CROSSLINKING CELLULOSE ACETATE

IN SOLUTION WITH CERTAIN METAL

CHELATING AGENTS
JOHN E . KIEFER AND GEORGE P. TOUEY
Research Laboratories, Tennessee Eastman Co.. Division of Eastman Kodak Co., Kingsport, Tenn.

Unique crosslinking agents for increasing the viscosity of cellulose acetate solutions were investigated. The
purpose of modifying the solutions was to facilitate the spinning of extremely fine denier fibers. Several
aluminum, titanium, and zirconium coordination complexes were prepared. Low concentrations of the co-
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ordination complexes, or chelates, had a pronounced effect on the viscosity of the solutions, but the physical
properties of the cellulose acetate remained unchanged. The crosslinking agents included the aluminum,
titanium, and zirconium chelates of dihydroxy, diketo, and hydroxy keto compounds, and keto carboxylic
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acid esters. One of these, the titanium chelate of ethyl acetoacetate, was studied in detail as a crosslinking
agent for cellulose acetate solutions. Some of the variables encountered were investigated. The modi-
fied solutions of cellulose acetate were stable to heat and storage. They were spun into fibers of 0.75
to 1.0 denier per filament.

^pHE possibility of modifying the viscosity of cellulose acetate Experimental

* solutions by means of crosslinking agents was studied to
develop spinning solutions which would produce fibers of
extremely fine denier.
When cellulose acetate is spun from acetone by the usual dry
spinning process, the denier of the fiber is dependent on the size
of the spinneret orifice, the spinning draft, and the solids
concentration of the spinning solution. The relationship of
these factors to the fiber denier is illustrated by the following
equation:
Denier/filament =
A simple screening test was used to determine the effect of
crosslinking agents on the viscosity of a cellulose acetate solu-
tion. Cellulose acetate with an acetyl content of approxi-
mately 40% was dissolved in acetone. The solution contained
1.5% water, which was included in this formula because it is
usually present in cellulose acetate spinning dopes. The solu-
tion, which contained 20% solids, was divided into 400-gram
portions. One portion was diluted with 25 grams of acetone
and used as the control. To each of the remaining 400-gram
portions was added 4 grams of the crosslinking agent being
tested dissolved in 25 grams of acetone. Each solution was
mixed for 30 minutes, and then its viscosity was measured with

a Brookfield viscometer. The following is a representative list

K{dope density) (orifice diam.)2(solids concn., %)
spinning draft
K is a constant, and spinning draft is defined as the linear speed
of yarn take-up divided by the linear extrusion speed of the
spinning solution. Cellulose acetate cannot be drafted ex-
tensively under normal spinning conditions, and therefore this
variable is not very useful in controlling fiber size. The orifice
diameter is the variable ordinarily used to control denier size;
however, practical considerations put a lower limit on the
size of orifice which can be used successfully. Since it is not
desirable to change the spinning solvent, the dope density
cannot be varied to control the denier size. Lowering the dope
solids concentration appears to be the most effective method
for spinning fine denier fibers. However, when solutions of
low solids concentration are spun, the solution viscosity is too
low, and the extruded solution cannot be pulled into a fiber.
This investigation was limited to the use of crosslinking agents
as a means of modifying the viscosity of a cellulose acetate
solution of low solids concentration. A variety of crosslinking
agents was tested for this purpose. The most effective cross-
linking agents were organic chelates of aluminum, titanium,
and zirconium. One of these products, a titanium chelate of
ethyl acetoacetate (EAAT), was studied in some detail. Solu-
tions containing this additive were spun and the properties
of the fibers measured.
of the crosslinking agents tested:
Formaldehyde + 5% oxalic acid
Glyoxal + 5% oxalic acid
2-Methyl-jft-phenylene diisocyanate
/j-Bis(2,3-epoxypropoxy)benzene
Isopropyl aluminum)III)
Butyl titanate(IV)
2-Ethylhexyl titanate(IV)
Octadecyl titanate(lV)
The aldehydes, diisocyanates, and diepoxy compounds had
noeffect on the viscosity of the solutions. It was thought that
the water in the dopes prevented the cross linking agents from
reacting with the free hydroxy groups of the cellulose acetate.
Therefore, the experiments were repeated with distilled acetone
and dry cellulose acetate. Again, no increase in viscosity was
observed.
Titanium esters and acylates and aluminum esters were also
unsatisfactory. The esters decomposed when dissolved in the
acetone and their corresponding oxides precipitated. When
the esters were added to the cellulose acetate solutions, they
reacted too rapidly, and highly crosslinked gel particles formed
in the dopes. No increase in viscosity was observed. The
titanium acylates are reported to be more stable than the
esters; however, they had no effect on the viscosity of the
cellulose acetate solution. These esters could probably be used
as viscosity modifiers if the solutions were anhydrous, but this

VOL. 4 NO. 4 DECEMBER 1 965 253

would not be practical, since both acetone and cellulose
acetate absorb water from the atmosphere under normal
humidity conditions.
The following structural formulas show some titanium
chelates which were reported to be crosslinking agents for
cellulose esters. Schmidt (7) claimed that when these com-
plexes were added to certain lacquer formulations containing
a cellulose ester, no immediate viscosity change occurred; but
when the solution was cast into a film and the solvent was
evaporated, the cellulose ester crosslinked, which caused the
film to have a higher softening temperature. We found that
when these chelates were dissolved in acetone and added to a
cellulose acetate solution, the viscosity of the solution increased
rapidly for 20 to 30 minutes and then no further change took Figure 1. Effect of concentration of titanium
place. As little as 0.2% of the chelate, based on the weight of chelate of ethyl acetoacetate on viscosity of
cellulose acetate, increased the viscosity of the solution three- cellulose acetate solutions
fold. The modified solutions were smooth, contained no gel
particles, and were easily filtered. 2 moles of the ethyl acetoacetate per mole of isopropyl
C2Hs
i titanate(IV) was used, the complex was still an effective
modifier, but the crosslinking reaction was more rapid and
CH3(CH2)2CHCHCH2 therefore more difficult to control. The use of more than 2
I
[ moles of ethyl acetoacetate per mole of the titanium ester did
HO JO not produce a more effective crosslinking agent.
I X
I
y/
CH3(CH2)30-yTi—0(CH2)3CH3
o o
' OH
i CH3CCH2COC2H5
CH2CHCH(CH2)2CH3 Ti[OCH(CH3)2]4 + \\
-

CH3C=CHCOC2H5
c2h5
OH O
ch3c=chcoc2h6
CH3C=CHCOC2H5
O P O yO
(CH3)2CHO—Ti—OCH(CH3)2
(CH3)2CHO—Ti—OCH(CH3)2 + 2(CH3) 2choh

!!
o' o
||
C2H5OCCH=CCH3 |

C2H5OCCH=CCH3
ch3c=chcch3
¡ Ü Since the titanium chelates were so effective as viscosity
modifiers, the following chelates of aluminum and zirconium
Xo were prepared and evaluated. They were prepared by a
(CH„) 2CHO—Ti—OCH(CH3) 2 method similar to that used to make the titanium chelates.
z
z
1

| For example, 1 mole of 2,4-pentanedione was mixed with 1

o' o mole of aluminum triisopropoxide, and 1 mole of isopropyl
ch3cch=cch3
The titanium chelate of 2-ethyl-l,3-hexanediol was obtained
from E. I. du Pont de Nemours & Co., Inc. The others were
prepared in our laboratory. The following equation shows
the reaction involved in preparing one of the chelates. Two
moles of ethyl acetoacetate were mixed with 1 mole of isopropyl
titanate(IV), and 2 moles of isopropyl alcohol were removed by
distillation. EAAT prepared in this manner was an amber
liquid which was immiscible with water. Actually it was not
necessary to remove the alcohol from the reaction mixture.
When ethyl acetoacetate was mixed with the isopropyl titanate-
(IV), the chelate formed was an effective modifier, regardless
of whether or not the alcohol was present. However, it was
desirable to remove the alcohol, since, if not removed, it
complicated recovery of the spinning solvent. When less than
alcohol was removed by distillation to obtain the aluminum
chelate of 2,4-pentanedione. Although some of the aluminum
and zirconium chelates were comparable to the titanium
chelates in terms of their ability to increase the viscosity of
cellulose acetate solutions, in general they had no advantage
over the corresponding titanium compounds. Therefore, the
remainder of the work consisted of a more thorough study of
dopes modified with one type of chelating agent. EAAT,
prepared from 1 mole of isopropyl ti tanate (IV) and 2 moles of
ethyl acetoacetate, was chosen for this evaluation, since it was
one of the best chelates tested. Cellulose acetate spinning
dopes modified with this chelate were studied to determine the
effects of: the crosslinking agent concentration on the dope
viscosity, heat and storage on the crosslinked dope, tempera-
ture on the crosslinked dope, and water in the dope on the
efficiency of the crosslinking agent.

254 l&EC PRODUCT RESEARCH AND DEVELOPMENT

 CH,C=CHCOC2Hs

o p
XA1"
(CH3)2CHO// \)CH(CH3)2

ch3c=chcch3
l II

°\V -'°
TEMPERATURE, °C.
(CH3)2CHOv/ XOCH(CH3)2 Figure 2. Effect of temperature on viscosity of
crosslinked cellulose acetate solution

CH3C=CHCOC2H5

°\
(CH3) 2CHO—ZÍ—OCH (CH3) 2
^
o'' Xo
I! I
il
C2H5OCCH =
CCH3

1 illustrates the effect of EAAT concentration on the

Figure
viscosity of cellulose acetate solutions. A very small amount
of the crosslinking agent added to the cellulose acetate solution
produced a remarkable increase in its viscosity—for example,
0.1% of the additive, based on the weight of cellulose acetate,
increased the viscosity of the system by 50%, 0.2% increased Figure 3. Effect of amount of water on viscosity
of cellulose acetate solutions
it by 300%, and 0.3% increased it by 600%. The solution
contained 20% cellulose acetate with an acetyl content of
40%. The solvent was acetone and the dope contained 1.5%
water. The large increases in viscosity are believed to be due acetone, the viscosity of the redissolved crosslinked ester was
to the crosslinking of the cellulose acetate. One possible 300% higher than that of the uncrosslinked starting material.
crosslinking reaction is: Experimental data also showed the crosslinked solutions to
be stable to heat and storage, which indicates that they can be
CH3C=CHCOC2H5 used under any of the conditions normally encountered in
I II spinning. Crosslinked solutions were heated at 50° C. for
o o 2 hours, then stored for 3 months at 30° C. without any sig-

\/
(CH3) 2CHO—Ti—OCH(CH3) 2 + 2 HOCell
nificant change in viscosity.
In Figure 2, the viscosity-temperature relationship of a
crosslinked solution is compared with that of the unmodified
o o solution. The solution represented by the broken line con-
tained 20% cellulose acetate and 0.2% EAAT, based on the
C2H5OCCH=CCH3 weight of cellulose acetate. The solid line represents a cellu-
lose solution which contained 28% cellulose acetate. The
ch3c=chcoc2h5 viscosity-temperature curve for the modified solution has a
greater slope than that for the unmodified solution. Therefore,
Q O when the amount of chelate required to obtain the desired
viscosity increase is calculated, the temperature at which the
CellO—Ti—OCell + 2 (CH3)2CHOH dope will be used must be taken into consideration.
/ \O The amount of water in the modified solutions also produced
very marked effects on viscosity. Solutions with varying
amounts of water were modified with 0.2% EAAT, based on
C2H5OCCH=CCH3 the weight of the cellulose acetate. The results are shown
in Figure 3. The solutions contained 20% cellulose acetate.
Although we are not sure that this is the reaction which takes W a ter was added to the dopes, then an acetone solution of the
place, we know that the crosslink is permanent. For example, chelate was added. It is obvious from these data that excess
a crosslinked solution containing 20% cellulose acetate was water retards the reactivity of the crosslinking agent. How-
poured onto a glass plate and the acetone was removed by ever, when 2% water was added to a solution in which the
evaporation. The inherent viscosity (measured on a 0.25% cellulose acetate had already been crosslinked with EAAT,
solution in dichloromethane at 28° C.) of the dried material no significant change in viscosity was noted.
was only 9% higher than that of the uncrosslinked starting To determine if these crosslinked solutions could be spun by
material. Flowever, when the dried ester was redissolved in using normal spinning techniques, a typical spinning solution

VOL. 4 NO. 4 DECEMBER 1 965 255

 finer than those obtained from the unmodified solutions. As
Table I. Effects of Chelate Concentration on Fiber Properties expected, the solutions containing the lower amounts of dis-
Tensile Properties solved solids produced the finer fibers.
Solids Stick
EAATf Concn..
C7
Denier / Elong., temp.,
0 Conclusions
/C ;e filament O./ denier % c.
0 28 1.6 1.30 30 230
Increasing the viscosity of cellulose acetate solutions by
0.1 25 1.3 1.24 31 224
0.2 20 0.9 1.34 27 232
means of certain crosslinking agents offers a promising method
0.25 15 0.7 1 .22 29 234 for spinning fine denier fibers. Several titanium, aluminum,
“
Concentration of ethyl acetoacetate titanium chelate, based on weight of and zirconium chelates were found to be excellent crosslinking
cellulose acetate.
agents for this purpose. The EAAT was studied in detail.
The addition of only 0.2% of this compound, based on the
weight of the cellulose acetate, to a spinning solution resulted
in a threefold increase in viscosity. The modified solution
containing 28% cellulose acetate was prepared and divided was stable to heat and storage conditions normally encountered
into four portions. Increasing amounts of EAAT dissolved in spinning cellulose acetate. Yarns of very fine denier were
in acetone were added to three of the solutions. Enough spun from the modified solutions.
acetone was added to each of the modified solutions to make
them all have approximately the same viscosity. The amounts Literature Cited
of EAAT and solids present in the solutions are shown in
(1) Schmidt. F. (to Farbenfabriken Bayer. A. G.), U. S. Patent
Table I. The solutions were spun under identical conditions 2,680,108 (1954).
by using a conventional acetate spinning cabinet. The data Received for review March 19, 1965
in the table indicate that the solution modifier has little or no Accepted September 22, 1965
effect on the physical properties of the fiber. However, the Division of Cellulose, Wood, and Fiber Chemistry, 147th Meeting,
deniers of the fibers from the modified solutions were much ACS, Philadelphia, Pa., April 1964.

EPOXIDIZED CELLULOSE ESTERS

MARTIN E , ROWLEY AND GORDON D . HIATT
Cellulose Technology Division, Eastman Kodak Co., Rochester, N. Y.

Unsaturated cellulose mixed esters were prepared, then treated with peracids to yield epoxidized cellulose
esters that retained the solubility characteristics of the original esters. Conversion of the double bond to
the oxirane ring ranged from 2 to 80%; the products contained 0.02 to 0.20 equivalent of oxirane oxygen
1

per 100 grams. m-Chloroperbenzoic acid was more efficient than peracetic acid in the epoxidation of
cellulose acetate crotonate. Epoxidized cellulose acetate 10-undecenoate showed good properties for
a wood lacquer.

^pHE object of this investigation was to prepare cellulose
* esters containing potentially reactive groups which could
be activated at the desired time by heat or a suitable catalyst.
Specifically, unsaturated cellulose esters were converted to
epoxides. Peras (9) has described the oxygenation of an allyl-
cellulose with various reagents to produce derivatives con-
taining up to about 0.1 mole of active oxygen per 100 grams of
product; these oxygenated cellulose ethers were insoluble in
organic solvents. The epoxidized cellulose mixed esters
described in this article were soluble in organic solvents and
readily insolubilized when used as a coating material.
Methods
Table I lists the unsaturated cellulose esters that
epoxidized.
Peracetic Acid Epoxidation. Peracetic acid was used to
convert the unsaturated esters to the epoxides by two methods.
In the first method, the peracid was formed in the presence
of the unsaturated cellulose ester, using hydrogen peroxide,
acetic acid, and an acidic ion exchange resin. This method is
essentially that described by Greenspan and Gall (2), but
with some modification since we were dealing with solid
polymeric esters that required larger amounts of solvent.
In the second method, known concentrations of peracetic
acid in acetic acid (or mixtures of acetic acid and ethyl ace-
tate) were used. The peracid solutions were prepared in a
manner similar to that described in Method I, then added to
the unsaturated cellulose ester. Typical examples are cited
for the two methods.
Method I. To 5 grams of acetic acid and 20 grams of ethyl
acetate was added 15 grams (0.04 mole of unsaturated sub-
stituent) of a cellulose butyrate 10-undecenoate containing
43.3% 10-undecenoyl. After the ester had completely dis-
solved, 1.5 grams of Amberlite CG-120 resin (acid form, wet
with an equal weight of acetic acid) was added and the flask
were placed in a 70° C. bath. To the continuously stirred mixture
was slowly added 4 grams (0.07 mole) of 59% hydrogen per-
oxide (EMC Corp.). Stirring was continued for 4 hours to
complete the epoxidation. The solution was diluted with
acetone and filtered to remove the resin catalyst. The product
was isolated by precipitating into distilled water, washed with a
50: 50 mixture of methanol-water, then dried at room tempera-
ture under vacuum. Analysis showed 0.2 equivalent of oxirane
oxygen per 100 grams of product (about 80% conversion of the
double bond).

256 I & E C PRODUCT RESEARCH AND DEVELOPMENT