited prior art sizing
agents. Moreover, the novel sizing agents of this
5~5~
~1 5-
invention impart to paper sized therewith a particularly
good resistance to acidic liquids such as acid inks,
05 citric acid, lactic acid etc. as compared to paper sized
with the si~ing agents of the cited prior art~ In addi-
tion to the properties already mentioned, these sizing
agents may also be used in combination 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 wlth
other si2ing agents so as to obtain additive sizing
efects. A still further advantage is that thay do not
detract from the strength o the paper and when used wlth
certain adjuncts will, in ~act, 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 papar is subject to a number of variations
in technlque any of which may be further modified in light
of the specific requirements of the practitioner. ~t is
important to emphasiæe, however, that with all of these
procedures, it is most essential to achieve a uniform
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 dispersal may be
obtained by adding the sizing agent to the pulp with vigo-
rous agitation 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
utilization of the sizing agents of this invention
involves their use in conjunction with a material which is
either cationic in nature or is, on the other hand, capa-
ble of ionizing or dissociating in such a manner as toproduce one or more cations or other positively charged
moieties. These cationic agents, as they will be herein-
after referred to, have been found useful as a rneans for
aiding in the retention of sizing agents herein as well as
for bringing the latter into close proximity t:o the pulp
5~
~1 -6-
fibers. Among the materials which may be employed as
cationic agents in the sizing proces;, one may list alum,
oS aluminum chloride, long chain fatty amines, sodium alumi-
nate r 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 derivatives including primary,
secondary, tertiary or quaternary amine starch derivatives
and other cationic nitrogen substituted starch deriva-
tives, as well as cationic sulEonium and phosphoni~m
starch derivatives. Such derivatives may be prepared from
all types o~ starches including corn, tapioca, pota~o,
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
2U 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
subsequent to or in direct combination with the sizing
agent. The actual addition to the stock of either the
cationic 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 example, these sizing agents may be added to the pulp
while She latter is in the headbox, beater, hydropulper or
stock chest.
In order to obtain good sizing, it is desirable
that the sizing agents be uniformly dispersed throughout
the fiber slurry in as small a particle size as is pos-
sible to obtain. One method for accomplishing this is to
emulsify the sizing agent prior to its addition to the
stock utilizing either mechanical means, such as high
speed agitators, mechanical homogenizers, or by the addi-
tion of a suitable emulsifying agent. Where possible, it
is highly desirable to employ the cationic agent as the
emulsifier and this procedure is particularly successful
-
5~5~
Ql _7_
where cationic starch derivatives are utilized. Among the
applicable non-cationic emulsifiers which may be used as
oS emulsifying agents for the sizing agents, one may list
such hydrocolloids as ordinary starches, non-cationic
starch derivatives, dextrines, carboxymethyl cellulose,
gum arabic, gelatin, and polyvinyl alcohol as well as
various surfactants. Examples of such surfactants include
polyoxyethylene sorbitan trioleate, polyoxyethylerle
sorbitol hexaoleate, polyoxyethylene sorbitol laurate, and
polyoxyethylene sorbitol oleate-laurate. When such non-
cationic emulsiflers are used, it is oten deslrabl0 to
separately add a cationic agent to the pulp slurry after
the addition to the latter of the emulsified sizing agent.
In preparing these emulsions with the use of an emulsi-
fier, the latter is usually first dispersed in water and
the sizing agent is then introduced along with vigorous
agitation. Alternatively, the emulsification techniques
described in U.S. Patent No. 4,040,900 may be employed.
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 150C for
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
sulfite, bleached and unbleached soda, neutral sulfite,
semi-chemical chemiground-wood, ground wood, and any
combination 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
s~
Ol -8-
industry. In addition, synthetic fibers of the viscose
rayon or regenerated cellulose type can also be used.
05 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 sul-
fate, and diatomaceous 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~ o the dry weight of the pulp in ~he Einished
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
higher concentration of sizing agent than paper which does
not. The same factors also apply in relation to the
amount of cationic agert which may be used in conjunction
with these sizing agents. The practitioner will be able
to use these materials in any concentration which is found
to be applicable to his specific operating conditions.
.However, under ordinary circumstances a range of from 0.5
to 2.0 parts by weight of cationic agent per 1.0 part of
sizing agent is usually adequate. It can be noted that
the cationic agent is present in a quantity of at least
0.025% of the dry weight of the pulp in the paper.
The alkenyl succinic anhydride compositions of
the present invention may also be used to impart water-
repellency to cellulosic fabrics. The water-repellent
compositions described above may be applied to the cloth
in aqueous emulsion~ similar to those used for paper
sizing. The emulsion may be sprayed onto the fabric or
~7~
~1 9
the fabric may be dipped into the emulsion in order to
distribute the derivative evenly throughout the fabric.
OS The impregnated fabric is then withdrawn from the solution
and air dried~ After air drying the cloth i9 then heated,
preferably to a temperature in excess of 100C, to effect
a curing of the impregnated agent within the cloth. 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 e~fect
the curing process. To be commercially practical the cur-
ing time should be as short as possible and ~enerally less
than one hour. At higher temperature~ 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 temperatures at which
fabrics begin to brown or become discolored. Using the
composition of the present invention, it is preferred to
- 20 impregnate the fabric with from about 0.7 to 2.5~ by
weight of the fabric of the alkenyl succinic anhydride.
The following examples are provided to
illustrate 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
This example describes the preparation of a
standard straight chain alkenyl succinic anhydride suit-
able for sizing applications.
The feed olefin was derived from cracking petro-
leum wax and originally contained about 88% straight chain
alpha olefin. It consisted of a mixture of homologs from
C15 to C20 containing about 18g C15, 19% C16, 18% C17,
18% C18, 15% Clg and 12~ C20~ This mixture was isomerized
using an acidic catalyst until the alpha olefin content
was reduced to 7~. The double bond had been moved to the
2-position and further internal positions.
01 --10-
The above straight chain internal olefin mixture
(3299, 1.35 moles) was heated with maleic anhydride (98g,
05 1.0 mole) in an autoclave for 3 1/4 hours at 230C~ Over
95~ of the maleic anhydride reacted with the olefin to
give an alkenyl succinic anhydride product. This crude
product was stripped of unreacted maleic anhydride and
olefin by heating up to 260C a-t 25mm Hg with nitrogen
I0 sparging over a 40-minute period~
The remaining alkenyl succinic anhydride3 wa~ a
straw-colored llguid with a pour point of about 5C which
remained fluid but formed some solids on standing over-
night at this temperature.
IS This product is very similar to normal commer-
ci~l straight chain alkenyl succinic anhydride. Xt glves
good paper sizing results in a variety of tests, such as
those described in U~S. Patent No. 4,040,900 ~Rs. 29,960).
Example 2
2~ An alkenyl succinic anhydride was made as
described in Example 1, except that tha carbon number
range of the feed olefin consisted of ~5~ C15r 30~, C16,
29% C17, and 15% C18. The alpha olefin content r~maining
after isomerization was 7%. The derived alkenyl succinic
anhydride was a clear liquid which did not produce solids
on standing overnight at 5C.
Exam~le 3
An alkenyl succinic anhydride was made from the
same straight chain alpha olefins as descrihed in
3U Example 1, except that the olefin isomerization step was
omitted. The alkenyl succinic anhydride product was a
solid, completely unsuitable for sizing by the normal
aqueous emulsion techniques.
Example 4
The alpha olefin feed used in Exampls 1 was
distilled to produce a lower boiling fraction which ~as
88~ C15 and 9% C16, with an average molecular waight of
212. An alkenyl succinic anhydride was made from this
olefin using the steps of Example 1 except that the
'10
5~
isomerization step was omitted. This alkenyl succinic
anhydride was a solid, unsuitable for sizing.
05 Example 5
An example of the composition of the present
invention was made by using the alkenyl succinic anhydride
of Example 4 as component A and a Cl6_l8 alkenyl succinic
anhydride as component B. The Cl6_l~ alpha olefin frac-
tion was in the bottoms from distilling out the ClS cut o~
Example 4~ This Cl6_l8 fraction contained about 34~ Cl6,
34% Cl7, and 27~ Cl8, with an averag0 molecular weight of
237. The Cl~_l8 raction waq isomerized to recluce the
alpha ole~in content to 7%~ and an alkenyl succinic anhy
dride was made a~ in Example l. The final alkenyl
succinic anhydride mixture contained 22.5% of component A
and 77.5~ of componént B. This composition was a clear
liquid at room temperature. It remained fluid but formed
some solids on standing overnight at 5C.
2~ Example 6
Another example of the composition of the
present invention was made as described in Example 5,
except that the Cl6_l8 olefin used to make the alkenyl
succinic anhydride of component B was isomerized more
completely before reactin~ with maleic anhydride. In
this case, instead of 7% alpha olefin rsmaining, only 2
alpha olefin remained after isomerizing. This Cl6_l8
olefin was reacted with maleic anhydride and the resulting
alkenyl succinic anhydride was mixed with the alkenyl
succinic anhydride of Example 4 in a 22.5/77,5 ratio as in
Example 5. This composition was a liquid at room
temperature and did not form any solids on standing
overnight at 5C.
Example 7
Paper sizing experiments and size effectiveness
evaluations were run using techniques described in U.S.
Patent No. 4,040,900 (Re. 29,960). For each alkenyl
succinic anhydride tested, eight results were obtained.
The alkenyl succinic anhydride was added to paper at two
different levels: 0.2~ and 0.4~, based on dry fiber
~ ~7S~
~1 -12-
weight~ A cationic starch adjuvant was employed at twotimes the alkenyl succinic anhydride level, in each
05 case. At both alkenyl succinic anhydride levels, tests
were also made with 0.5% added alum. The sized papers
were evaluated using both the Hercules size test ~80~
reflectance end point), and the potassium permanganate
test described in U.S. Patent No. 4,040,900.
For each alkenyl succinic anhydride, the times
to obtain each end-point were averaged to give tho results
shown in Table 1.
Tabl~ 1
15 Alkenyl Succinic Anhydride 'rime, in seconds,
to end-polnt
Example No. Carbon Ran~e (averaqe of 8 tests)
1 15-20 104
2 15-18 110
2U 15-18 121
6 15-18 165
The results of Table 1 demonstrate that the
alkenyl succinic anhydrides of the present invention,
namely Examples 5 and 6, give superior sizing effective-
ness compared to the known alkenyl succinic anhydride
compositions of Examples 1 and 2.
Example 8
A composition similar to those descrihed in
Examples 5 and 6 was made by blending 20~ of the alkenyl
succinic anhydride from Example 4 with 80% of an alkenyl
succinic anhydride derived from a branched olefin mixture
in the C15 to C20 range made by oligomerizing propylene.
This composition was a liquid at room temperature and did
not form any solids on standing overnight at 5C.
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