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U.S. Pat. No. 3,395,708 and Reissue No. 26,939 to Hervey and George dated
Aug. 6, 1968 and Aug. 18, 1970 and French Pat. No. 1,265,818 disclose that
treatment of unfiberized wet cellulose pulp with a surfactant before or
during the formation of the cellulose pulp on a drying machine or on a
paper machine reduces the interfiber bonds of the cellulose. The
improvement is accomplished by impregnating a wet slurry of wood pulp with
a cationic debonding agent, forming the wet slurry into a wet pressed wood
pulp sheet, and mechanically fiberizing the dried sheet to form a
substantially completely fiberized fluffed fibrous wood pulp batt. The
result of this treatment is a cellulose batt, sheet or paper having
improved softness and a low degree of mechanical strength. Among the
surfactants said to be useful in this way are long chain cationic
surfactants, preferably with at least twelve carbon atoms in at least one
alkyl chain, and illustrative, but non-limiting, specific examples of same
are fatty dialkyl amine quaternary salts, mono fatty alkyl tertiary amine
salts, primary amine salts, and unsaturated fatty alkyl amine salts.
The hydrophilic cationic portion of the surfactant is considered to be
attracted to the negatively-charged cellulose fibers, while the
hydrophobic portions of the molecule are exposed on the surface, thus
rendering the surface of the fibers hydrophobic. The interbonds between
the cellulose fibers are reduced, and the defibration into cellulose fluff
is thereby facilitated. However, a highly hydrophilic cellulose pulp when
treated with such cationic surfactants will exhibit more hydrophobic
properties than the corresponding untreated cellulose pulp. If the
cellulose pulp or paper is intended to be used in the production of highly
absorbent products, such as sanitary products, hydrophobicity is not
desirable, since it reduces absorptivity. Consequently, in the treatment
of such cellulose derivatives, it has been necessary in order to improve
the wettability of the cellulose fibers after the treatment to add a
wetting agent, which is preferably added to the cellulose pulp sheet in a
separate operation, owing to the low degree of affinity to cellulose of
these wetting agents.
Tobler et al. U.S. Pat. No. 3,636,114 dated Jan. 18, 1972 describes
tertiary amines and quaternary ammonium compounds and a method for
preparing such amines and quaternary ammonium compounds. The quaternary
ammonium compounds have the formula:
##STR1##
wherein R.sub.1 is alkyl, aryl, aralkyl or alkaryl, and R.sub.2 is alkyl,
aralkyl, alkaryl, 2-hydroxy alkyl, 1-alkoxymethyl, and R.sub.1
CHOHCH.sub.2 ; R.sub.3 and R.sub.4 are lower alkyl, HOCH.sub.2 CH.sub.2 or
HO--CH.sub.2 CH.sub.2 CH.sub.2 ; and X is a hydroxyl or salt-forming
anion. These quaternary ammonium compounds are prepared from tertiary
amines of the formula:
(R.sub.1 [OCH.sub.2 ].sub.n CHOHCHR.sub.5).sub.2 NR.sub.3
these compounds are said to have utility as fabric softening agents and as
anti-bacterial compounds or germicides. There is no indication that such
compounds will impart antistatic properties to fabrics or other
substrates. Neither is there any disclosure of oxyalkylene groups
containing more than one carbon atom per unit.
In accordance with the invention, it has been determined that
bis(alkoxy(2-hydroxy)propylene) quaternary ammonium compounds which
contain both cationic and nonionic hydrophilic groups when used to treat
textile materials impart improved antistatic properties and/or softness
while at the same time preserving good hydrophilic properties. The
quaternary ammonium compounds in accordance with the invention have the
general formula:
##STR2##
In this formula:
R.sub.1 and R.sub.2 are aliphatic hydrocarbon groups, which can be either
saturated or unsaturated, having from about eight to about twenty-two
carbon atoms;
R.sub.3 and R.sub.4 are methyl, ethyl or hydroxyethyl;
n is a number from 2 to 4, representing the number of carbon atoms in the
oxyalkylene substituent, which can thus be oxyethylene, oxypropylene-1,2
or -1,3 or oxybutylene-1,2 -1,3, -1,4 or -2,3;
n.sub.1 and n.sub.2 are numbers within the range from 0.5 to about 10,
representing the number of oxyalkylene groups present in each substituent;
n.sub.1 and n.sub.2 usually represent average values, and therefore need
not be integers. When n.sub.1 and/or n.sub.2 are less than one, they
represent an average of molecules having zero and one or more oxyalkylene
groups; and
X is a salt-forming anion.
The quaternary ammonium compounds in accordance with the invention impart
superior antistatic properties to substrates than the alkyl quaternary
ammonium compounds heretofore used, such as those of U.S. Pat. No.
3,395,708. The improvement in antistatic properties is believed due to the
presence of the 2-hydroxy-oxypropylene group and the oxyalkylene groups.
Compounds having from one to two oxyalkylene groups and one
2-hydroxy-oxypropylene group impart the best antistatic properties, and
are therefore preferred. In these compounds, n.sub.1 and n.sub.2 are
numbers within the range from 0.5 to 2.
Quaternary ammonium compounds falling within the above formula in which
R.sub.1 and R.sub.2 have from about eight to about fourteen carbon atoms
are freeze-thaw stable in aqueous solutions at concentrations of from
about 5% to about 10%; that is, at these concentrations they have no or
only a slight tendency to gel and freeze-separate when subjected to
repeated freezing and thawing. In concentrated or pure form, these
compounds are liquids, which facilitates their formulation into consumer
products.
The quaternary compounds in accordance with the invention can be applied to
the substrate in the form of solids, such as powders or pastes, or as
solutions, in water or in an organic solvent. In such solutions, the
concentration of quaternary ammonium compound can range from about 0.01 to
about 25%, preferably from about 0.1 to about 10%.
In the case of solutions for application to textile materials, the
concentration of the quaternary ammonium compound can be within the range
from about 0.01 to about 0.05 gram, and preferably from about 0.05 to
about 0.15 gram, per liter of solution. Aqueous solutions of such
concentrations are quite useful, for example, as rinsing solutions at any
of the stages of textile processing during which aqueous rinsing solutions
are used. Due to their good affinity for textile fibers, the quaternary
ammonium compounds can be introduced into any rinsing solution in the
course of the process, but the best and most lasting effect is obtained if
the quaternary ammonium compound is included in the last rinsing solution.
The compounds can also be added at the prewash or in the main wash
operations, but in these cases the antistatic effects may be less per unit
weight of compound applied to the textile material, probably because of
losses of the compound during later processing.
The usual solvent used is water. However, if rapid volatilization of the
solvent is desired, the quaternary ammonium compounds of the invention can
be applied from a solution in a rapidly volatilizable organic solvent,
such as acetone, methanol, ethanol, isopropanol, or mixtures thereof. In
this case, the concentrations are the same as aqueous solutions, within
the range from about 5% to about 10% by weight of the quaternary ammonium
compound.
The solutions of the quaternary ammonium compounds of the invention can
also be applied by dipping, spraying, or coating, using conventional
techniques. This sort of application is useful on textile materials which
normally are very seldom washed, or are not washed at all, or on leather
or plastic sheet material, or on plastic films coated on other base such
as wood. When applied in this way, the composition usually contains the
quaternary ammonium compound in a concentration within the range from
about 5% to about 10%.
The application solution can also include nonionic surfactants, such as
adducts of ethylene oxide or propylene oxide and aliphatic alcohols or
alkyl phenols, to improve the rewettability of the treated material.
Solubility-enhancing additives, such as the monoethyl ether of diethylene
glycol, can also be added.
The quaternary ammonium compounds of the invention are applied to the
substrate in an amount within the range from about 0.001% to about 2% by
weight of the substrate.
The compounds of the invention impart antistatic properties to textile
materials of all kinds including both woven and nonwoven materials made of
natural or synthetic fibers or mixtures thereof, such as, for example,
rayon, acetate rayon, cellulose acetate-propionate, cellulose
acetate-butyrate, polyvinyl chloride, polyamide, polypropylene,
polyethylene, polyacrylonitrile, polyesters such as ethylene
glycol-terephthalic acid polymers, cotton, linen, jute, ramie, sisal,
wool, mohair, alginate fibers, zein fibers, glass, potassium titanate,
bast, bagasse, polyvinylidene chloride, and fur fibers of various kinds
such as beaver, rabbit, seal, muskrat, otter, mink, caracul, lamb and
squirrel.
The textile materials can take any form, including nonwoven materials such
as felts, bats and mats; woven materials such as fabrics, cloth, carpets,
rugs and upholstery; synthetic fur materials; curtains, and covering
materials of all kinds.
The compounds of the invention are applicable to impart antistatic
properties to leather materials, such as leather furniture and leather
clothing.
They are also applicable to plastic surfaces, many of which have a
pronounced tendency to develop a static charge, such as synthetic
phonograph records which are usually made of polyvinyl chloride; to
painted, varnished and lacquered surfaces which bear a synthetic resinous
coating film; to metal foils, and chassis for electric and electronic
devices, such as radios, hi-fis, phonograph systems, sound amplification
systems, amplifiers, television, and sound-recording equipment.
The synthesis of the alkoxy-2-hydroxy-propylene quaternary ammonium
compounds in accordance with the invention includes the following reaction
steps:
##STR3##
In the above reaction formulae, R.sub.1, R.sub.3, R.sub.4, n and n.sub.1
have the meanings earlier mentioned.
The alkoxyalkylene oxy-(2-hydroxy)propylene quaternary ammonium compounds
in accordance with the invention can be prepared by reaction of from 1 to
about 10 mols of ethylene oxide with one mol of an aliphatic alcohol
having from about eight to about twenty-two carbon atoms. The reaction of
alkylene oxide with the alcohol is carried out in the presence of an
alkali catalyst, preferably sodium hydroxide, at an elevated temperature.
If no oxyalkylene unit is present, of course this reaction step is
omitted.
The resulting alkoxy glycol ether is reacted with epichlorhydrin, producing
the corresponding chloroglyceryl or chlorohydroxypropylene ether, which is
then reacted with a secondary amine having the formula R.sub.3 R.sub.4 NH,
where R.sub.3 and R.sub.4 are methyl, ethyl, or hydroxyethyl. The product
is a quaternary ammonium compound of the invention, in the form of its
chloride salt. The chloride ion can then be exchanged by another ion,
using known techniques, for example, by addition of a sodium salt with a
higher solubility constant than sodium chloride, or by ion exchange in an
anion exchanger. Among anions other than chloride ion which can serve as X
in the quaternary ammonium compounds of the invention are nitrate,
carbonate, hydroxyl, phosphate, iodide, bromide, methyl sulfate, acetate,
carbonate, formate, citrate, propionate, and tartrate. The monovalent
anions are preferred.
The reaction between the alkylene oxide adduct and the epichlorhydrin
proceeds at an elevated temperature within the range from about
100.degree. to about 150.degree.C in the presence of a catalyst, such as
stannic chloride, boron trifluoride, and perchloric acid, HClO.sub.4.
These give a rapid easily controllable reaction, but other acid catalysts
such as toluene sulfonic acid and sulfuric acid can also be used.
In order to ensure complete reaction of the alkylene oxide adduct, an
excess of epichlorhydrin is generally added.
The quaternization of the secondary amine with the chloroglyceryl ether is
carried out in the presence of alkali, generally sodium hydroxide, at an
elevated temperature within the range from about 100.degree. to about
150.degree.C. The reaction is carried out in the presence of an organic
solvent with a boiling point of at least 60.degree.C. Suitable organic
solvents include methanol, ethanol, and the monoethylether of diethylene
glycol.
It is also possible to react the chloroglyceryl ether with ammonia or with
a primary amine having a methyl, ethyl, or hydroxyethyl group, and the
resulting product may then be quaternized with methyl or ethyl chloride or
dimethyl or diethyl sulfate. However, this procedure is more complicated
than the previously described procedure, and it involves more reaction
steps, and results in larger amounts of byproducts and lower total yields
of the desired quaternary ammonium compounds.
Alkylene oxides which can be used include ethylene oxide; propylene
oxide-1,2; propylene oxide-1,3; butylene oxide-1,2; butylene oxide-1,3;
butylene oxide-2,3; butylene oxide-1,4.
The aliphatic alcohols having from about eight to about 22 carbon atoms
which can be used in the reaction products of the invention include both
saturated and unsaturated alcohols, such as octyl alcohol, decyl alcohol,
lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl
alcohol, oleyl alcohol, ricinoleyl alcohol, linoleyl alcohol, and
eicosenyl alcohol. The alcohol can also be a mixture of such alcohols,
such as are obtained from natural fats and oils by reduction of the fatty
acid or fatty acid ester mixtures obtained from such oils, such as coconut
oil fatty alcohols, palm oil fatty alcohols, soya oil fatty alcohols,
linseed oil fatty alcohols, corn oil fatty alcohols, castor oil fatty
alcohols, fish oil fatty alcohols, whale oil fatty alcohols, tallow fatty
alcohols, and lard fatty alcohols. Mixtures of synthetic alcohols prepared
by the Ziegler procedure or the Oxo process can also be used. Most
alcohols manufactured by Oxo process have a branched chain, which makes
possible a large number of isomers. The physical properties of these
alcohol mixtures are very similar to those of the straight-chain primary
alcohols.
Secondary amines which can be used in accordance with the invention include
dimethyl amine, diethyl amine, diethanol amine, methyl amine, and methyl
hydroxyethyl amine. Primary amines which can be used include methyl amine,
ethyl amine, and hydroxyethyl amine.
The following Examples in the opinion of the inventors represent preferred
embodiments of their invention.
PREPARATION OF ADDITIVES
Additive A
In a reaction vessel provided with a heating coil, a stirrer, and a reflux
condenser for cooling, was placed 300 grams (1 mol) of a melt of tallow
fatty alcohol (a mixture of cetyl, stearyl and eicosyl alcohols), which
has previously been reacted with 0.5 mol of ethylene oxide per mol of
alcohol. The melt was brought to 75.degree.C with stirring, whereupon 3
grams of stannic chloride was introduced, and 101 grams (1.1 mol)
epichlorhydrin was then added over 1 hour. After all of the epichlorhydrin
had been added, the temperature was increased to 125.degree.C, and held
there for a further reaction time of 2 hours. The remaining epichlorhydrin
was then removed under vacuum, and the reaction product obtained was 390
grams of a pale yellow viscous liquid.
In an autoclave fitted with a heater and a stirrer was placed 350 grams
(0.9 mol) of this reaction product, 125 grams of ethanol, in which 20
grams (0.45 mol) of dimethyl amine had been dissolved, and 23 grams (0.56
mol) of sodium hydroxide dissolved in 15 grams of water. The mixture was
held at 125.degree.C in the autoclave for 3 hours. At the conclusion of
this time, the unreacted dimethyl amine was removed by bubbling nitrogen
gas through the mixture. The rection product was a pale beige substance,
having a melting point of 37.degree. to 40.degree.C. Analysis showed that
it contained 57% quaternary amine, 10% tertiary amine, 23 grams ethanol,
6% sodium chloride and 4% water, and had the formula:
##STR4##
Additive B
Using the above procedure, 2 mols tallow fatty alcohol, 1 mol butylene
oxide, 2 mols epichlorhydrin and 1 mol dimethyl amine were reacted to form
the product:
##STR5##
Additive C
Using the above procedure, 2 mols tallow fatty alcohol, 4 mols ethylene
oxide, 2 mols epichlorhydrin and 1 mol dimethyl amine were reacted to form
the product:
##STR6##
Additive D
Using the above procedure, 2 mols tallow fatty alcohol, 8 mols ethylene
oxide, 2 mols epichlorhydrin and 1 mol dimethyl amine were reacted to form
the product:
##STR7##
Additive E
Using the above procedure, 2 mols of a mixture C.sub.20 -C.sub.22 fatty
alcohols, 8 mols ethylene oxide, 2 mols epichlorhydrin and 1 mol dimethyl
amine were reacted to form the product:
##STR8##
Control I
Using the procedure for Additive A, 2 mols of alcohol, 2 mols
epichlorhydrin and 1 mol dimethyl amine were reacted, to form the product:
##STR9##
Control II
Using the procedure for Additive A, 2 mols of tallow fatty alcohol, 2 mols
of epichlorhydrin and 1 mol dimethyl amine were reacted to form the
product:
##STR10##
Additive F
Using the same procedure as in Additive A above, a fatty alcohol mixture (1
mol, 15% decyl alcohol, 47% dodecyl alcohol and 38% tetradecyl alcohol)
was reacted with ethylene oxide (1 mol), epichlorhydrin (1.1 mols) and
dimethyl amine (0.5 mol), using monoethyl ether of dialkylene glycol as
the solvent. The product by analysis contained 57% quaternary ammonium
compound in accordance with the invention, having the formula:
##STR11##
In addition, the reaction mixture contained 2.8% of a tertiary amine
containing an alkyl ether group and two methyl groups and 25% monoethyl
ether of diethylene glycol. The remainder was water, sodium chloride, and
unreacted starting material. The product mixture had a softening point of
12.degree.C, became clear at 33.degree.C, and when allowed to cool had a
hardening point of 10.degree.C.
Twelve parts by weight of this reaction product was dissolved in 88 parts
by weight of water. The resulting solution was liquid at room temperature;
it became solid at 0.degree.C. When cooled further, so that the water
solution was frozen, and then thawed, no tendency towards gelation was
noted.
EXAMPLES 1 to 5
The antistatic properties of Additives A to E above were evaluated in
comparison with Arquad 2 HT 75, distearyl dimethyl ammonium chloride, and
Controls I and II, above, using a sequence of washing tests in a drum
washing machine and test swatches of nylon cloth as the textile material.
The test swatches were washed with the same commercial nonsoap detergent
in each test, at 22.degree.C. In the last rinsing water, a solution of one
of the additives was used in an amount corresponding to 0.5 gram per
kilogram of nylon. After treatment, the time required for discharge of
half the electric charge applied to the nylon in a Rothschild Static
Voltmeter R-1020 was determined. The following results were obtained:
TABLE I
______________________________________
Half-life
Example No. Additive (seconds)
______________________________________
Control Commercial product
12
Control I 10
Control II 10
1 A 6
2 B 6
3 C 5
4 D 6
5 E 6
______________________________________
It is apparent from the above results that while Controls I and II, which
do not contain oxyethylene units, have better antistatic properties than
the commercial additive, the addition of oxyethylene units improved
(Additives A, B, C, D and E) the anti-static effect so that the half-life
for the nylon swatches treated with these additives is half or less that
for the commercial additive.
It is apparent from these data that the quaternary ammonium compounds in
accordance with the invention have a better antistatic effect than the
closely-related quaternary ammonium compounds of the prior art. It is
further evident that the compounds wherein n.sub.1 and n.sub.2 are within
the range from 0.2 to 2 have a superior antistatic effect.
EXAMPLE 6
The antistatic properties of Additive F were evaluated against distearyl
dimethyl ammonium chloride, Arquad 2 HT 75, for comparison. Test swatches
of cotton terry cloth were washed with commercial nonsoap detergent at
90.degree.C in a drum washing machine. The last rinsing water contained
either the Additive F or the distearyl dimethyl ammonium chloride,
applying 1.2 grams of dry additive per kilogram of cotton terry cloth
swatches. This washing cycle was repeated five times.
The water absorptivity of the treated terry cloth swatches was determined
by pressing a circular testing piece against the upper surface of a glass
fiber plate while the entire undersurface was in contact with water. By
measuring the decrease in the amount of water as a function of time, the
water absorption was determined. The following results were obtained:
TABLE II
______________________________________
Water Absorption
ml of water/g cloth
absorbed after 50 secs.
______________________________________
Untreated terry cloth 3.1
Terry cloth treated with 1.2 g/kg of
distearyl dimethyl ammonium chloride
1.1
Terry cloth treated with 1.2 g/kg of
the cation surfactant according to
the invention 2.4
______________________________________
Antistatic properties were evaluated on nylon cloth swatches which had been
washed at 20.degree.C, using a nonsoap synthetic detergent with the
additive in accordance with the invention added to the last rinse in the
same manner as in Examples 1 to 5. After conditioning the nylon swatches
for 24 hours at a relative humidity of 65% and 20.degree.C, the time
required for discharge of half the electric charge applied to the nylon in
a Rothschild Static Voltmeter R-1020 was determined. A strip of the cloth
was stretched between two metal clips, to which a potential of 100 volts
was applied. The following results were obtained:
TABLE III
______________________________________
Half-life
Product (seconds).sup.1
______________________________________
Untreated nylon cloth 74
Nylon cloth treated with 1.2 g/kg of distearyl
dimethyl ammonium chloride 34
Nylon cloth treated with 1.2 g/kg of the cation
surfactant according to the invention
9
______________________________________
.sup.1 Due to different testing conditions, no direct comparison with the
results from Examples 1 to 5 can be made.
The above data show that this compound is a liquid at room temperature, and
forms a freeze-thaw-stable aqueous solution at a concentration of 12%.
Compared to distearyl dimethyl ammonium chloride, the quaternary ammonium
compound according to the invention imparts softening, antistatic and
water-absorption effects to the textile material treated.
* * * * *
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