U.S. patent number 3,884,631 [Application Number 05/335,861] was granted by the patent office on 1975-05-20 for preparation of cellulose n,n-dimethylformimidate chloride in textile form, and conversion to halogenodeoxycelluloses and cellulose formate.
This patent grant is currently assigned to The United States of America as represented by the Secretary of. Invention is credited to Donald J. Daigle, Tyron L. Vigo, Clark M. Welch.
United States Patent |
3,884,631 |
Vigo , et al. |
May 20, 1975 |
PREPARATION OF CELLULOSE N,N-DIMETHYLFORMIMIDATE CHLORIDE IN
TEXTILE FORM, AND CONVERSION TO HALOGENODEOXYCELLULOSES AND
CELLULOSE FORMATE
Abstract
The preparation in textile form of a new, flame resistant,
chemically reactive cellulose derivative, cellulose
N,N-dimethylformimidate chloride, is accomplished by reacting
chlorodimethylformiminium chloride in N,N-dimethylformamide at
20.degree.-30.degree.C with cellulosic yarn or fabric preswollen in
N,N-dimethylformamide. At a reaction temperature of
50.degree.-110.degree.C, the product is chlorodeoxycellulose.
Conversion of cellulose N,N-dimethylformimidate chloride to
iododeoxycellulose is accomplished by reaction of the former with
an alkali metal iodide at 60.degree.-150.degree.C in
N,N-dimethylformamide. Conversion of the cellulose
N,N-dimethylformimidate chloride to cellulose formate occurs by
contact with water at 20.degree.-30.degree.C. The
chlorodeoxycellulose and iododeoxycellulose possess rot resistance
and flame resistance. Cellulose formate has altered dyeability.
Inventors: |
Vigo; Tyron L. (Kenner, LA),
Daigle; Donald J. (New Orleans, LA), Welch; Clark M.
(Metairie, LA) |
Assignee: |
The United States of America as
represented by the Secretary of (Washington, DC)
|
Family
ID: |
23313540 |
Appl.
No.: |
05/335,861 |
Filed: |
February 26, 1973 |
Current U.S.
Class: |
8/194;
252/608 |
Current CPC
Class: |
D06M
13/322 (20130101); D06P 5/22 (20130101); D06P
3/004 (20130101) |
Current International
Class: |
D06P
3/00 (20060101); D06P 5/22 (20060101); D06M
13/322 (20060101); D06M 13/00 (20060101); D06p
003/00 () |
Field of
Search: |
;8/194 ;252/8.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Attorney, Agent or Firm: Silverstein; M. Howard Hensley; Max
D.
Government Interests
A non-exclusive, irrevocable, royalty-free license in the invention
herein described, throughout the world for all purposes of the
United States Government, with the power to grant sublicenses for
such purposes, is hereby granted to the Government of the United
States of America.
Claims
We claim:
1. As a textile material, fibrous cellulose N,N-dimethylformimidate
chloride possessing the structure
Cell--O--CH=N.sup.+(CH.sub.3).sub.2 Cl.sup.-, wherein Cell
represents a portion of a cellulose molecular chain, said material
comprising a chlorine content of from 0.5 to 6 percent as well as a
nitrogen content of from 0.2 to 2.4 percent, the ratio of chlorine
atoms to nitrogen atoms being 1:1 and the formimidate groups being
characterized by rapid hydrolysis to formate groups on contact with
water, said textile material also being characterized by increased
flame resistance relative to the original untreated textile.
2. A process for preparing a fibrous cellulose
N,N-dimethylformimidate chloride in textile form which process
comprises:
a. immersing air-equilibrated fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight of chlorodimethylformiminium chloride in
N,N-dimethylformamide at a temperature of from 20.degree.C to
30.degree.C for about from 3 minutes to 180 minutes, in order to
react the cellulose with the chlorodimethylformiminium
chloride,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess chlorodimethylformiminium chloride,
e. washing the cellulosic textile with an inert, volatile, aprotic
solvent miscible with N,N-dimethylformamide, and
f. drying the cellulosic textile.
3. The process of claim 2 where the textile form is a yarn.
4. The process of claim 2 where the textile form is a fabric.
5. The process of claim 2 where the inert, volatile, aprotic
solvent is benzene.
6. A process for preparing a fibrous iododeoxycellulose in textile
form, which process comprises:
a. immersing air-equilibrated fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight of chlorodimethylformiminium chloride in
N,N-dimethylformamide at a temperature of from 20.degree.C to
30.degree.C for about from 3 minutes to 180 minutes, in order to
react the cellulose with the chlorodimethylformiminium
chloride,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess chlorodimethylformiminium chloride,
e. immersing the cellulosic textile in a solution of an alkali
metal iodide in N,N-dimethylformamide for a period of from 0.25
hour to 2 hours at a temperature of about from 60.degree.C to
150.degree.C, the concentration of the alkali metal iodide being
about from 5 to 25 percent by weight in the N,N-dimethylformamide,
in order to react the cellulose N,N-dimethylformimidate chloride
with the alkali metal iodide,
f. washing the cellulosic textile from 20.degree.C to 30.degree.C
with N,N-dimethylformamide to remove excess alkali metal
iodide,
g. washing the cellulosic textile with ice water and then with
water at 20.degree.C to 30.degree.C to remove N,N-dimethylformamide
and further traces of alkali metal iodide, and
h. drying the cellulosic textile.
7. The process of claim 6 where the textile form is a yarn.
8. The process of claim 6 where the textile form is a fabric.
9. The process of claim 6 where the alkali metal iodide is sodium
iodide.
10. The process of claim 6 where the alkali metal iodide is
potassium iodide.
11. A process for preparing a fibrous cellulose formate in textile
form, which process comprises:
a. immersing air-equilibrated fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight of chlorodimethylformiminium chloride in
N,N-dimethylformamide at a temperature of from 20.degree.C to
30.degree.C for about from 3 minutes to 180 minutes, in order to
react the cellulose with the chlorodimethylformiminium
chloride,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess chlorodimethylformiminium chloride,
e. washing the cellulosic textile with ice water and then with
water at 20.degree. to 30.degree.C, for from 5 minutes to 60
minutes, to hydrolyze the cellulose N,N-dimethylformimidate
chloride to cellulose formate, and
f. drying the cellulosic textile.
12. A process for preparing a fibrous chlorodeoxycellulose in
textile form, which process comprises:
a. immersing air-equilibrated fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight of chlorodimethylformiminium chloride in
N,N-dimethylformamide at a temperature of from 50.degree. to
110.degree.C for about 0.25 hour to 2 hours in order to react the
cellulose with the chlorodimethylformiminium chloride,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess chlorodimethylformiminium chloride,
e. washing the cellulosic textile with ice water and then with
water at 20.degree.C to 30.degree.C to remove N,N-dimethylformamide
and further traces of chlorodimethylformiminium chloride,
f. drying the cellulosic textile.
13. The process of claim 12 where the textile form is a yarn.
14. The process of claim 12 where the textile form is a fabric.
Description
GENERAL FEATURES
This invention relates to a new cellulose derivative, its
preparation in yarn and fabric form, and its conversion to other
cellulose derivatives having useful textile properties. More
specifically, the invention relates to the preparation, properties
and reactions of cellulose N,N-dimethylformimidate chloride, which
possesses the chemical structure ##SPC1##
Wherein Cell represents a portion of a cellulose molecular chain.
Alternative names for this cellulose derivative are
(celluloseoxymethylene) dimethylammonium chloride and cellulose
N-methylformimidate methochloride. Also embodied in the present
invention is the conversion of the above specified cellulose
N,N-dimethylformimidate chloride to chlorodeoxycelluloses,
iododeoxycelluloses, cellulose formate, and other useful cellulose
derivatives in textile form.
OBJECTS OF THE INVENTION
The main object of the present invention is the preparation of a
new and highly reactive cellulose derivative, cellulose
N,N-dimethylformimidate chloride, having utility as an intermediate
in the preparation of a variety of other cellulose derivatives.
A second object is to provide a means of reducing the flammability
of cellulosic textiles.
A third object of the present invention is to provide a means of
rendering cellulosic textiles resistant to rotting by
microorganisms.
A fourth object is to provide a means of introducing halogen
substituents into cellulose to yield chlorodeoxycellulose and
iododeoxycellulose in textile form, while retaining the fiber
structure, whiteness, and most of the tensile strength of the
original cellulose.
A fifth object is to provide a means of introducing halogen
subtituents into cellulose without prior application of
alkali-swelling or solvent-exchange pretreatments to the cellulose.
Other objects of the present invention will become evident in the
description which follows.
COMPARISONS WITH PRIOR ART
The prior literature contains several studies on the preparation of
chlorodeoxycellulose. Boehm, J. Organic Chem. 23, 1716-1720 (1958),
added thionyl chloride to a mixture of alkaliswollen,
solvent-exchanged cotton linters and pyridine. A strong degrading
action on the cellulose was stated to occur as evidenced by the low
viscosity of solutions of the product in cuprammonium hydroxide.
The product also showed a dark discoloration.
Polyakov and Rogovin, J. Polymer Sci. (U.S.S.R.) 4 (4) 610-618
(1963), prepared chlorodeoxycellulose by reacting alkali-swollen,
solvent-exchanged cotton linters at 60.degree.-98.degree.C with
thionyl chloride in N,N-dimethylformamide. A yellow discoloration
was noted in the product. The swollen linters required for this
process were prepared by steeping the cotton in 18 percent aqueous
sodium hydroxide, followed by washing with water, methanol, and
then benzene. Subsequently, Vigo and Welch, Textile Research J. 40,
109-115 (1970), found that in the treatment of cotton yarn by the
process of Polyakov and Rogovin, yellowing and tendering could be
avoided by the use of lower reaction temperatures
(25.degree.-30.degree.C), but no method was found of avoiding the
laborious and expensive alkali-swelling and solvent-exchange steps
required to activate the cotton cellulose.
In a subsequent patent application (Ser. No. 109,964), now U.S.
Patent 3,698,857, it was disclosed by Vigo, Margavio, and Welch
that the preswelling of cellulose, as required in the Polyakov and
Rogovin process, can be carried out with water in place of aqueous
alkali, if only a moderate chlorine content in the product is
needed, but this process still necessitates solvent-exchange
treatments to displace the water in the cellulose with an aprotic
solvent inert to thionyl chloride. Moreover, the chlorine content
obtainable in the product is less than 1 percent by this
method.
The present invention makes it possible for the first time to
prepare chlorodeoxycellulose in yarn and fabric form without prior
application of alkali- or water-swelling treatments to the
cellulose. The processes to be disclosed eliminate the need for
solvent-exchange treatments prior to reaction. Moreover, the
present invention permits the use of elevated reaction temperatures
without cellulose discoloration or tendering, thus permitting
higher chlorine contents to be introduced into the cellulose than
are possible in processes conducted at room temperature. The
processes of this invention are applicable to celluloses derived
from cotton and wood pulp, which celluloses may be native,
mercerized or regenerated, and which may be in the form of loose
fibers, sliver, yarn or fabric.
DESCRIPTION OF THE INVENTION
The above advantages of the present invention are unexpectedly
obtained by use of chlorodimethylformiminium chloride in place of
thionyl chloride as the reagent employed to introduce the desired
substituents into the cellulose. Chlorodimethylformiminium
chloride, hereafter referred to as DMFCl.sub.2 for brevity, is
readily prepared from thionyl chloride and N,N-dimethylformamide by
the method of Bosshard et al., Helv. Chim. Acta 42, 1653-1658
(1959), and is known to possess the structure
ClCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.-.
DMFCl.sub.2 undergoes two types of reaction with cellulose. The
low-temperature reaction, conducted at 20.degree.-30.degree.C,
yields cellulose N,N-dimethylformimidate chloride:
1. Cell--OH + ClCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.- .fwdarw. HCl +
Cell-OCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.-. The high temperature
reaction of DMFCl.sub.2 with cellulose is conducted at
50.degree.-110.degree.C, and produces mainly
chlorodeoxycellulose:
2. Cell--OH + ClCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.- .fwdarw. HCl +
Cell-Cl + O=CH-N(CH.sub.3).sub.2.
Thus the means are now available for the direct preparation of
cellulose N,N-dimethylformimidate chloride and also of
chlorodeoxycellulose.
Moreover, the cellulose N,N-dimethylformimidate chloride is highly
reactive, and can be converted to iododeoxycellulose by treatment
with an alkali metal iodide in N,N-dimethylformamide at
60.degree.-150.degree.C, as follows:
3. Cell--OCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.- + KI .fwdarw. Cell-I
+ KCl + O=CH-N(CH.sub.3).sub.2.
Alternatively, the cellulose N,N-dimethylformimidate chloride can
be reacted with water to yield cellulose formate:
4. Cell--OCH=N.sup.+(CH.sub.3).sub.2 Cl.sup.- + H.sub.2 O --
Cell-OCH=O + (CH.sub.3).sub.2 N.sup.+H.sub.2 Cl.sup.-.
Not only are chlorodeoxycellulose, iododeoxycellulose, and
cellulose formate readily obtainable by the processes of this
invention, but mixed derivatives of cellulose containing iodo and
formyl substituents, chloro and formyl substituents, iodo and
chloro substituents, or iodo, chloro, and formyl substituents on
the same cellulose chains, are readily prepared by the proper
sequence of treatments and choice of reaction temperatures and
times.
Preparation of Cellulose N,N-Dimethylformimidate Chloride
The preparation of cellulose N,N-dimethylformimidate chloride by
the present invention comprises the following steps:
a. immersing air-equilibrated, fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide by wringing,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight DMFCl.sub.2 in N,N-dimethylformamide at a
temperature of from 20.degree.C to 30.degree.C for about from 3
minutes to 180 minutes, in order to react the cellulose with the
DMFCl.sub.2,
d. washing the cellulosic textile with N,N,dimethylformamide to
remove excess DMFCl.sub.2,
e. washing the cellulosic textile with an inert, volatile, aprotic
solvent miscible with N,N-dimethylformamide, and
f. drying the celulosic textile.
Immersing the cellulose in N,N-dimethylformamide prior to treatment
with DMFCl.sub.2 solution, as specified in step (a) above, is
critical to the process, in that this step swells the cellulose
fibers and greatly increases the rate of subsequent reaction of the
cellulose with the DMFCl.sub.2. The magnitude of this effect is
surprising inasmuch as N,N-dimethylformamide is also present during
the reaction and would be expected to exert the same effect then.
The cellulose to be used in this process should be at equilibrium
with the atmosphere at ordinary humidity so that the moisture
content of the cellulose is of the order of 2-12 percent. The
presence of this moisture renders the fibers much more accessible
to swelling by N,N-dimethylformamide and to the subsequent reaction
with DMFCl.sub.2. The cellulose should not be subjected to any
deswelling treatment such as oven-drying, prior to immersion in the
N,N-dimethyl formamide.
Removing excess N,N-dimethylformamide, in step (b) above may be
accomplished by ordinary mechanical methods of wringing, such as
passing the fabric through squeeze rolls, centrifugation, draining,
or by pressing the cellulose against a filter.
The reaction of the cellulosic textile with DMFCl.sub.2, as
specified in step (c) above, is preferably carried out in
N,N-dimethylformamide as the reaction medium since this solvent
maintains the cellulose in a swollen state, and also the
DMFCl.sub.2 has considerable solubility in this medium. The weight
ratio of DMFCl.sub.2 to cellulose which may be used can be varied
over a wide range. The most practical ratio to use depends to some
extent on whether the cellulose is in the form of loose fibers,
sliver, yarn, or fabric, since the wet pickup of DMFCl.sub.2
-dimethylformamide mixture of the cellulose varies with the form of
cellulose being treated. The preferred ratio also varies with the
degree of cellulose substitution desired, but usually is in excess
of 1 part by weight of DMFCl.sub.2 to 4 parts by weight of
cellulose. The ratio of DMFCl.sub.2 to N,N-dimethylformamide also
may be varied considerably but below a weight ratio of 0.03 of
DMFCl.sub.2 / solvent, the reaction with cellulose becomes very
slow, and above a weight ratio of 0.15 the solubility limit of
DMFCl.sub.2 is exceeded to the extent that little practical benefit
results from still higher ratios.
By adjusting the DMFCl.sub.2 concentration and the reaction time,
the degree of cellulose substitution obtained can be varied
considerably so that the chlorine content of the product is in the
range of about 0.5 to 6 percent and the nitrogen content is in the
range of 0.2 to 2.4 percent.
The washing step (d) listed above is preferably carried out using
N,N-dimethylformamide as the solvent to remove excess DMFCl.sub.2,
and must be done under anhydrous conditions. The presence of water
causes immediate hydrolysis of cellulose N,N-dimethylformimidate
chloride to yield cellulose formate.
The washing step (e) above is preferred in order to remove
N,N-dimethylformamide, since the latter solvent is high boiling and
is difficult to remove by heat drying. Solvents suitable for this
washing are those solvents whose boiling points are less than
100.degree.C at 1 atmosphere pressure, are miscible with
N,N-dimethylformamide, and are inert to DMFCl.sub.2. Examples of
suitable solvents are benzene, carbon tetrachloride, chloroform,
and ethylene chloride, with benzene being preferred because of its
low cost.
The drying step, listed as (f) above, removes the solvent used in
washing step (e) and may be carried out at any temperature below
about 50.degree.C. At higher temperatures there is some tendency
for chlorodeoxycellulose formation. Drying may be conducted with a
stream of dry air, by vacuum, or by mild heating. The washing step
(e) and drying step (f) may be omitted if the cellulose
N,N-dimethylformimidate chloride is to be converted immediately to
other cellulose derivatives.
PREPARATION OF IODODEOXYCELLULOSE
The preparation of iododeoxycellulose by the present invention
comprises the following steps:
a. immersing air-equilibrated, fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight DMFCl.sub.2 in N,N-dimethylformamide at a
temperature of from 20.degree.C to 30.degree.C for about from 3
minutes to 180 minutes in order to react the cellulose with the
DMFCl.sub.2,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess DMFCl.sub.2,
e. immersing the cellulosic textile in a solution of an alkali
metal iodide in N,N-dimethylformamide for a period of from 0.25
hour to 2 hours at a temperature of about from 60.degree.C to
150.degree.C, the concentration of the alkali metal iodide being
about from 5 to 25 percent by weight in the N,N-dimethylformamide
in order to react the cellulose N,N-dimethylformimidate chloride
with the alkali metal iodide,
f. washing the cellulosic textile at 20.degree.C to 30.degree.C
with N,N-dimethylformamide to remove excess alkali metal iodide and
traces of DMFCl.sub.2,
g. washing the cellulosic textile with ice water and then with
water at 20.degree. to 30.degree.C to remove N,N-dimethylformamide
and further traces of alkali iodide, and
h. drying the cellulosic textile.
Steps (a) through (d) are the same as for the preparation of
cellulose N,N-dimethylformimidate chloride. Step (e), the reaction
of this derivative with an alkali metal iodide, is preferably
carried out in N,N-dimethylformamide as the reaction medium since
several of the alkali iodides have high solubility in this medium
which also maintains the cellulosic fibers in a swollen and
accessible condition. Of the alkali metal iodides, sodium iodide
and potassium iodide are preferred as having the optimum compromise
between low cost, high ionic character and reactivity and high
solubility in N,N-dimethylformamide. Potassium iodide is
particularly preferred in these respects.
Steps (f) and (g) remove unreacted iodide and DMFCl.sub.2. If the
DMFCl.sub.2 used for step (c) contains some thionyl chloride as an
impurity, the iododeoxycellulose formed will also have present
appreciable amounts of sulfur-containing cellulose derivatives such
as cellulose sulfite. The sulfites may be decomposed by washing the
product with 2-5 percent aqueous ammonia followed by water washing.
The ammonia wash also removes any formate ester groups present.
The drying step (h) may be carried out at any temperature below
90.degree.C but preferably at 20.degree.C to 40.degree.C since
organic iodides such as iododeoxycellulose tend to undergo
dehydrohalogenation and other side reactions with unusual ease.
PREPARATION OF CELLULOSE FORMATE
The preparation of cellulose formate by the present invention
comprises the following steps:
a. immersing air-equilibrated, fibrous cellulose in textile form in
N,N-dimethylformamide at a temperature of about from 20.degree.C to
30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight DMFCl.sub.2 in N,N-dimethylformamide at a
temperature of from 20.degree.C to 30.degree.C for about 3 minutes
to 180 minutes, in order to react the cellulose with the
DMFCl.sub.2,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess DMFCl.sub.2,
e. washing the cellulosic textile with ice water and then with
water at 20.degree.C to 30.degree.C for 5 minutes to 60 minutes to
hydrolyze the cellulose N,N-dimethylformimidate chloride to
cellulose formate, and
f. drying the textile.
Steps (a) through (d) are the same as for the preparation of
cellulose N,N-dimethylformimidate chloride.
PREPARATION OF CHLORODEOXYCELLULOSE
The preparation of chlorodeoxycellulose by the present invention
comprises the following steps:
a. immersion of air-equilibrated fibrous cellulose in textile form
in N,N-dimethylformamide at a temperature of about from 20.degree.C
to 30.degree.C for a period of from 1 to 60 minutes to swell the
fibers,
b. removing excess N,N-dimethylformamide,
c. immersing the cellulosic textile in a mixture of about from 3 to
15 percent by weight chlorodimethylformiminium chloride in
N,N-dimethylformamide at a temperature of from 50.degree.C to
110.degree.C for about from 0.25 hour to 2 hours in order to react
the cellulose with the DMFCl.sub.2,
d. washing the cellulosic textile with N,N-dimethylformamide to
remove excess DMFCl.sub.2,
e. washing the cellulosic textile with ice water and then with
water at 20.degree.C to 30.degree.C to remove N,N-dimethylformamide
and further traces of DMFCl.sub.2, and
f. drying the textile.
Steps (a) and (b) are the same as for the preparation of cellulose
N,N-dimethylformimidate, while step (c) differs primarily in the
use of a higher reaction temperature. Step (d) also is the same as
for preparing cellulose N,N-dimethylformimidate. Step (e) can be
modified to include a wash with 2-5 percent aqueous ammonia if
needed to remove sulfur-containing impurities in the product. The
ammonia wash also removes any formate ester groups present. The
sulfur-containing impurities arise if the DMFCl.sub.2 employed
contains appreciable amounts of thionyl chloride. Drying (step f)
is preferably done at moderate temperatures not exceeding
80.degree.C in order to avoid dehydrochlorination.
SPECIAL FEATURES AND UTILITY
It is evident that DMFCl.sub.2 undergoes only single-ended
attachment to cellulose as a result of the present processes, since
the cellulose N,N-dimethylformimidate produced is completely
soluble in 0.5 M cupriethylenediamine and no crosslinking of
cellulose can be detected. A solution of purified DMFCl.sub.2 in
N,N-dimethylformamide differs in composition from a solution of
thionyl chloride in N,N-dimethylformamide. The latter solution
appears to be an equilibrium mixture of thionyl chloride,
N,N-dimethylformamide, a 1:1 addition complex of thionyl chloride
and the amide, as well as sulfur dioxide and some DMFCl.sub.2. The
presence of the 1:1 complex having the structure [(CH.sub.3).sub.2
N.sup.+ = CHOSOCl] Cl.sup.- has been discussed by Bosshard et al,
as cited above, who found it necessary to remove the sulfur dioxide
under vacuum in order to shift the equilibrium towards formation of
DMFCl.sub.2. As already indicated above, the use of thionyl
chloride to treat cellulose always gives rise to sulfur-containing
cellulose derivatives as byproducts, whereas highly purified
DMFCl.sub.2, when reacted with cellulose, yields a sulfur-free
product.
The celluose N,N-dimethylformimidate chloride prepared from
DMFCl.sub.2 and cellulose is found to have appreciable flame
resistance. This is unexpected since the product contains neither
phosphorus nor bromine, the two most common elements in flame
retardant finishes.
Chlorodeoxycellylose and iododeoxycellulose produced by the present
processes exhibit increased flame resistance also, as well as rot
resistance. Cellulose formate exhibits enhanced dyeability by
disperse dyes.
METHODS OF TEXTILE EVALUATION
In the examples that follow, yarn breaking strength was measured by
the procedure of ASTM-D1682-64, using an Instron tester. Fabric
breaking strength was measured by the strip method (ASTM D39-49).
Flame resistance was measured by determining the maximum angle from
the vertical that a sample could be positioned, such that when
ignited from the lower end by a match, the flame was
self-extinguising after the match was withdrawn (Reeves, McMillan
and Guthrie, Textile Research J. 23, 527-532 (1953) ). Rot
resistance was determined by burial of the samples in inoculated
soil (AATCC 30-1957T). Formyl content of cellulose format was
determined by modified Eberstadt titration (ASTM D-871-63). The
infrared spectra of cellulose formate samples was recorded on a
Perkin-Elmer Model 137B Infracord spectrophotometer for pellets of
the powdered samples pressed into potassium bromide discs.
In all cases the yarns or fabrics to be used in the following
examples were stored in air at 30-80 percent relative humidity
prior to use and contained the equilibrium amount of regain
moisture.
In the examples, all parts and percentages given are by weight. The
term D.S. refers to the degree of cellulose substitution, i.e., the
number of substituent groups introduced per anhydroglucose unit of
cellulose.
EXAMPLE 1
Preparation of Cellulose N,N-dimethylformimidate chloride from
Cellulose Yarn
Kiered, 12/3 cotton yarn was immersed in excess
N,N-dimethylformamide for 30 minutes at 25 .degree.C, then excess
N,N-dimethylformamide was removed from the yarn by centrifugation
at 2850 rpm for 1 minute. The yarn was subsequently reacted for 5
minutes at 25.degree.C with 6 percent chlorodimethylformiminium
chloride (DMFCl.sub.2) in N,N-dimethylformamide in a stoppered
flask with agitation, utilizing 40 grams of solution per gram of
cotton. The yarn was then subsequently washed three times with
excess N,N-dimethylformamide, three times with excess benzene,
centrifuged for 1 minute at 2850 rpm, and allowed to air-dry to
constant weight. The resultant yarn had only trace amounts of
sulfur and a chlorine content of 3.34 percent and a nitrogen
content of 1.36 percent. The chlorine/nitrogen atomic ratio was 1.0
as required for the structure Cell--O--CH=N.sup.+(CH.sub.3).sub.2
Cl.sup.- , cellulose N,N-dimethylformimidate chloride. This
cellulose derivative had a breaking strength of 5.6 lbs. compared
to 5.2 lbs. for untreated, native cotton yarn and also had a match
angle test value of 60.degree. compared to 0.degree. for native
cotton yarn.
Conducting the reaction for a longer time (3 hours) with all other
conditions comparable to those described above, produced the
cellulose N,N-dimethylformimidate chloride yarn having only trace
amounts of sulfur, a chlorine content of 5.10 percent, and a
nitrogen content of 2.24 percent. The resultant cellulose
derivative had a breaking strength of 4.7 lbs. compared to 5.2 lbs.
for untreated, native cotton yarn; it also had a match angle test
value of 120.degree. compared to 0.degree. for native cotton
yarn.
EXAMPLE 2
Reaction of DMFCl.sub.2 with Cotton Yarn in Absence of Preswelling
Step
Kiered 12/3 cotton yarn was immersed in a 6 percent solution of
DMFCl.sub.2 in N,N-dimethylformamide at 25.degree.C for 5 minutes
in a stoppered, mechanically agitated flask, utilizing 40 grams of
solution per gram of cotton. The yarn was subsequently washed three
times with excess N,N-dimethylformamide, three times with benzene,
was centrifuged for 1 minute at 2850 rpm, and allowed to air-dry to
constant weight. The resultant yarn contained only 0.46 percent
chlorine, 0.12 percent nitrogen and no sulfur. By comparison, yarn
which was first preswollen in N,N-dimethylformamide, and then was
reacted with 6 percent DMFCl.sub.2, followed by washing and drying,
contained 3.34 percent chlorine and 1.36 percent nitrogen, as shown
in Example 1.
The results show that the yarn given the preswelling treatment in
N,N-dimethylformamide, prior to treatment with DMFCl.sub.2 reacted
more than 7 times as fast as did the yarn not given the preswelling
treatment. Even if a reaction time of 1 hour were allowed for yarn
not preswollen, a chlorine content of only 2.45 percent and a
nitrogen content of only 0.51 percent were reached, which values
are less than those reached in 5 minutes with the preswollen
yarn.
EXAMPLE 3
Preparation of Cellulose Formate by Reaction of Cotton Yarn with
DMFCl.sub.2 at 25.degree.C
Kiered, 12/3 cotton yarn was immersed in excess
N,N-dimethylformamide for 10 minutes, then excess
N,N-dimethylformamide was removed from the yarn by centrifugation
for 1 minute at 2850 rpm. The yarn was subsequently reacted for 1
hour at 25.degree.C (in a stoppered flask with agitation) with 6
percent DMFCl.sub.2 in N,N-dimethylformamide, using a bath ratio of
40 grams of solution per gram of cotton. The yarn was subsequently
washed with ice water, then with tap water for 30 minutes, and
air-dried to produce cellulose formate (D.S. of 0.16) having only
trace amounts of sulfur (0.25 percent) and chlorine (0.19 percent).
The resultant yarn had a breaking strength of 4.4 lbs. compared to
native cotton yarn which had a breaking strength of 5.2 lbs. The
presence of formate ester groups in the treated yarns was
demonstrated by an intense absorption peak at 5.8-5.9 millimicrons
in the infrared spectrum of the treated yarn. This peak, which is
absent for untreated yarns, has been assigned to the carbonyl
stretching frequency characteristic of the formyl groups. The same
spectrum was obtained in yarn esterified with 90 percent formic
acid. If the cotton yarn were treated under the same conditions,
with the exception that it was not preswollen in
N,N-dimethylformamide prior to reaction, the resultant D.S. with
respect to formate ester groups was only 0.04, with the yarn having
a breaking strength of 4.8 lbs. compared to 5.2 lbs. for untreated
cotton yarn.
EXAMPLE 4
Preparation of Chlorodeoxycellulose Yarn from Cellulose and Excess
DMFCl.sub.2
Kiered, 12/3 cotton yarn was immersed in excess
N,N-dimethylformamide for 30 minutes at 25.degree.C and excess
N,N-dimethylformamide was then removed from the yarn by
centrifugation at 2850 rpm for 1 minute. The yarn was subsequently
reacted with 6 percent DMFCl.sub.2 in N,N-dimethylformamide for 1
hour at 50.degree.C in a tube immersed in a constant temperature
bath, utilizing 40 grams of solution per gram of cotton. After
cooling to room temperature, the yarn was washed with
N,N-dimethylformamide until the washings were colorless. The yarn
was subsequently washed with ice water and then tap water in excess
for 30 minutes, and allowed to air-dry. The resultant
chlorodeoxycellulose yarn had a D.S. of 0.05 (1.05 percent Cl), a
sulfur content of 0.77 percent, and a D.S. of 0.28 with respect to
formate ester groups. The yarn had a breking strength of 3.8 lbs.
compared to 5.2 lbs. for untreated cotton yarn.
In another experiment, the reaction was conducted under the same
experimental conditions, but the wash procedure was modified. After
an initial tap water wash for 15 minutes, the yarn was washed with
excess 3 ammonium hydroxide, and then tap water for another 15
minutes prior to air-drying. The resultant chlorodeoxy cellulose
yarn had a D.S. of 0.04 (percent Cl = 0.97), a sulfur content of
0.39 percent, a D.S. of only 0.01 with respect to formate ester
groups, and a breaking strength of 4.0 lbs.
Conducting the reaction for the same time and concentration of
DMFCl.sub.2 at 75.degree.C with only a water wash, produced a
chlorodeoxycellulose yarn having a D.S. of 0.25 (5.27 percent Cl),
a sulfur content of 1.33 percent, and a D.S. of 0.31 with respect
to formate ester groups. If an ammonia wash were utilized, the
resultant chlorodeoxycellulose yarn had a D.S. of 0.26 (5.55
percent Cl), a sulfur content of 0.88, and a D.S. of only 0.08 with
respect to formate ester groups introduced. The breaking strengths
of the chlorodeoxycellulose yarns with and without the ammonia wash
were, respectively, 3.3 and 3.1 lbs.
When the reaction was conducted at 100.degree.C under otherwise
comparable experimental conditions, the resultant
chlorodeoxycellulose yarn (with a water wash only) possessed 6.53
percent Cl (D.S. of 0.31), a sulfur content of 0.97, and a D.S. of
0.18 with respect to formate ester groups introduced. Utilizing an
ammonia wash produced a chlorodeoxycellulose yarn with a D.S. of
0.34 (7.13 percent Cl), a sulfur content of 0.71 and a D.S. of only
0.04 with respect to formate ester groups. The breaking strengths
of the resultant yarns with and without the ammonia wash were 1.8
and 1.6 lbs., respectively.
EXAMPLE 5
Reaction of Cellulose Yarn without Utilizing Excess DMFCl.sub.2
Kiered, 12/3 cotton yarn was immersed in excess
N,N-dimethylformamide for 30 minutes at 25.degree.C, and then
excess N,N-dimethylformamide was removed from the yarn by
centrifugation at 2850 rpm for 1 minute. The yarn was subsequently
reacted with 6 percent DMFCl.sub.2 in N,N-dimethylformamide for 1
hr. at 25.degree.C with shaking in a stoppered flask, utilizing 40
grams of solution per gram of cotton. Excess DMFCl.sub.2 was
removed from the cotton yarn by washing with N,N-dimethylformamide,
and then the yarn was subsequently centrifuged for 1 minute at 2850
rpm to remove excess solvent. The yarn was then heated for 1 hour
at 100.degree.C in a tube containing N,N-dimethylformamide with the
bath ratio being 40 grams of solvent per gram of cotton. After
cooling to room temperature, the yarn was washed with water only as
described in the first part of Example 1. The resultant yarn had
only 0.21 percent Cl, representing a D.S. of 0.01, but also
contained 0.24 percent S and had a D.S. of 0.13 with respect to
formate ester groups. The breaking strength was 4.0 lbs.
EXAMPLE 6
Preparation of Chlorodeoxycellulose Fabric Utilizing Excess
DMFCl.sub.2
Desized, scoured and bleached 80 .times. 80 cotton printcloth was
immersed in excess N,N-dimethylformamide at 25.degree.C for 30
minutes, put through laboratory wringers to remove excess
N,N-dimethylformamide, and then reacted for 1 hour at 75.degree.C
with 6 percent DMFCl.sub.2 in N,N-dimethylformamide under the same
experimental conditions described for the cotton yarn in Example 1.
Utilizing the water-wash-only procedure, the resultant
chlorodeoxycellulose fabric had 6.0 percent Cl (D.S. - 0.28), and a
sulfur content of 3.13 percent; the fabric had a warp breaking
strength of 25.2 lbs. compared to 49.7 lbs. for untreated
printcloth. After two weeks of the soil burial test, the untreated
printcloth had disappeared, whereas the chlorodeoxycellulose
printcloth had a breaking strength of 22.1 lbs. After four weeks of
the soil burial test, the chlorodeoxycellulose printcloth still had
a breaking strength of 22.9 lbs.
EXAMPLE 7
Preparation of Iododeoxycellulose Utilizing DMFCl.sub.2 and Iodide
Ion
Kiered, 12/3 cotton yarn was immersed at 25.degree.C for 10 minutes
in N,N-dimethylformamide and then the excess N,N-dimethylformamide
was removed by centrifugation for 1 minute at 2850 rpm. The yarn
was reacted for 1 hour in a stoppered flask with shaking at
25.degree.C with 6 percent DMFCl.sub.2 in N,N-dimethylformamide,
utilizing a bath ratio of 40 grams of solution per gram of cotton.
Subsequently, the yarn was washed with N,N-dimethylformamide to
remove excess DMFCl.sub.2, centrifuged for 1 minute at 2850 rpm,
and then reacted in a constant temperature bath for 1 hour at
100.degree.C with 12 percent potassium iodide in
N,N-dimethylformamide. The bath ratio was 40 to 1. The yarn was
then cooled to room temperature, washed with N,N-dimethylformamide,
washed with ice water, excess tap water for 30 minutes, and was
air-dried. The resultant iododeoxycellulose yarn had an iodine
content of 2.12 percent (D.S. of 0.03), 0.10 percent Cl, 0.16
percent S, and a D.S. of only 0.19 with respect to formate ester
groups. The yarn had a breaking strength of 4.7 lbs. and a match
test angle of 15.degree. with a black residue. Untreated yarn
leaves no residue.
When 20 percent potassium iodide in N,N-dimethylformamide was
utilized at 100.degree.C by the above procedure, the resultant yarn
possessed 1.88 percent I (D.S. of 0.02), 0.93 percent Cl, 0.29
percent S, and a D.S. of 0.15 with respect to formate ester groups.
The breaking strength of the yarn was 4.9 lbs. and it had a match
test angle of 45.degree. and left a black residue. When an ammonia
wash was used, the iododeoxycellulose yarn had 2.34 percent I, 0.30
percent Cl, 0.19 percent S, and a D.S. of only 0.02 with respect to
formate ester groups. The yarn had a match test angle of 60.degree.
and a breaking strength of 5.0 lbs.
When 20 percent potassium iodide in N,N-dimethylformamide was
utilized at 125.degree.C by the above procedure, followed by the
water wash, the resultant yarn had 3.86 percent I, (D.S. of 0.05),
0.53 percent Cl, 0.13 percent S, and a D.S. of 0.13 with respect to
formate ester groups; utilizing the ammonia wash produced a yarn
containing 3.54 percent I (D.S. of 0.05), 0.28 percent Cl, 0.07
percent S, and a D.S. of only 0.05 in formate ester groups. The
breaking strengths, respectively, of the yarns with and without the
ammonia wash, were 4.0 and 4.3 lbs; match tests, respectively, were
90.degree. and 60.degree..
EXAMPLE 8
Preparation of Iododeoxycellulose Fabric Utilizing DMFCl.sub.2 and
Iodide Ion
Desized, scoured and bleached 80 .times. 80 cotton printcloth was
immersed in excess N,N-dimethylformamide at 25.degree.C for 30
minutes, put through laboratory wringers to remove excess
N,N-dimethylformamide, and then shaken in a stoppered flask for 1
hour at 25.degree.C with 10 percent DMFCl.sub.2 in
N,N-dimethylformamide, using a bath ratio of 40 grams of solution
per gram of cotton. The fabric was washed free of excess
DMFCl.sub.2 with N,N-dimethylformamide, put through wringers again
to remove excess N,N-dimethylformamide, and then reacted in a
constant temperature bath at 125.degree.C for 1 hour with 20
percent potassium iodide in N,N-dimethylformamide (bath ratio of 40
grams of solution per gram of cotton). After cooling to room
temperature, the fabric was given the conventional water wash and
air-drying. The resultant fabric had an iodine content of 7.56
percent (D.S. of 0.10), 14 percent Cl, and 0.53 percent S. The
fabric had a warp breaking strength of 35.8 lbs. compared to 49.7
lbs. for untreated cotton printcloth. After two weeks of the soil
burial test, the untreated printcloth disappeared whereas the
iododeoxycellulose fabric had a breaking strength of 32.9 lbs. The
resultant fabric also had a match test angle of 75.degree. and gave
a black residue.
* * * * *