Note: Descriptions are shown in the official language in which they were submitted.
13326~-1
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TITLE
STAIN-RESISTANT AROMATIC/MALEIC ANHYDRIDE POLYMERS
FILED OF THE INVENTION
The present invention relates to polyamide
textile substrates treated with stain-resistant
compositions comprising hydrolyzed ethylenically
unsaturated aromatic/maleic anhydride polymers, and
processes for their preparation. The substrates of
this invention possess stain resistance but do not
suffer from yellowing to the extent that previously
known materials do.
BACKGROUND OF THE INVENTION
Polyamide substrates, such as nylon carpeting,
upholstery fabric and the like, are subject to
staining by a variety of agents, e.g., foods and
beverages. An especially troublesome staining agent
is FD&C Red Dye No. 40, commonly found in soft drink
preparations. Different types of treatments have
been proposed to deal with staining problems. One
approach is to apply a highly fluorinated polymer to
the substrate. Another is to use a composition
containing a sulfonated phenol-formaldehyde
condensation product.
For example, Liss and Beck, in Canadian Patent
No. 1,176,410, which issued on 1990 November 20
disclose stain-resistant synthetic polyamide textile
substrates having modified sulfonated phenol-
formaldehyde polymeric condensation products.
However, sulfonated phenol-formaldehyde condenation
products are
:
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1 3~584
r 2
themselves sub~ect to discoloration; commonly they turn
- yellow. Yellowing problems are descr~bed ~y W. H.
Hemmpel ~n a March 19, 1982 nrticle ~n ~merica's
~ex~ , entitled Reversible Yellow$na ~5~_Eirishe~'s
Fault. ~emmpel attributes yellowin~ to ~xposure of a
phenol-~ased finish to nitrogen ox~des ~nd/or ultra-
- violet radiation. Critchley et ~1., He~t ~es~stant
Polvmers, TechnoloaicallY_Useful Materials, ~lenum
Pr~ss, N.Y. l9B3, state that the thermo-oxidat~ve
; 10 stability of phenol-formaldehyde condensation products
; can be improved by etherifying or esterifying the
phenolic hydroxyl groups.
To deal wi~h the yellowing problem, M~rshall,
.- ~ in U.S. Patent 4,833,009, ISSUed 1989 May 23,
removes color-formers by dissolving the condensation
product ~n aqueous base, ac~difying the solu~ion to
form ~ slurry, heating the slurry so as to cause p~ase
separation, recovering water-insoluble material and
dissolving the water-insoluble mater~al ~n aqueous
-~ 20 base. On the other band, ~iss and Beck, in their
aforesaid application, remove color-for~ers by
acylating or etherifying some of the phenolic hydroxyls
of the condensat~on product, and in ~ preferred
embodiment, dissolving the modi~ed condensation
product in a hydroxy-cont~ining solvent, ~uch a5
; ethylene glycol, pr~or to its being appl~ed to the
text~le substrate.
Allen et al., in U.S. P~tent 3,835,071,
disclose rug shampoo compos~tion~ which upon drying
:; 30 leave very brittle, non-tacky res~dues which are easily
removed when dry. The compositions comprise water-
soluble metal, ammonium or amin~ salt of a styrene-
maleic anhydride copolym~r, or its half ester, and a
detergent. Water-soluble metal ~alts of Group II and
tlle alkali metals (par'icularly magnesium and sodium)
-2-
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are preferred and ammonium salts are most preferred by
Allen et al.
BRIEF SUMMARY OF THE INVENTI~
The present invention provides polyamide
textile substrates treated with hydrolyzed
ethylenically unsaturated aromatic/maleic anhydride
polymers so as to impart stain resistance to the
substrates, and methods for preparing the same.
Commonly materials known in the past to be useful as
stain blockers were sulfonated. Finding a non-
sulfonated material, such as the hydrolyzed
ethylenically unsaturated aromatic/maleic anhydride of
this invention, to be useful for this purpose was
unexpected.
DETAILED DESCRIPTION OF THE INVENTION
The hydrolyzed polymers suitable for the
purposes of this invention contain between about one
and two polymer units derived from one or more
ethylenically unsaturated aromatic monomers per polymer
unit derived from maleic anhydride (hydrolyzed polymers
containing three ethylenically unsaturated aromatic
polymer units per maleic anhydride polymer unit are not
suitable). Hydrolyzed polymers containing about one
polymer unit derived from one or more ethylenically
unsaturated aromatic monomers per polymer unit derived
from maleic anhydride are most effective in imparting
stain resistance to textile substrates. A variety of ~;
ethylenically unsaturated aromatic compounds can be
used for the purpose of preparing the hydrolized
polymers of this invention. Those aromatic compounds
can be represented by the formula
-3- ;
~.. ., . ~, . . , - .
4- 13~268 4
~' 5
. R4
- w~erein
. ................................. R2
R is Rl-CH-C- or CH2-C~-CH2-;
- lQ Rl is H-, CH3-or
- R2 is H- or CH3-;
~3 i~ ~-or CH30-:
`' 15 q
R4 ~s H-, CH3-, or CH3~0-, and
R3 plus R4 ~ -0-CH2-0-
Specific examples of ethylenically unsaturated arsmatic
. compounds suitable for the purposes o~ this invention
; 20 include styrene, ~lpha-~ethylstyrene, 4-~thyl styrene,
~ ~tilbene, 4-acetoxystilbene (used to prepare a
hydrol~zed polymer from Daleic ~nhydride and 4-hydroxy-
stilbene), eugenol, isoeugenol, 4-allylphenol, ~afrole,
mixtures of the s~e, and the like. ~rom the stand-
point of cost-e~fect$veness, a copolymer prepared from
styrene ~nd maleic ~nhydride at a 1:1 molar ratio is -
preferred. ~he hydrolyzed polymers can have ~olecular
weights (number aver~ge) in the range between about 500
and 4000, preferably between about 800 and 2000. They
are readily soluble, even ~t high concentrations, in
.: water at neutral to alkal~ne pH: increasing dilution is
needed at a p~ below 6. ~hey are also soluble in lower
alcohols, such as methanol, and are somewhat soluble in
acetic acid.
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The polymers suitable for the purposes of
this invention can be prepared by hydrolyzing
ethylenically unsaturated aromatic/maleic anhydride
polymers. However, not just any hydrolyzin~ agent will
give products of equivalent utility for the purposes of
this invention. Alkali metal hydroxides are suitable
hydrolyzing agents. While potassium and/or lithium
hydroxides can be subtituted for sodium hydroxide in
whole or in part as a hydrolyzing agent, the latter is
preferred. Hydrolysis can be effected in the presence
of more than or less than a molar amount of an alkali
metal hydroxide, such as NaOH. But unless special
measures are taken, hydrolysis of the polymer in the
presence of ammonium hydroxide gives a product which
does not provide satisfactory stainblocking properties
to a polyamide textile substrate. Thus, if the polymer
is hydrolyzed in the presence of ammonium hydroxide, it
is essential that it be held at elevated temperature
for an extended period of time thereafter; otherwise,
the polymer imparts unsatisfactory stainblocking
properties to polyamide substates. On the other hand,
hydrolysis of the polymer in the presence of excess
ammonium hydroxide results in a product which fails to ~;
impart satisfactory stainblocking properties to
polyamide substrates even after having been held for an
extended period of time at elevated temperature. -
Neither should hydrolysis be carried out in the
presence of an alcohol. Even in the presence of any of ~ ;
the bases described above, the ethylenically
unsaturated aromatic/maleic anhydride polymer can react
with the alcohol to form a half-ester which will be
deleterious to the stain-resist performance of the
hydrolyzed polymers.
The hydrolyzed ethylenically unsaturated
aro~atic/maleic anhydride polymers of this invention
-5-
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~dJl b~ used as such in treating polyamide textile
substrates. They can be applied to dyed or undyed
polyamide textile substrates. They can be applied to
such substrates in the absence or presence of a
polyfluoroorganic oil-, water-, and/or soil-repellent
materials. In the alternative, such a
polyfluoroorganic material can be applied to the
textile substrate before or after application of the
hydrolyzed polymers of this invention thereto. The
hydrolyzed polymers can be applied to textile
substrates in a variety of ways, e.g. during
conventional beck and continuous dyeing procedures.
The quantities of the polymers of this invention which
are applied to the textile substrate are amounts
effective in imparting stain-resistance to the
substrate. The amounts can be varied widely; in
general, one can use between 0.1 and 2% by weight of
them based on the weight of the textile substrate,
usually 0.6% by weight or less. The polymers can be
applied, as is common in the art, at pHs ranging
between 4 and 5. However, more effective exhaust
deposition can be obtained at a pH as low as 2. When
pH of 2 is used, the preferred level of application to
the textile substrate is about 0.6% by weight, based on
the weight of the textile su~strate. More effective
stainblocking is obtained if the hydrolyzed polymers
are applied to the textile substrate at higher
temperatures. For example, at pH 2, 170-F is
preferred, and 200-F is preferred at pH 5. However,
stainblocking can be obtained when application is
effected at room temperature, or even at that of cold
tap water (10-15C).
The hydrolyzed polymers of this invention can
also be applied in-place to polyamide carpeting which
J~ has already been .nstalled in a dwelling place, office
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or other locale. They can be applied as a simple
aqueous preparation or in the form of aqueous shampoo
preparation, with or without one or more polyfluoro-
organic oil-, water-, and/or soil-repellent ~aterials.
They may be applied at the levels described above, at
temperatures described, and at a pH between about l and
12, preferably between about 2 and 9.
The following Examples are illustrative of
the invention. Unless otherwise indicated, all parts
and percentages are by weight and temperatures in the
Examples and Tests are in degrees Celsius. In the
examples that follow, stain resistance and yellowing
were measured by the techniques described below.
Exhaust A~lication of Stain-Resists to Car~e~ina
Launder-O-Meter Method
Exhaust application of stain-resists to
carpeting is carried out in a Launder-O-Meter automated
dyeing machine. One carpet piece is contained in each
of several (up to twenty) stainless steel, screw-cap
canisters. The canisters are held in a rack that
rotates in a water bath whose temperature is
automatically controlled for rate of heating, time at
temperature and cooling. For a typical application
bath, one uses a 20 to 1 liguor to goods ratio with 2.5
weight % of the stain-resistant composition. The
stain-resistant compositions can be applied at pH 2 or
pH 5. At pH 2, an excess of sulfamic acid is used. At
pH 5, an excess of ammonium sulfate is used, as well as
3g/L of magnesium sulfate and lg/L of an alkyl aryl
sulfonate (AlkanolND) or a suitable leveling agent.
After the bath is made up, a solution of the stain-
resist composition is added to the Launder-o-Meter
canister. The carpet sample to be treated is then
placed in t`~e canister, tufted side out, the size of
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the carpet sample, relative to the size of the
canister, being such that the no portion of the sample
touches another portion of the sample. The canisters
are placed in the Launder-O-Meter and the water bath
temperature is held at 110F for 5 minutes. The
temperature of the water bath is then raised to the
desired temperature for application of the stain-resist
composition. For application at pH 2, the temperature
of the water bath is raised to 170F + 5-F, and for
application at pH 5, the temperature of th~ water bath
is raised to 200F + 5-F. After the bath water reaches
the des-ired temperature, it is held there for 20 min.
and then cooled to lOO-F. The treated carpet sample is
removed from the canister and rinsed by squeezing in
deionized water at room temperature. Three successive
rinses in fresh deionized water are given, each rinse
being at 40 volumes of water per volume of sample. The
rinsed carpet sample is centrifuged to remove excess
liquid and dried at 200-F. in a forced draft oven for
30 minutes. The dry carpet sample can then be tested
by use of the tests described below.
Stain Tests
~. Stain Test A is used to measure the extent
to which carpeting is stained by a commercial beverage
composition which contains FD&C Red Dye No. 40 (an acid
dye). The staining liquid, if sold commercially as a
liquid, is used as is. Usually the commercial product
is in the form of a solid. In that event, the beverage
preparation, in dry, solid form, is dissolved in
deionized water so as to provide 0.1 g of FD~C Red Dye
l~o. 40 per liter of water. Sufficient wetting agent
(Du Pont MerpolSE liquid nonionic ethylene oxide
condensate) is added to the dye solution to provide 0.5
~3 of the wetting age;~t per liter of dye solution.
',' ' .
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Unless otherwise specified, the test sample is
DuPont type 1150 Nylon 6,6 (white); Superba*
heatset, mock dyed level loop carpet, 3/8 inch pile
height, 30 ounces per yard, 1/10 inch gauge, 10
stitches per inch, woven polypropylene primary
backing. The test sample is wetted completely with
water, and excess water is removed by centrifuging.
The damp sample is placed tufted face down in a pan
and covered with ten times its face weight of stain
fluid. Entrained air is expelled from the sample by
squeezing or pressing. The sample is turned over
and again the air is expelled. The sample is then
returned to a face down position, and the pan is
covered for storage for desired test period, namely
30 minutes or 24 hours. The stored stain sample is
rinsed in running cool water until no more stain is
visually detectable in the rinse water. The rinsed
sample is extracted in a centrifuge and dried at 200
degrees F. Staining is evaluated with the Minolta*
Chroma Meter tristimulus color analyzer in the L*A*B
Difference Mode with the target sample set for the
unstained carpet. The "a" value is a measure of
redness, with a value of 43 equal to that obtained
on an untreated carpet.
B. In Stain Test B, a 6 inch x 6 inch (15 cm
x 15 cm) specimen of carpet is placed on a flat non-
absorbent surface. 20 ml of the staining fluid
described in Stain Test A is applied to the specimen
of carpet by placing a 1~ inch x 2 inch ~3.8 cm x
5.1 cm) cylinder tightly over the specimen and
pouring the staining liquid solution into the
cylinder to contact the carpet specimen thereby
forming a circular stain. the cylinder is then
removed and excess staining solution is worked into
the carpet tufts to achieve uniform staining. The
stained carpet specimen is left undisturbed for 24 +
4 hours, after which it is rinsed
* denotes trademarks
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133268~
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thoroughly with cool water, squeezed dry, and excess
solution removed. The stain resistance of the
resulting carpet sample is visually determined by the
amount of color left in the stained area of the carpet
sample according to the following scale:
5 = no staining
4 = slight staining
3 = noticeable staining -
2 = considerable staining
1 = heavy staining.
UV YELLOWING TEST
The light-fastness of carpet samples treated
with a stainblocker is determined by exposing the
lS treated samples to W light for 20 Hours. A sample
piece of carpet that has been treated with a stain-
blocker is placed in a box containing its hinged top a
standard fluorescent fixture fitted with two forty watt
lamps. Centered under the pair of lamps in the bottom
of the box is a sliding tray having a 3 inch x 40 inch
recess for holding carpet specimens. The depth of the
recess is such that the distance from the carpet face
to the plane defined by the lamp surfaces is 1 inch.
The current to the lamp is controlled by a timer so
that a twenty-hour exposure can be obtained
automatically. After the twenty-hour exposure, the
reflectance of CIE White Light Source C from the carpet
is compared with the reflectance from an unexposed
sample and the CIELAB delta nb~ noted. Delta "b" is a
measure of the yellow component of white light. A
Minolta Chroma Meter model CR-llO reflectance meter is
used to make the measurements and to calculate delta
"b" automatically from stored data on the unexposed
sample. The value of nb~ is reported as the measure of
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yellowing with increasing positive values of "b"
corresponding to increased degrees of yellowing.
the Minolta Chroma Meter is used in the Hunter
L*a*b color-deviation measuring mode tRichard
Hunter, "Photoelectric Colorimetry with Three
Filters," J. Opt. Soc. Am., 509-538 (1942)]. In the
measuring mode, the inetrument measures the color
differences between a "target" color, whose
tristimulus color values have been entered into the
microprocessor as a reference, and the sample color
presented to the measuring head of the instrument.
In examining carpet samples for yellowing and for
FD&C Red Dye No. 40 staining, the "target" color
entered is that of the carpet before yellowing or
staining. The color reflectance of the yellowed or
stained carpet is then measured with the instrument
and reported as:
*E, the total color difference, *L, the
lightness value,
*a, the redness value, if positive, or
greenness, if negative, and
*b, the yellowness value, if pGsitive, or
blueness, if negative.
EXAMPLE 1
In a 7 gallon paste pail, 4800 gms of a 1/1
molar styrene/maleic anhydride copolymer having a
number average molecular weight of 1600 (SMA*1000
from Sartomer) were stirred into 3000 gms of
deionized water to give a smooth slurry. It
dispersed well (no exotherm) in about 15 minutes.
Then over a~out 1 hour, 5400 gms of 30% NaOH were
added. The reactor was cooled during addition to
maintain temperature in the 30-40C range. If the
temperature went over about 40C, addition of
caustic solution was stopped. (Above 45C, the
polymer may melt and coagulate into large
* denotes trademark
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1332~8~
-12-
sticky globs which are very slow to hydrolyze.) After
all of the NaOH solution has been added, the reaction
mass was stirred for 15 minutes, then the reactor was
heated to 70~c and stirred for 3 hours. Heating was
stopped, and 2800 gms of deionized water was added with
stirring, following by cooling to 50OC. A light
yellow, slightly viscous, clear alkaline solution of a
polysodium salt of styrene/maleic acid copolymer was
obtained.
The solution thus obtained was applied to
nylon carpet at 2-1/2 percent on weight of fiber in a
simulated beck dyeing apparatus. The dried carpet was
tested by saturating it with a solution of FD&C Red Dye
No. 40 and letting it stand for 1/2 hsur a~ room
temperature (Stain Test A described above). It was
then rinsed with cold water. ~he treated carpet showed
no evidence of staining while an untreated control was
deeply stained red. In a similar test the carpet was
allowed to stand for 24 hours in the acid dye solution;
on rinsing, the carpet treated with the above product
solution of this Example 1 showed a noticeable pink
stain while the untreated carpet was again stained a
deep red. Carpets treated with the product solution of
this Example 1 did not yellow on 24 hr. exposure to UV
light (Yellowing Test described above).
Control
Example 1 was repeated using 2460 g. of
ammonium hydroxide solution (28% NH3) instead of the
5400 g. of sodium hydroxide. A product similar in
appearance to the product from Example 1 was obtained.
However, it provided little or no stain resistance in
th~ 1/2 hr. Stain Test described above.
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EXAMPLE 2
To 40 g. of SMA 1000 dispersed in 30 ml. of
water were added over the course of 1-1/4 hrs. 72 g. of
30% by weight potassium hydroxide with cooling to
maintain the temperature at 30-40OC. After additio~
was completed, the solution was stirred for 1 hr.
without heating. The mass was allowed to stand
overnight. In the morning, a trace of undissolved
polymer was removed by filtration to yield the product
which had stain resist and non-yellowing properties
similar to the product of Example 1.
EXAMPLE 3
A solution of styrene (15.0 g., 0.14 mols),
maleic anhydride (7.1 g., 0.14 mols), and dodecyl
mercaptan (2.8 g., 0.014 mols), in toluene (101 g.) was
heated to 70CC under nitrogen. Vazo~ 67 initiator
[2,2'-azo-bis-(2-methylbutyronitrile)], 0.31 g., was
added. A lO-C heat rise was noted,. After the exotherm
subsided, the reaction mass was heated for 6 hrs. at
70 C. The polymer solution was then cooled to O-C in
an ice water bath. The resulting white polymer
precipitate was filtered and suction dried to constant
weight, 19.2 g. This material was hydrolyzed according
to the procedure of Example 1. A light yellow somewhat
opaque solution was obtained.
EXAMPLE 4
Example 3 was repeated using stilbene (20.0
g., 0.21 mols) and maleic anhydride (10.9 g., 0.21
mols), and dodecyl mercaptan (2.3 g., 0.011 mols).
There obtained 29.2 g. of white polymer which on
hydrolysis provided a white opaque dispersion with
limited water solubility.
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~XAMPLE 5
A solution of styrene (7.5 g., 0.072 mol),
trans-stilbene (13.0g., 0.072 mol), maleic anhydride
(14.1 g., 0.144 mol) and dodecyl mercaptan (2.6 g.,
0.013 mol) in deoxygenated methylisobutyl ketone (150
g) was heated to 60-C under nitrogen. To initiate
polymerization, 2,2'-azo-bis-(2-methylbutyronitrile)
(0.3 gram Vazo~ 67 brand) was added, resulting in a 5~c
exotherm. After the exotherm subsided, the reaction
mixture was heated for 8 hours at 70-C under nitrogen.
Methylisobutyl ketone was then removed by distillation
under reduced pressure, yielding a slightly off-white
solid mass (36.8 g) which was hydrolyzed according to
the procedure of Example 1, giving a clear light yellow
solution.
Example 6
A cut pile, beige saxony carpet produced from 15
dpf Suessen set nylon 66 staple yarn, stain-resist
treated (the composition of Example 9 of said Liss and
Beck U.S. patent application) and latexed and finished
with a secondary polypropylene backing at a carpet
mill, was tested per Stain Test B, and was found to
exhibit slight staining (i.e. a stain rating of 4).
The carpet was cleaned in three passes with a 1:150
diluted shampoo (described below) using a Stanley
Steemer truck mount. The carpet was treated in this
manner "in placen at room temperature and was allowed
to dry at room temperature. The dried treated carpet
showed a very faint stain (a satisfactory stain rating
of 4-5) when tested by Stain Test 2 (24 hours).
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ShamPoo Formulation
Inqredient g6
Water 48
SMAC 10
Na C12 SO4 18
PGME 10
DPM 10
Fluorosurfactant 4
Total 100
Definitions
SMAC: 30 parts styrene/maleic anhydride copolymer
(ARCO SMA 1000 resin), 36.2 parts water, 33.8 parts
30% NaOH combined and heated ~o hydrolyze the resin,
using the procedure described in Example 1.
Na C12 SO4: 30% aqueous sodium lauryl sulfate.
PGME: Propylene glycol monomethyl ether
DPM: Dipropylene glycol monomethyl ether
Fluorosurfactant: A mixture of Li fluoroalkyl mercapto
propionate and diethanolammonium fluoroalkyl phosphate
in a 1.0:1.1 ratio.
EXAMPLE 7
Methyl isobutyl ketone (951.3 g) in a 4-neck
2.0 L flask fitted with mechanical agitation,
condenser, temperature controller, nitrogen bubbler and
heating mantle was heated to 70-C and sparged with
nitrogen for one hour then cooled to room temperature.
To this solution were added maleic anhydride (98.06 g,
1.0 mol), stilbene (45.06 g, 0.25 mol), styrene (78.11
g., 0.75 mol), and dodecylmercaptan (16.6 g., 0.082
.,_. . . .
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1332~8~
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mol). This mixture was heated to a steady 70C with
stirring under a nitrogen sweep. VAZ0~ 67 initiator
[2,2'-azobis--(2-methylbutyronitrile)] (2.21 g, 0.0115
mol) was then added in one portion as a solid, no
appreciable exotherm was noticed. The reaction was
stirred at 70 C for 3 hours then additional VAZ0~ 67
(1.1 G, 0.0057 mol) was added. The reaction continued
to stir at 70-C for another 3 hours, then it was cooled
to room temperature. Approximately 3/4 of the MIBK was
then removed by rotary evaporation (or vacuum
distillation at 10 mmHg). To the residual solution was
added petroleum ether (ca. 1 L) to induce
solidification of the polymer. The solid was collected
by vacuum filtration and dried in a vacuum oven at 60-C
to give the terpolymer as a light yellow powder (233.9
g., 97% yield, MW = 1090 (VP0)).
To 560 g of water in a 4-neck 2.0 L flask
fitted with mechanical agitation, temperature
controller, condenser and heating mantle was added with
stirring the terpolymer (200.0 g, ca. 0.84 mol). To
this partially dispersed solution was added slowly at
30% sodium hydroxide solution (240 g, amount based on
two mols of sodium hydroxide per mol of anhydride
residue). The solution was heated to 80-C and stirred
for 6 hours. The reaction was cooled to room
temperature and any large residual particles were
removed by vacuum filtration through a large buchner
funnel ~6.8 g of solid was collected). A light yellow,
slightly viscous, slightly cloudy alkaline solution of
30 the polysodium salt of stilbene-styrene-maleic acid ,~
terpolymer was obtain (996 g, 99.5% yield, 19.4% solids
(active ingredient).
The product solution thus obtained was
applied to nylon carpet at 5 percent (1 percent active
ingre~ient) an weight of fiber i:- a simulated beck
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dyeing apparatus at a pH of 2Ø The dried carpet was
tested by saturating it with a solution of FD&C Red Dye
No. 40 and letting it stand for 24 hours at room
temperature. It was then rinsed with cold water. The
treated carpet showed no evidence of staining while an
untreated control was deeply stained red. Carpets
treated with the terpolymer alone did not yellow on 24
hour exposure to W light.
In the simulated beck dying operation, a bath
of the stain resist solution is made up in a glass
screw cap container. A typical application bath
utilizes a 20 to 1 liquor to goods ratio with 1.0
weight % of stain resist active ingredient on weight of
fiber. An alkyl aryl sulfonate (Alkanol~ ND) or
suitable leveling agent is also added at 15 % leveling
agent on weight of stain resist active ingredient. The
carpet piece ~DuPont type 1150 Nylon 6,6 white; Superba
heat set, mock dyed level loop carpet, 3~8 inch pile
height, 30 ounces per yard, 1/10 inch gauge, 10
stitches per inch, woven polypropylene primary backing)
is then fully immersed with the tuft side facing the
center and no overlap. The required pH adjustment is
then made. A pH of 2.0 is standard unless otherwise
noted. All pH adjustments were accomplished utilizing
an aqueous 30 % sulfamic acid solution. The jar is
then capped and placed in a 70-C constant temperature
water bath. The jar is removed after 40 minutes and
the sample allowed to cool to room temperature. The
carpet sample is removed, rinsed under running
deionized water and squeezed dry by hand. The carpet
thus prepared is then fully immersed in a screw cap jar
containing 0.1 g of FD & C red dye # 40 per 1 liter of
water. The jar is capped and the carpet allowed to
stand in the solution for 2~ hours. The carpet is
removed and rinsed with tap ~ater until no more ~tain
-17-
- . -
! :
13~268~
-18-
is visually detectable in the rinse. The carpet is
then dried in a 60xC oven and evaluated as described
above.
EXAMPLE 8
A terpolymer was prepared in accordance with
the procedure of Example 7, utilizing the following
amounts of reactants and solvents:
MBIK (104.4 g)
Styrene (4.1 g, 0.04 mol)
Stilbene (10.8 g, 0.06 mol)
Maleic Anhydride (9.8 g, 0110 mol)
Dodecylmercaptan (1.4 g, 0.007 mol)
Vazo 67 (0.26 g, 0.0013 mol).
Yield: 16.9 g
The terpolymer was hydrolyzed in accordance
with the procedure of Example 7, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (29.1 g)
Aqueous NaO~I, conc. 30% (10.9 g).
EXAMPLE 9
A terpolymer was prepared in accordance with ~ t
the procedure of Example 7, utilizing the following
amounts of reactants and solvents:
MIBK (101.6 g)
Styrene (5.2 g, 0.05 mol)
Stilbene (9.0 g, 0.05 mol)
Maleic Anhydride (9.8 g, 0.10 mol)
Dodecylmercaptan (1.4 g, 0.007 mol)
VAZO~ 67 (0.25 g, 0.0013 mol).
Yield: 19.1 g
-18-
~' ' ,,, ;
.-~ ' ' . ,
.
.. :
,, ~
1332~8~
--19--
The terpolymer was hydrolyzed in accordance
with the procedure of Example 7, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (28.9 g)
Aqueous NaOH, conc. 30% (11.1 g).
EXAMPLE 10
A terpolymer was prepared in accordance with
the procedure of Example 8, utilizing the following
amounts of reactants and solvents:
MIBK (98.4 g)
Styrene (6.2 g, 0.06 mol)
Stilbene (7.2 g, 0.04 mol)
Maleic Anhydride (9.8 g, 0.10 mol)
Dodecylmercaptan (1.4 g, 0.07 mol)
VAZO 67 (0.24 g, 0.0012 mol)
Yield: 19.1 g
The terpolymer was hydrolyzed in accordance
with the procedure of Example 7, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (28.5 g)
Aqueous NaOH, conc. 30% (11.5 g).
EXAMPLE 11
A terpolymer was prepared in accordance with
the procedure of Example 7, utilizing the following
amounts of reactants and solvents:
MIBK (92.4 g)
Styrene (8.3 g, 0.08 mol~
Stilbene (3.6 g, 0.02 moi)
Maleic Anhydride (9.8 g, 0.10 mol)
Dodecylmercaptan (1.4 g, 0.007 mol)
VAZO~ 67 (0.23 g, 0.0012 mol)
--19-- .
,' `
:.
~- ' : ' . ,; :
. ~ .. .. .
. .
1332~84
-20-
Yield: 20.3 g
The terpolymer was hydrolyzed in accordance
with the procedure of Example 7, utilizng the following
amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (2B.2 g)
Aqueous NaOH, conc. 30% (11.8 g).
EXAMPLE 12
A terpolymer was prepared in accordance with
the procedure of Example 7, utilizing the following
amount~ of reactants and solvents:
MIBK (92.4 g)
Styrene (8.3 g, 0.08 mol)
15 Stilbene (3.6 g, 0.02 mol)
Maleic Anhdyride (9.8 g, 0.10 mol)
Dodecylmercaptan (1.4 g, 0.007 mol)
VAZO~ 67 (0.23 g, 0.0012 mol)
Yield: 20.3
The terpol,vmer was hydrolyzed in accordance
with the procedure of Example 7, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (27.7 g)
25 Aqueous NaOH, conc. 30% (12.3 g).
EXAMPLE 13
A terpolymer was prepared in accordance with
the procedure of Example 7, utilizing the following
amounts of reactants and solvents:
MIBK (89.6 g)
Styrene (9.4 g, 0.09 mol)
Stilbene (1.8 g, 0.01 mol)
Maleic Anhydride (9.B g, 0.10 mol)
Dodecylmercaptan (1.4 g, 0.007 m~l)
-20-
. ,
~ .
1332~84
-21-
VAZOX 67 (0.21 g, 0.0011 mol)
Yield: 19.6.g
The terpolymer was hydrolyzed in accordance
with the procedure of Example 7, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (27.3 g)
Aqueous NaOH, conc. 30% (12.7 g3.
1o EXAMPLE 14
To a 4-neck 1 L flask fitted with nechanical
agitation, condenser, addition funnel, nitrogen
bubbler, and temperature controller was added, in
order, THF (450 g), triethylamine (12.2 g, 0.12 mol),
and 4-hydroxy stilbene (19.6 g, 0.10 mol). To this
solution at room temperature was slowed added with
stirring, via addition funnel, acetic anhdyride (12.3
g, 0.12 mol). When the addition of acetic anhydride
was complete, the reaction solution was heated to 60-C
and held at this temperature with stirring for 2 hours.
The reaction was cooled to room temperature then THF
was removed in vacuo. The resulting residue was
diluted with methylene chloride (500 mL) then extracted
with 0.1 N HCl (1 X 500 mL), 30% saturated NaHCO3 (1 X
500 mL) and saturated NaCl (1 X 500 mL). The organic
layer was dried over anhydrous sodium sulfate then
filtered and concentrated in vacuo to give the
4-acetoxy stilbene as a light tan needle-like
crystalline powder (22.7 g, 95~).
EXAMPLE 15
Methyl isobutyl ketone (1025 g) in a ~-neck
5.0 L flask fitted with mechanical agitation,
condenser, temperature controller, nitrogen bubbler and
heatin(~ mantle was heated to 70C and sparged with
i -21-
.,~ ~ , . ,
. . . . .
. . , ~ ., ~ .
~, ~, ~ . . . :
133268~
-22-
nitrogen for one hour then cooled to room temperature.
To this solution were added maleic anhydride (98.06 g,
1.0 mol), 4-acetoxy stilbene (S9.6 g, 0.25 mol),
styrene (78.11 g, 0.75 mol), and dodecylmercaptan (17.6
5 g, 0.0~7 mol). This mixture was heated to a steady
70~C with stirring under a nitrogen sweep. VAZO~ 67
initiator (2,2'-azobis-(2-methylbutyronitrile)] (2.3 g,
0.012 mol) was then added in one portion as a solid, no
appreciable exotherm was noticed. The reaction was
stirred at 70~C for 3 hours then additional VAZO0 67
(1.3 g, 0.067 mol) was added. The reaction was
continued with stirring at 70C for another 5 hours;
then it was cooled to room temperature. Approximately
3/4 of the MIBK was then removed by rotary evaporation t
15 (or vacuum distillation at 10 mmHg). To the residual
solution was added petroleum ether (ca. 1 L) to induce
solidification of the polymer. The solid was collected
by vacuum filtration and dried in a vacuum oven at 60 D C
to give the terpolymer as a light yellow powder 256 g,
100%).
To 689 g of water in a 4-neck 2.0 L flask
fitted with mechanical agitation, temperature
controller, condenser and heating mantle was added with
stirring the terpolymer (256 g, ca. 1.0 mol). To this
partially dispersed solution was added slowly a 30%
sodium hydroxide solution (333 g, amount based on two
mols of sodium hydroxide per mol of anhydride residue
plus the amount needed to hydrolyze the acetate group
on the phenolic hydroxyl). The solution was heated to
80C and stirred for 6 hours. The reaction was cooled
to room temperature and any large residual particles
were removed by vacuum filtration through a large
buchner funnel. A light brown, slightly viscous,
slightly cloudy alkaline solution of the polysodium
salt of 4-hydroxy stilbene/styrene/maleic acid
-22-
1332~8~
-23-
terpolymer was obtained (1264 g, 98.9% yield, 20
solids (active ingredient~).
The product solution thus obtained was
applied to nylon carpet at 5 percent on weight of fiber
(1 percent active ingredient) in a simulated beck
dyeing apparatus as described in ~XAMPLE 7 at pH 2.0,
2.5, and 3Ø At pH 2.0 there was no evidence of
staining, pH 2.5 showed a barely discernable pink
stain, pH 3.0 was noticeably stained, while the
untreated carpet was deeply stained red. Carpets
treated with the terpolymer alone did not yellow on 24
hour exposure to W light.
EXAMPLE 16
A terpolymer was prepared in accordance with
the procedure of Example 15, utilizing the following
amounts of reactants and solvents:
MIBK (93.0 g)
Styrene (9.37 g, 0.09 mol)
4-Acetoxy Stilbene (2.38 g, 0.01 mol)
Maleic Anhydride (9.80 g, 0.10 mol)
Dodecylmercaptan (1.61 g, 0.008 mol)
VAZO 67 (0.23 g, 0.0012 mol)
Yield: 19.7.
The terpolymer was hydrolyzed in aecordance
with the procedure of Example 15, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (28.7 g)
Aqueous NaOH, conc. 30% (12.2 g)
Yield: 48.7 g.
3~
-23-
,','' ' ' "''~'`' ~ ~
!:'
~ . `; ' ~ .
-24- 13 3 2 68 4
EXAMPLE 17
A terpolymer was prepared in accordance with
the procedur~ of Example 15, utilizing the following
amounts of reactants and solvents:
MIBK (146.0 g)
Styrene (5.20 g, 0.05 mol)
4-Acetoxy Stilbene (11.9 g, 0.05 mol)
Maleic Anhydride (9.80 g, 0.10 mol)
Dodecylmercaptan (2.01 g, 0.0015 mol)
Yield: 24.6 g.
The terpolymer was hydrolyzed in accordance
with the procedure of Example 15, utilizing the
following amounts of reactants and solvents:
Terpolymer (10.0 g)
Deionized water (26.2 g)
Aqueous NaOH, conc. 30% (13.8 g)
Yield: 47.7 g.
EXAMPLE 18
Cumene (300 mls) was refluxed under nitrogen
for one hour, cooled to 70-C and 14.7 g of maleic
anhydride was added, followed by 20.28 g of styrene and
0.44 g of VAZO 67. White solids formed after 15
minutes. One hour after addition of the reactants was
completed, the reaction mixture was cooled to room
temperature and filtered. The resulting copolymer was
then washed with 6 X 100 ml of petroleum ether. Yield
of copolymer was 28.35 g. A portion of the copolymer
(27.85g) was then added to 40 g of 30~ sodium hydroxide
solution and 53 g of water and heated at 70-C for 6
hours. Yield was 111.6 g of a water solution of the
hydrolyzed copolymer.
-24-
-25- 133268~
EXAMPLE l9
Methylisobutylketone (MIBK - 100 mls) was
heated to 70CC with a stream of nitrogen bubbling below
the surface of the liquid for 2-1/2 hours. The
nitrogen stream was then removed from below the
surface. However, the system was kept under a nitrogen
atmosphere. Maleic anhydride (9.8 g) was added along
with 1.82 g of dodecylmercaptan, 14.5 g of styrene and
0.26 g of VAZO~ 67 in that order. After heating for 3
lo hours at 75 C, an additional 0.13 g of VAZ0~ 67 was
added and the reaction maintained at this temperature
for 3 more hours. Yield of copolymer was 27.0 g.
EXAMPLE 20
Cumene (300 mls) was refluxed for one hour.
The temperature was then lowered to 75C and 14.7 g of
maleic anhydride along with 30.0 g of eugenol acetate
were added. Subsequently, 0.89 g of di-tert-butyl-
peroxide was added. The reaction was then heated to
20 130-C and kept there for 12 hours. The copolymer was
then filtered and washed with petroleum ether yielding
35.5 g of purified copolymer.
EXAMPLE 21
Example 20 was repeated except eugenol
acetate was replaced with isoeugenol acetate. Yield of
copolymer was 38.7 g.
-25-
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r ~:
`' `' ", ` ` ` ';'` , . ~,, ; j
i, .
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