U.S. patent application number 10/953102 was filed with the patent office on 2005-02-17 for antistatic and antidust agents, compositions thereof, and methods of manufacture.
Invention is credited to Avadhani, Chilukuri Ver, Chowdhury, Sanjoy Kumar, Hoeks, Theodorus Lambertus, Rajaraman, Suresh K., Sarwade, Bhimrao D., Wadgaonkar, Prakash P..
Application Number | 20050038275 10/953102 |
Document ID | / |
Family ID | 31713848 |
Filed Date | 2005-02-17 |
United States Patent
Application |
20050038275 |
Kind Code |
A1 |
Chowdhury, Sanjoy Kumar ; et
al. |
February 17, 2005 |
Antistatic and antidust agents, compositions thereof, and methods
of manufacture
Abstract
A quaternary onium aromatic sulfonate represented by the
formula: 1 wherein each R.sup.1 independently comprises substituted
or unsubstituted, aliphatic or aromatic, hydrocarbyl, carbocyclic
or heterocyclic radicals, each X is selected from the group
consisting of phosphorus and nitrogen; wherein "a" has a value of
0, 1 or 2, and "b" has a value of 0 or 1 with the proviso that
(a+b) is equal to 1 or 2; G.sup.1 is an aromatic group; E comprises
a bis(carbonyloxyalkyl) polydiorganosiloxane, a
bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage;
each Y.sup.1 independently comprises hydrogen, a monovalent
hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine;
nitro; and OR, wherein R is a monovalent hydrocarbon group; "q"
represents any integer from and including zero through the number
of positions on G.sup.1 available for substitution; "t" represents
an integer equal to at least one; "s" represents an integer equal
to either zero or one; and "u" represents any integer including
zero; with the proviso that when E is an ether linkage, then X is
phosphorus.
Inventors: |
Chowdhury, Sanjoy Kumar;
(Calcutta, IN) ; Wadgaonkar, Prakash P.; (Pune,
IN) ; Hoeks, Theodorus Lambertus; (Bergen op Zoom,
NL) ; Rajaraman, Suresh K.; (Newburgh, NY) ;
Sarwade, Bhimrao D.; (Pune, IN) ; Avadhani, Chilukuri
Ver; (Pune, IN) |
Correspondence
Address: |
CANTOR COLBURN LLP
55 GRIFFIN RD SOUTH
BLOOMFIELD
CT
06002
US
|
Family ID: |
31713848 |
Appl. No.: |
10/953102 |
Filed: |
September 29, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10953102 |
Sep 29, 2004 |
|
|
|
10064792 |
Aug 16, 2002 |
|
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Current U.S.
Class: |
556/404 ;
562/84 |
Current CPC
Class: |
C08K 5/0075 20130101;
C08K 5/42 20130101; C07C 303/32 20130101; C07C 303/32 20130101;
C08K 5/0075 20130101; C07C 309/42 20130101; C08L 69/00
20130101 |
Class at
Publication: |
556/404 ;
562/084 |
International
Class: |
C07F 009/02 |
Claims
1. A method of making a quaternary onium aromatic sulfonate
compound comprising: preparing in a solvent a first solution
comprising an aromatic sulfonic acid salt having the formula:
27wherein "T" is an alkali metal, "a" is 0, 1 or 2, and "b" is 0, 1
or 2 with the proviso that (a+b) is an integer greater than or
equal to 1; G.sup.1 is an aromatic group; "E" is an ether linkage;
each Y.sup.1 independently comprises hydrogen, a monovalent
hydrocarbon group, halogen, or OR, wherein "R" is a monovalent
hydrocarbon group; "s", "t", and "u" each represents an integer
equal to one, "X" is phosphorus and "q" represents any integer from
and including zero through the number of positions on G.sup.1
available for substitution; contacting the first solution with an
acidic medium to convert the alkali metal aromatic sulfonic acid
salt to an aromatic sulfonic acid; mixing the aromatic sulfonic
acid with a quaternary compound; extracting the aromatic sulfonic
acid and quaternary salt mixture with an organic solvent to provide
a second solution; and evaporating the organic solvent from the
second solution to obtain the quaternary onium aromatic sulfonate
represented by the formula: 28wherein each R.sup.1 independently
comprises aliphatic or aromatic, substituted or unsubstituted,
carbocyclic or heterocyclic radicals, "a" has a value of 0, 1 or 2,
and "b" has a value of 0, 1 or 2, with the proviso that (a+b) is
greater than or equal to 1; G.sup.1 is an aromatic group; "E" is an
ether linkage; each Y.sup.1 independently comprises hydrogen, a
monovalent hydrocarbon group, halogen, or OR, wherein "R" is a
monovalent hydrocarbon group; "s", "t", and "u" each represents an
integer equal to one, "X" is phosphorus and "q" represents any
integer from and including zero through the number of positions on
G.sup.1 available for substitution.
2. The method of claim 1, wherein said alkali metal is selected
from the group consisting of lithium, sodium, potassium, rubidium,
and cesium.
3. The method of claim 1, further comprising maintaining a
temperature at about 10.degree. C. to about 50.degree. C. during
the method of making the quaternary onium aromatic sulfonate.
4. The method of claim 1, wherein the acidic medium is selected
from the group consisting of strong mineral acids and strongly
acidic type ion exchange resins.
5. The method of claim 1, wherein the quaternary compound is
represented by formula:Y--X(R.sup.4).sub.4wherein X is phosphorus;
each R.sup.4 independently comprises aliphatic or aromatic,
substituted or unsubstituted, carbocyclic or heterocyclic radicals;
and Y comprises hydroxide, OCOR.sup.5, and OR.sup.5, and wherein
R.sup.5 comprises aliphatic and aromatic, substituted or
unsubstituted radicals.
6. The method of claim 1, wherein the quaternary compound comprises
tetra-n-butylphosphonium hydroxide.
7. The method of claim 1, further comprising adjusting a pH of the
first solution to about 4 to about 6.
8. The method of claim 1, wherein the solvent for said aromatic
sulfonic acid salt comprises water, C.sub.1-C.sub.4 aliphatic
alcohols, tetrahydrofliran, acetonitrile, C.sub.7-C.sub.9 aromatic
hydrocarbons, or combinations containing at least one of these
solvents.
9. The method of claim 1, wherein said organic solvent for
extraction comprises halogenated aliphatic and aromatic compounds,
aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and
combinations containing at least one of these solvents.
10. A method of making a quaternary onium aromatic sulfonate
comprising: preparing in a solvent a first solution comprising an
aromatic sulfonic acid salt having the formula: 29wherein "T" is an
alkali metal, "a" has a value of 1 or 2, and "b" has a value of 0 ;
G.sup.1 is an aromatic group; each Y.sup.1 independently comprises
hydrogen, a monovalent hydrocarbon group, halogen, or "OR", "R" is
a monovalent hydrocarbon group; "s" and "u" each represents an
integer equal to zero, "q" represents any integer from and
including zero through the number of positions on G.sup.1 available
for substitution, "t" represents an integer equal to one;
contacting the first solution with an acidic medium to convert the
alkali metal aromatic sulfonic acid salt to an aromatic sulfonic
acid; mixing the aromatic sulfonic acid with a quaternary compound;
extracting the mixture with an organic solvent to provide a second
solution; and evaporating the organic solvent from the second
solution to obtain the quaternary onium aromatic sulfonate
represented by the formula: 30wherein each R.sup.1 independently
comprises aliphatic or aromatic, substituted or unsubstituted,
carbocyclic or heterocyclic radicals, each "X" is selected from the
group consisting of phosphorus and nitrogen; "a" has a value of 1
or 2 and "b" has a value of zero; G.sup.1 is an aromatic group;
each Y.sup.1 independently comprises hydrogen, a monovalent
hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine;
nitro; or OR, wherein "R" is a monovalent hydrocarbon group; "t"
represents an integer equal to one; "s" and "u" each represents an
integer equal to zero, and "q" represents any integer from and
including zero through the number of positions on G.sup.1 available
for substitution.
11. The method of claim 10, wherein said alkali metal is selected
from the group consisting of lithium, sodium, potassium, rubidium,
and cesium.
12. The method of claim 10, further comprising maintaining a
temperature of about 10.degree. C. to about 50.degree. C. during
the preparation.
13. The method of claim 10, wherein the quaternary compound
comprises the formula X(R.sup.4).sub.4--Y, wherein X is selected
from the group consisting of phosphorus and nitrogen; each R.sup.4
independently comprises aliphatic or aromatic, substituted or
unsubstituted, carbocyclic or heterocyclic radicals; and Y
comprises hydroxide, OCOR.sup.5, and OR.sup.5, wherein R.sup.5
independently comprises aliphatic and aromatic, substituted or
unsubstituted radicals.
14. The method of claim 10, wherein the acid medium is an ion
exchange resin bearing sulfonic acid groups.
15. The method of claim 10, wherein the quaternary compound is
tetra-n-butylphosphonium hydroxide.
16. The method of claim 10, further comprising adjusting a pH of
the first solution to about 4 to about 6.
17. The method of claim 10, wherein the solvent for said aromatic
sulfonic salt comprises water, C.sub.1-C.sub.4 aliphatic alcohols,
tetrahydrofuran, acetonitrile, C.sub.7-C.sub.9 aromatic
hydrocarbons, and mixtures thereof.
18. The method of claim 10, wherein said organic solvent for
extraction comprises halogenated aliphatic and aromatic compounds,
aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and
mixtures thereof.
19. A method of making a polyorganosiloxane-functionalized aromatic
sulfonate comprising: forming a reaction mixture comprising: a
hydroxyalkyl- or a hydroxyaryl-terminated polydimethylsiloxane
represented by the formula: 31wherein "Z" is selected from the
group consisting of (CH.sub.2).sub.m', wherein "m'" has a value
from about 2 to about 10, and divalent substituted and
unsubstituted aromatic radicals; and n' has a value of about 5 to
about 20; a quaternary sulfonate salt of an aromatic
sulfocarboxylic acid having the formula: 32wherein each R.sup.1 is
independently selected from aliphatic or aromatic, substituted or
unsubstituted, carbocyclic or heterocyclic radicals, and X is
selected from the group consisting of phosphorus and nitrogen; a
catalyst composition, and a solvent; stirring the reaction mixture;
and heating the reaction mixture to a temperature and time
effective to produce the polyorganosiloxane-functionalized aromatic
sulfonate having the formula: 33wherein each R.sup.1 independently
selected from aliphatic or aromatic, substituted or unsubstituted,
carbocyclic or heterocyclic radicals, and X is selected from the
group consisting of phosphorus and nitrogen; "Z" is selected from
the group consisting of (CH.sub.2).sub.m', wherein M' has a value
from about 2 to about 10, and divalent substituted and
unsubstituted aromatic radicals; and n' has a value of about 5 to
about 20.
20. The method of claim 19, wherein R.sup.1 comprises an n-butyl
group.
21. The method of claim 19, wherein the catalyst composition is
selected from the group consisting of a carbodiimide compound of
the formula:R.sup.6--N.dbd.C.dbd.N--R.sup.6,wherein R.sup.6 is
independently selected from monovalent alkyl and aryl, substituted
and unsubstituted radicals; 1-hydroxybenzotriazole, tertiary amines
of the formula (R.sup.7).sub.3N, wherein R.sup.7 is independently
selected from C.sub.1-C.sub.8 linear and branched alkyl groups; and
a heterocyclic nitrogen base.
22. The method of claim 21, wherein the carbodiimide compound is
selected from the group consisting of 1,3-dicyclohexylcarbodiimide,
1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride,
1,3-diisopropylcarbodiimide, and mixtures thereof.
23. The method of claim 21, wherein the heterocyclic nitrogen base
is selected from the group consisting of substituted and
unsubstituted pyridine, imidazoles, pyrrolidines, and mixtures
thereof.
24. The method of claim 19, wherein the solvent comprises
C.sub.1-C.sub.4 aliphatic nitriles, dichloromethane,
1,2-dichloroethane, chlorobenzene, dichlorobenzene, and
chlorotoluenes.
25. The method of claim 19, further comprising heating the reaction
mixture to a temperature of about 50.degree. C. to about a
refluxing temperature of the reaction mixture for about 8 to about
30 hours.
26. A method of making a
benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabut-
ylphosphoniumsulfonate compound comprising: contacting an aqueous
solution of an alkali metal salt of a
benzene-1-methoxy-3-n-pentadecyl-4,6-disulfo- nic acid with a
strongly acidic type ion exchange resin to generate a free acid of
the alkali metal salt in the aqueous solution; contacting the
aqueous solution with tetra-n-butylphosphonium hydroxide in an
amount effective to lower a pH of the solution to about 5 to about
6; mixing the aqueous solution with an organic solvent; separating
the organic solvent from the aqueous solution; and evaporating the
organic solvent to obtain the
benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfona-
te compound.
27. A method of making an alkylated diphenyloxide
tetrabutylphosphoniumsul- fonate compound having the formula:
34wherein a' has a value of zero or one, R.sup.2 can occupy an
ortho or a para position on the aromatic ring, and is independently
selected from the group consisting of C.sub.6 to C.sub.20 linear
and branched alkyl groups; said method comprising: contacting an
aqueous solution with an acidic type ion exchange resin, wherein
the aqueous solution comprises a compound represented by the
formula: 35wherein a' has a value of zero or one, T is selected
from hydrogen and sodium; contacting the aqueous solution with
tetra-n-butylphosphonium hydroxide in an amount effective to adjust
a pH of the aqueous solution to about 5 to about 5.5; mixing the
aqueous solution with an organic solvent; separating the organic
solvent from the aqueous solution; and evaporating the solvent from
the solution to obtain the alkylated diphenyloxide
tetrabutylphosphoniumsulfonate compound.
28. A method of making a bis(tetrabutylphosphonium)
polyorganosiloxane-functionalized aromatic sulfonate compound
having the formula: 36wherein n" is an integer having a value of
about 7; said method comprising: forming a reaction mixture
comprising: a hydroxyalkyl-terminated polydimethylsiloxane having
the formula: 37wherein n" is an integer with a value of about 7; a
quaternary sulfonate salt of an aromatic sulfocarboxylic acid
having the formula, 38a catalyst composition comprising
1-(3-dimethylaminopropyl)-3-ethylcarb- odiimide hydrochloride,
1-hydroxybenzotriazole, and triethylamine; a solvent; and heating
the reaction mixture to a temperature and for a time effective to
produce the bis(tetrabutylphosphonium)
polyorganosiloxane-functionalized aromatic sulfonate compound.
29. The method of claim 28, wherein the temperature is maintained
from about 50.degree. C. to the refluxing temperature of the
reaction mixture.
30. The method of claim 28, wherein said solvent comprises
C.sub.1-C.sub.4 nitriles, dichloromethane, 1,2-dichloroethane,
chlorobenzene, dichlorobenzene, and chlorotoluenes.
31. A method of making an antistatic or antidust thermoplastic
polymer molding composition comprising: dry-blending an aromatic
sulfonate compound with a thermoplastic resin to produce a molding
composition, wherein the aromatic sulfonate compound is represented
by the formula: 39wherein each R.sup.1 independently comprises
aliphatic or aromatic, substituted or unsubstituted, carbocyclic or
heterocyclic radicals, each X is selected from the group consisting
of phosphorus and nitrogen; wherein "a" is 0, 1 or 2, and "b" is 0,
1 or 2 with the proviso that (a+b) is an integer greater than or
equal to 1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, or an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; or OR, wherein R
is a monovalent hydrocarbon group; "q" represents any integer from
and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when E is an ether linkage, then X is phosphorus.
32. A method of making an antistatic or antidust thermoplastic
polymer molding composition comprising: combining an aromatic
sulfonate compound with a thermoplastic resin melt processing
equipment, wherein the aromatic sulfonate compound is represented
by the formula: 40wherein each R.sup.1 independently comprises
aliphatic or aromatic, substituted or unsubstituted, carbocyclic or
heterocyclic radicals, each X is selected from the group consisting
of phosphorus and nitrogen; wherein "a" is 0, 1 or 2, and "b" is 0,
1 or 2 with the proviso that (a+b) is an integer greater than or
equal to 1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, or an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; or OR, wherein R
is a monovalent hydrocarbon group; "q" represents any integer from
and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when E is an ether linkage, then X is phosphorus.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 10/064,792 filed on Aug. 16, 2002, which is herein incorporated
by reference.
BACKGROUND OF THE INVENTION
[0002] This disclosure generally relates to compositions comprising
at least one polymer and at least one antistatic agent and more
particularly, relates to fibers, films, fabrics, coatings, and
molded or blown articles comprising the antistatic polymer
compositions. In other aspects, this disclosure also relates to
processes for imparting antistatic characteristics to
substrates.
[0003] Static electricity is generated whenever dissimilar
materials move or abrade against another object. In the case of
immobile objects, even friction on the surface with ambient air can
create static electricity. The charge capacity of a substance,
defined as the capacity to generate static electricity, depends on,
among others, the condition of its surface, the dielectric
constant, the surface resistivity, and the relative humidity.
Because charge capacity is directly proportional to the surface
resistivity, it follows that a material with higher surface
resistivity, or one that is better insulator will tend to generate
a greater static charge. Accumulated static charge on an insulating
surface can range from a few volts up to several hundred thousand
volts. Thus, electrostatic discharge becomes an increasingly
worrying issue at higher levels of static charge buildup. High
levels of static electricity can cause permanent damage to
electronic components that work typically at microvolt levels.
[0004] Most of the polymers that are used to make plastics are
extremely good insulators, or in other words, they have an
extremely low surface conductance, or an extremely high surface
resistivity. This property makes polymers useful for fabricating
electrical equipment. However, polymers can build large electrical
charges that create dirt-attracting forces and naturally seek a
conductive discharge path. Moreover, polymers generally have very
low surface conductance, thus, the decay or discharge rate lasts a
very long time, a time during which the material would retain the
charge, and thus attract and retain dirt particles.
[0005] Antistatic agents constitute a unique class of polymer
additives and provide a measure of safety by preventing any fire,
resulting from sparking, caused by an accumulation of static
electricity on the surface of an article fabricated of the polymer.
They also offer aesthetic values by preventing the accumulation of
surface dust on the article. For example, lenses of automotive
headlamps are typically made of polymers, such as polycarbonates,
which have the desirable combination of heat stability, dimensional
stability, transparency, and ductility. In the past, the optics
system (also sometimes called "Fresnel") necessary to properly
focus the headlight beam on the road did not have a smooth profile.
Consequently, the dust that accumulated on the lens surface, either
during the lens molding step, or during the service life of the
headlamp, was not conspicuously visible. But with the automotive
industry moving towards lenses with a smoother profile, the
accumulated dust becomes more easily visible, therefore leading to
aesthetics issues. Thus, automotive headlamp manufacturers are
looking for alternative materials that have enhanced antistatic
properties without, of course, compromising on the other desirable
properties the current materials already possess.
[0006] Another important area, where mitigation of static charge
buildup is critical, is in conveyor belt design. For the most part
nowadays, metal conveyor belts have been replaced and are made
mostly of plastics and/or synthetic polymeric materials. The
replacement of metal with plastic has led to several distinct
advantages in conveyor belt technology, such as cleanliness
(plastic parts shed fewer particles), reliability (plastic conveyor
belts work for very long hours without attention), relatively lower
noise (plastic parts naturally damp out clanging and resonant
vibration that typically accompany metal based processes), low cost
to lifetime ratio (plastic parts undergo much slower mechanical
abrasion than metal-based systems), modularity and flexibility,
precision due to tight tolerances in the original plastic conveyor
components, and automation adaptability made possible by simple
retrofit of external systems under electric control.
[0007] The advantages of the plastic conveyor belts, outlined
above, have served very well in meeting the needs of modern
production needs over the past two decades. Then in the 1990's,
plastics-based conveyor systems began to be used in hyper-clean
environments (Class 100 or higher) essential for manufacture of
advanced electronics products and systems. But as product
dimensions and tolerances began to approach sub-micron levels,
electrostatic discharge, a phenomenon inherent in plastic materials
formulated without antistatic agents, posed difficulties to the
high technology manufacturer employing plastic conveyor belt
components. The buildup of surface charge also results in secondary
dirt contamination, which has undesirable consequences, especially
for precision, high technology electronic components. Since the
conveyor belt functions through a combination of motion and
friction, the belts tend to build up large amounts of electrostatic
charge on their surface, thus leading to an increased possibility
of electrostatic discharge. The damaging consequences of an
electrostatic charge on precision electronic equipments have
already been described above. It therefore becomes clear that for
synthetic polymers to continue to serve the increasingly demanding
requirements of the conveyor belt market, more effective plastic
materials capable of effective surface charge dissipation are
required.
[0008] Antistatic agents have generally been applied in one of two
ways: externally and internally. Spraying the surface, or dipping
the polymeric plastic material in a medium containing the
antistatic agent can be used to externally apply the antistatic
agents. On the other hand, internally applied antistatic agents are
generally added to the polymer before processing. For this reason,
internal antistatic agents have to be thermally stable and be able
to migrate to the surface during processing to impart the most
effective antistatic decay behavior.
[0009] There are many antistatic agents having a surface-active
component (surfactant-like) within its structure. Internal
antistatic agents of the anionic surfactant type are generally
difficult to handle because they are inferior in compatibility and
uniform dispersibility. Cationic surfactants containing quaternary
nitrogen have good antistatic characteristics, but have limited
utility. Non-ionic surfactants generally have inferior antistatic
characteristics compared to the ionic varieties. Moreover, due to
the limited thermal stability of surfactants in general, they are
typically not used for processing engineering thermoplastics, such
as polycarbonates. Metal salts of organic sulfonic acids have been
used as antistatic agents, but they are not thermally stable, and
not sufficiently compatible with resins.
[0010] It is therefore desirable to identify more effective
antistatic agents as additives such that they can be incorporated
into polymers without adversely affecting the physical and chemical
properties of the resulting polymer compositions. The antistatic
additives and compositions thereof described herein are extremely
useful for producing articles with outstanding abilities to
dissipate static charge buildup, and mitigate or eliminate problems
due to dust attraction/repulsion. This in turn leads to enhanced
performance, safety, and aesthetic features for these articles.
SUMMARY OF INVENTION
[0011] Briefly, one embodiment of the disclosure is a quaternary
onium aromatic sulfonate having the formula: 2
[0012] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, each X is selected from the group consisting of
phosphorus and nitrogen; "a" is 0, 1 or 2, and "b" is 0, 1 or 2
with the proviso that (a+b) is an integer greater than or equal to
1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, and an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein
R is a monovalent hydrocarbon group; "q" represents any integer
from and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when E is an ether linkage, then X is phosphorus.
[0013] In another embodiment, an antistatic composition comprises a
melt blend of an aromatic sulfonate compound and a thermoplastic
polymer, wherein the aromatic sulfonate compound is represented by
the formula: 3
[0014] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, each "X" is selected from the group consisting of
phosphorus and nitrogen; "a" is 0, 1 or 2, and "b" is 0, 1 or 2
with the proviso that (a+b) is an integer greater than or equal to
1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, and an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein
"R" is a monovalent hydrocarbon group; "q" represents any integer
from and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when "E" is an ether linkage, then "X" is phosphorus.
[0015] A method of making a quaternary onium aromatic sulfonate
compound comprises preparing in a solvent a first solution
comprising an aromatic sulfonic acid salt having the formula: 4
[0016] wherein "T" is an alkali metal, "a" is 0, 1 or 2, and "b" is
0, 1 or 2 with the proviso that (a+b) is an integer greater than or
equal to 1; G.sup.1 is an aromatic group; "E" is an ether linkage;
each Y.sup.1 independently comprises hydrogen, a monovalent
hydrocarbon group, halogen, and OR, wherein "R" is a monovalent
hydrocarbon group; "s", "t", and "u" each represents an integer
equal to one, "X" is phosphorus and "q" represents any integer from
and including zero through the number of positions on G.sup.1
available for substitution; contacting the first solution with an
acidic medium to convert the alkali metal aromatic sulfonic acid
salt to an aromatic sulfonic acid; mixing the aromatic sulfonic
acid with a quaternary compound; extracting the aromatic sulfonic
acid and quaternary salt mixture with an organic solvent to provide
a second solution; and evaporating the organic solvent from the
second solution to obtain the quaternary onium aromatic sulfonate
represented by the formula: 5
[0017] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, "a" is 0, 1 or 2, and "b" is 0, 1 or 2 with the proviso
that (a+b) is an integer greater than or equal to 1; G.sup.1 is an
aromatic group; "E" is an ether linkage; each Y.sup.1 independently
comprises hydrogen, a monovalent hydrocarbon group, halogen, and
OR, wherein "R" is a monovalent hydrocarbon group; "s", "t", and
"u" each represents an integer equal to one, "X" is phosphorus and
"q" represents any integer from and including zero through the
number of positions on G.sup.1 available for substitution.
[0018] In another embodiment, a method of making a quaternary onium
aromatic sulfonate comprises preparing in a solvent a first
solution comprising an aromatic sulfonic acid salt having the
formula: 6
[0019] wherein "T" is an alkali metal, "a" is 1 or 2, and "b" is 0;
G.sup.1 is an aromatic group; each Y.sup.1 independently comprises
hydrogen, a monovalent hydrocarbon group, halogen, and "OR", "R" is
a monovalent hydrocarbon group; "s" and "u" each represents an
integer equal to zero, "q" represents any integer from and
including zero through the number of positions on G.sup.1 available
for substitution, "t" represents an integer equal to one;
contacting the first solution with an acidic medium to convert the
alkali metal aromatic sulfonic acid salt to an aromatic sulfonic
acid; mixing the aromatic sulfonic acid with a quaternary compound;
extracting the mixture with an organic solvent to provide a second
solution; and evaporating the organic solvent from the second
solution to obtain the quaternary onium aromatic sulfonate
represented by the formula: 7
[0020] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, each "X" is selected from the group consisting of
phosphorus and nitrogen; "a" is 1 or 2 and "b" is zero; G.sup.1 is
an aromatic group; each Y.sup.1 independently comprises hydrogen, a
monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine,
chlorine; nitro; and OR, wherein "R" is a monovalent hydrocarbon
group; "t" represents an integer equal to one; "s" and "u" each
represents an integer equal to zero, and "q" represents any integer
from and including zero through the number of positions on G.sup.1
available for substitution.
[0021] In another embodiment, a method of making a
polyorganosiloxane-func- tionalized aromatic sulfonate comprises
forming a reaction mixture comprising a hydroxyalkyl- or a
hydroxyaryl-terminated polydimethylsiloxane represented by the
formula: 8
[0022] wherein "Z" is selected from the group consisting of
(CH.sub.2).sub.m', wherein "m'" has a value from about 2 to about
10, and divalent substituted and unsubstituted aromatic radicals;
and "n'" has a value of about 5 to about 20; a quaternary sulfonate
salt of an aromatic sulfocarboxylic acid having the formula: 9
[0023] wherein each R.sup.1 is independently selected from
aliphatic or aromatic, substituted or unsubstituted, carbocyclic or
heterocyclic radicals, and "X" is selected from the group
consisting of phosphorus and nitrogen; a catalyst composition, and
a solvent; stirring the reaction mixture; and heating the reaction
mixture to a temperature and time effective to produce the
polyorganosiloxane-functionalized aromatic sulfonate having the
formula: 10
[0024] wherein each R.sup.1 is independently selected from
aliphatic or aromatic, substituted or unsubstituted, carbocyclic or
heterocyclic radicals, and X is selected from the group consisting
of phosphorus and nitrogen; "Z" is selected from the group
consisting of (CH.sub.2).sub.m', wherein "m'" has a value from
about 2 to about 10, and divalent substituted and unsubstituted
aromatic radicals; and "n'" has a value of about 5 to about 20.
[0025] In another embodiment, a method of making a
benzene-1-methoxy-3-(n--
pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate compound comprises
contacting an aqueous solution of an alkali metal salt of a
benzene-1-methoxy-3-n-pentadecyl-4,6-disulfonic acid with a
strongly acidic type ion exchange resin to generate a free acid of
the alkali metal salt in the aqueous solution; contacting the
aqueous solution with tetra-n-butylphosphonium hydroxide in an
amount effective to adjust a pH of the solution to about 5 to about
6; mixing the aqueous solution with an organic solvent; separating
the organic solvent from the aqueous solution; and evaporating the
organic solvent to obtain the
benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate
compound.
[0026] A method of making an alkylated diphenyloxide
tetrabutylphosphoniumsulfonate compound having the formula: 11
[0027] wherein "a'" has a value of about zero or one, R.sup.2 can
occupy an ortho or a para position on the aromatic ring, and is
independently selected from the group consisting of C.sub.6 to
C.sub.20 linear and branched alkyl groups; said method comprises
contacting an aqueous solution with an acidic type ion exchange
resin, wherein the aqueous solution comprises a compound
represented by the formula: 12
[0028] wherein "T" is selected from hydrogen and sodium, and "a'"
has a value of about zero or one; contacting the aqueous solution
with tetra-n-butylphosphonium hydroxide in an amount effective to
adjust a pH of the aqueous solution to about 5 to about 5.5; mixing
the aqueous solution with an organic solvent; separating the
organic solvent from the aqueous solution; and evaporating the
solvent from the solution to obtain the alkylated diphenyloxide
tetrabutylphosphoniumsulfonate compound.
[0029] A method of making a bis(tetrabutylphosphonium)
polyorganosiloxane-functionalized aromatic sulfonate compound
having the formula: 13
[0030] wherein "n"" is an integer having a value of about 7
comprises forming a reaction mixture comprising a
hydroxyalkyl-terminated polydimethylsiloxane having the formula:
14
[0031] wherein "n"" is an integer with a value of about 7; a
quaternary sulfonate salt of an aromatic sulfocarboxylic acid
having the formula, 15
[0032] a catalyst composition comprising
1-(3-dimethylaminopropyl)-3-ethyl- carbodiimide hydrochloride,
1-hydroxybenzotriazole, and triethylamine; a solvent; and heating
the reaction mixture to a temperature and for a time effective to
produce the bis(tetrabutylphosphonium)
polyorganosiloxane-functionalized aromatic sulfonate compound.
[0033] A method of making an antistatic or antidust thermoplastic
polymer molding composition comprises combining an aromatic
sulfonate compound with a thermoplastic resin melt processing
equipment, wherein the aromatic sulfonate compound is represented
by the formula: 16
[0034] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, each X is selected from the group consisting of
phosphorus and nitrogen; "a" is 0, 1 or 2, and "b" is 0, 1 or 2
with the proviso that (a+b) is an integer greater than or equal to
1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, and an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein
R is a monovalent hydrocarbon group; "q" represents any integer
from and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when E is an ether linkage, then X is phosphorus.
[0035] In accordance with another embodiment, a method of making an
antistatic or antidust thermoplastic polymer molding composition
comprises combining an aromatic sulfonate compound with a
thermoplastic resin melt processing equipment, wherein the aromatic
sulfonate compound is represented by the formula: 17
[0036] wherein each R.sup.1 independently comprises aliphatic or
aromatic, substituted or unsubstituted, carbocyclic or heterocyclic
radicals, each X is selected from the group consisting of
phosphorus and nitrogen; "a" is 0, 1 or 2, and "b" is 0, 1 or 2
with the proviso that (a+b) is an integer greater than or equal to
1; G.sup.1 is an aromatic group; E comprises a
bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl)
polydiorganosiloxane, and an ether linkage; each Y.sup.1
independently comprises hydrogen, a monovalent hydrocarbon group,
alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein
R is a monovalent hydrocarbon group; "q" represents any integer
from and including zero through the number of positions on G.sup.1
available for substitution; "t" represents an integer equal to at
least one; "s" represents an integer equal to either zero or one;
and "u" represents any integer including zero; with the proviso
that when E is an ether linkage, then X is phosphorus.
[0037] The embodiments of the present disclosure have many
advantages, including the ability to produce the antistatic
compounds described above, polymer molding compositions containing
these compounds, and fabrication of antistatic articles useful in
automotive, electronics, conveyor belt systems, and display devices
applications.
DETAILED DESCRIPTION
[0038] Disclosed herein are antistatic agents, compositions
thereof, and methods of manufacture. Preferably, the antistatic
agents are quaternary onium aromatic sulfonate salts represented by
formula (I): 18
[0039] wherein each R.sup.1 independently preferably comprises
substituted and unsubstituted, aliphatic, aromatic, hydrocarbyl,
carbocyclic, or heterocyclic radicals; each "X" is selected from
the group consisting of phosphorus and nitrogen; "a" is 0, 1 or 2,
and "b" is 0, 1 or 2 with the proviso that (a+b) is an integer
greater than or equal to 1; G.sup.1 is an aromatic group; "E"
comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a
bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage;
each Y.sup.1 independently comprises hydrogen, a monovalent
hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine;
nitro; and OR, wherein "R" is a monovalent hydrocarbon group; "q"
represents any integer from and including zero through the number
of positions on G.sup.1 available for substitution; "t" represents
an integer equal to at least one; "s" represents an integer equal
to either zero or one; and "u" represents any integer including
zero; with the proviso that when "E" is an ether linkage, then "X"
is phosphorus.
[0040] In one embodiment, "E" represents a polydiorganosiloxane of
the formula (II): 19
[0041] wherein "n.sub.1" has a value from about 5 to about 20; and
R.sup.3 is independently selected from C.sub.1-C.sub.6 linear and
branched alkyl groups. In a preferred embodiment, R.sup.3 is a
methyl group.
[0042] The R.sup.1 groups in the quaternary onium aromatic
sulfonate compounds shown in formula (I) can assume a wide
variation in their structures. Each R.sup.1 can be the same or
various combinations of the aliphatic, aromatic, hydrocarbyl,
carbocyclic, and heterocyclic radicals. Suitable examples of
R.sup.1 include, but are not limited to, C.sub.1-C.sub.18 linear
and branched alkyl radicals, aralkyl, and cycloalkyl radicals. In
an embodiment, R.sup.1 is one selected from the group consisting of
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl,
n-dodecyl, n-hexadecyl, and n-octadecyl. In a particular
embodiment, R.sup.1 is an n-butyl radical.
[0043] In other embodiments, suitable R.sup.1 radicals include, but
are not limited to, C.sub.6-C.sub.14 aromatic substituted and
unsubstituted aromatic radicals. In one embodiment, R.sup.1 is
preferably an unsubstituted aromatic radical selected from the
group consisting of phenyl, indenyl, biphenyl, 1-naphthyl,
2-naphthyl, anthracenyl, and fluorenyl. In another embodiment,
R.sup.1 is preferably a C.sub.6-C.sub.14 substituted aromatic
radical, which may or may not contain other heteroatom
substituents. Examples of these include, but are not limited to
halophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl,
polyhalophenyl, bromophenyl, fluorophenyl, difluorophenyl,
alkoxyphenyl, alkoxycarbonylphenyl, nitrophenyl, cyanophenyl,
alkylphenyl, polyalkylphenyl, tolyl, xylyl, benzyl,
isopropylphenyl, isobutylphenyl, chloronaphthyl, methylnaphthyl,
isopropylnaphthyl, and the like. R.sup.1 substituents may also
comprise mixtures of alkyl, cycloalkyl, aralkyl, and aromatic
groups.
[0044] Suitable examples of the [(R.sup.1).sub.4X.sup.+] fragment
of the quaternary onium aromatic sulfonate compound include, but
are not limited to, tetramethylammonium, tetramethylphosphonium,
tetraethylammonium, tetraethylphosphonium, tetra-n-butylammonium,
tetra-n-butylphosphonium, tetra-n-pentylammonium,
tetra-n-pentylphosphonium, tetra-n-hexylammonium,
tetra-n-hexylphosphonium, tetra-n-heptylammonium,
tetra-n-heptylphosphoni- um, tetra-n-octylammonium,
tetra-n-octylphosphonium, tetraphenylammonium,
tetraphenylphosphonium, methyltriphenylammonium,
methyltriphenylphosphoni- um, benzyltriphenylammonium,
benzyltriphenylphosphonium, benzyltrimethylammonium,
benzyltrimethylphosphonium, benzyltriethylammonium,
benzyltriethylphosphonium, (n-hexadecyl)(tri-n-butyl)ammonium,
(n-hexadecyl)(tri-n-butyl)phosphonium- ,
(n-octadecyl)trimethylammonium, (n-octadecyl)trimethylphosphonium,
(n-hexadecyl)trimethylammonium, (n-hexadecyl)trimethylphosphonium,
methyl(tri-n-octyl)ammonium, methyl(tri-n-octyl)phosphonium,
methyl(tri-n-decyl)ammonium, methyl(tri-n-decyl)phosphonium,
(tri-n-butyl)(n-tetradecyl)ammonium,
(tri-n-butyl)(n-tetradecyl)phosphoni- um,
ethyl(tri-n-butyl)ammonium, and ethyl(tri-n-butyl)phosphonium, and
the like.
[0045] The R.sup.1 groups preferably do not hinder formation of the
quaternary onium aromatic sulfonate compound. In one embodiment,
the R.sup.1 groups generally comprise 1 to 18 carbons that may
further include heteroatoms such as an oxygen atom, nitrogen atom,
sulfur atoms, or the like. Examples of organic groups containing
oxygen atoms are hydrocarbon groups substituted with hydroxyl or
alkoxy group. In other embodiments, the heteroatom containing group
includes, but is not limited to, hydroxyalkyl groups such as
hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl,
hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl; and
alkoxyalkyl groups such as methoxymethyl, ethoxymethyl,
ethoxyethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl,
n-butoxyethyl, iso-butoxyethyl, polyalkylene glycol, and the like,
including mixtures thereof.
[0046] Suitable examples of heterocyclic groups for the R.sup.1
group include, but are not limited to, substituted and
unsubstituted pyridinium, pyridazinium, pyrimidinium, imidazolium,
pyrazolium, pyrazinium, thiazolium, and oxazolium radicals. The
substituted heterocyclic radicals may optionally have substituents
selected from the group consisting of halogens (such as fluorine
and/or chlorine), monovalent C.sub.1-C.sub.6 linear and branched
alkyl, monovalent C.sub.1-C.sub.6 linear and branched alkoxy, and
monovalent C.sub.6-C.sub.12 aryloxy radicals, and mixtures
thereof.
[0047] In other embodiments, suitable R.sup.1 groups are those
obtained by different combinations of the aliphatic, aromatic, and
the heteroatom containing groups described hereinabove. Other
examples for the [(R.sup.1).sub.4X.sup.+] moiety obtained by other
combinations of different types of R.sup.1 groups in different
ways, as alluded to above, will be apparent to those skilled in the
art.
[0048] In another particular embodiment, the quaternary onium
aromatic sulfonate preferably has a structure in which each R.sup.1
is an n-butyl radical, X is nitrogen, "a" is 1 or 2 and "b" is
zero; "s" and "u" each represents an integer equal to zero, "t"
represents an integer equal to one; G.sup.1 is a tetravalent phenyl
radical, and "q" represents an integer equal to two such that
Y.sup.1 is a methoxy and an n-pentadecyl group.
[0049] In another particular embodiment, the quaternary onium
aromatic sulfonate preferably has a structure in which each R.sup.1
is an n-butyl radical, X is phosphorus, "a" is 1 or 2 and "b" is
zero; "s" and "u" each represents an integer equal to zero, "t"
represents an integer equal to one; G.sup.1 is a tetravalent phenyl
radical, and "q" represents an integer equal to two such that
Y.sup.1 is a methoxy and an n-pentadecyl group.
[0050] In another embodiment, the quaternary onium aromatic
sulfonate has a structure in which each R.sup.1 is an n-butyl
radical, "a" and "b" each is 1, X is phosphorus, "s", "t" and "u"
each represents an integer each being equal to one; G.sup.1 is a
divalent aromatic radical, "q" represents an integer equal to zero,
and "E" is a bis(carbonyloxyalkyl)po- lydiorganosiloxane linkage of
the formula (III): 20
[0051] wherein "m'" has a value in the range from about 3 to about
6, and "n'" has a value in the range from about 5 to about 20.
[0052] In other embodiments, the quaternary onium aromatic
sulfonate has the structure in which each R.sup.1 is an n-butyl
radical, "a" and "b" each is 1, X is nitrogen, "s" represents an
integer equal to one, "t" and "u" represent integers each being
equal to one, G.sup.1 is a divalent aromatic radical, "q"
represents an integer equal to zero, and "E" is the
bis(carbonyloxyalkyl)polydiorganosiloxane linkage of formula
(III).
[0053] In yet another embodiment, the quaternary onium aromatic
sulfonate preferably has a structure in which each R.sup.1 is an
n-butyl radical, "E" is an ether linkage, "X" is phosphorus, "a" is
0 or 1 and "b" is one with the proviso that (a+b) is 1 or 2;
R.sup.1 is an n-butyl radical, "s", "t", and "u" each represents an
integer equal to one; G.sup.1 is a tri- or tetra-substituted phenyl
radical, "q" represents an integer equal to one such that Y.sup.1
is an alkyl group selected from the group consisting of C.sub.1 to
C.sub.20 linear and branched alkyl groups.
[0054] The quaternary onium aromatic sulfonates described
hereinabove have antistatic characteristics that make them valuable
as additives for preparing antistatic polymer compositions. In
several embodiments of the disclosure, the term "antistatic" is
also meant to include the term "antidust" since an antistatic
additive, a polymer composition or an article comprising the
antistatic additive would also show the ability to repel surface
dust. Both thermoset and thermoplastic polymers can be used for
making polymer compositions comprising the quaternary onium
aromatic sulfonate. The thermoplastic polymer is preferably
selected from the group consisting of condensation and addition
polymers. In one embodiment, the thermoplastic polymer is an
aromatic polycarbonate, a polyestercarbonate, a polyphenylene
sulfide, a polyetherimide, a polyester, a polyphenylene ether, a
polyphenylene ether/styrene polymer blends, a polyamide, a
polyketone, acrylonitrile-butadiene-styrene copolymer, a
styrene-acrylonitrile copolymer, a polyolefin, blends thereof, and
blends thereof with other materials. Suitable other materials
include, but are not intended to be limited to, antioxidants,
thermal stabilizers, ultraviolet stabilizers, processing agents,
mold release agents, fillers, flame retardants, and like additives.
The polycarbonates and polyestercarbonates are preferably obtained
from polymerization processes that include melt transesterification
method, interfacial polymerization method, solid-state
polymerization, solution, or redistribution processes, or
combinations thereof.
[0055] In a particular embodiment, a thermoplastic polymer
composition comprises an antistatic additive selected from the
group of quaternary onium aromatic sulfonates as shown in formulas
(IV), (V), and (VI). The substituent "R.sup.2" (formula V)
preferably occupies an ortho or a para position on the aromatic
ring, and is independently selected from the group consisting of
C.sub.1 to C.sub.20 linear and branched alkyl groups. The term "a'"
(formula IV) preferably has a value of about zero or one. The term
"n"" (formula VI) has a value of about 7. 21
[0056] Depending upon the type of application and the type of
thermoplastic polymer, the amount of the antistatic additive to be
employed can vary. The thermoplastic polymer compositions
preferably comprise the additive at about 2.5.times.10.sup.-3 parts
to about 6 parts per 100 parts of the total amount of polymer in
the composition, with about 3.times.10.sup.-2 parts to about 6
parts per 100 parts more preferred, and with about 0.5 parts to
about 6 parts per 100 parts even more preferred.
[0057] In some embodiments, a method for preparing the quaternary
onium aromatic sulfonate salts of formula (I) comprises the use of
aromatic sulfonic acid salts generally represented by formula
(VII): 22
[0058] wherein "a", "b", "t", "s", "u" G.sup.1, Y.sup.1, and "q"
are the same described earlier for formula (I); "T" is an alkali
metal selected from the group consisting of lithium, sodium,
potassium, rubidium, and cesium.
[0059] In various embodiments, an acidic medium is used to generate
the corresponding sulfonic acid. Examples of suitable acidic
mediums include strong acids such as for example sulfuric acid,
fluoroalkylsulfonic acids and perfluoroalkylsulfonic acids. In a
particular embodiment, the acidic medium comprises a polymeric,
strongly acidic ion exchange resin bearing sulfonic acid groups.
Suitable examples of polymeric, strongly acidic ion exchange resin
bearing sulfonic acid groups include, but are not limited to
fluorinated polymeric sulfonic acid resins, such as the Nafion.RTM.
series of resins (available commercially from E. I. Dupont de
Nemours), and sulfonated styrene-divinylbenzene copolymers prepared
using from about 0.5 mole percent to about 20 mole percent of
divinylbenzene per hundred moles of styrene employed. In particular
embodiments, the sulfonated styrene-divinylbenzene copolymers
comprise gelular and macroreticular varieties, corresponding to the
sulfonated, low and high divinylbenzene-crosslinked styrene
copolymers, respectively. An example of a gelular resin is
Amberlyst-121 (sulfonated, 4% divinylbenzene-crosslinked
polystyrene resin) available commercially from the Rohm and Haas
Company. An example of a macroreticular resin is Amberlyst-15
(sulfonated, 20% divinylbenzene-crosslinked polystyrene resin),
also available commercially from the Rohm and Haas Company.
[0060] Generally, an excess of the acidic medium is preferably
employed to ensure complete conversion to the sulfonic acid. In one
embodiment, the acidic medium employed is a sulfonated
styrene-divinylbenzene resin, and is used in an amount from about
15 times to about 20 times the number of moles of the alkali metal
sulfonic acid salt. Higher amounts of the acidic medium can also be
employed, but they are generally not required.
[0061] In one embodiment, the process of contacting the polymeric,
strongly acidic resin with the alkali metal salt of the aromatic
sulfonic acid is accomplished by allowing the solution to pass
through a column packed with polymeric acidic resin. In another
embodiment, contacting is effected by pumping the solution from the
bottom of the packed bed column and the solution of the product
mixture is collected from the top of the bed. Suitable solvents for
preparing a solution comprising the alkali metal salt of the
aromatic sulfonic acid comprise water, C.sub.1-C.sub.4 aliphatic
alcohols, tetrahydrofuran, acetonitrile, C.sub.7-C.sub.9 aromatic
hydrocarbons, and mixtures thereof. Generally the presence of water
facilitates the alkali metal ion-hydrogen ion exchange process.
[0062] The aromatic sulfonic acid composition obtained from the
alkali metal salt complex of formula (VIII) is neutralized by
contacting it with a quaternary compound represented by formula
(VIII) as shown:
X(R.sup.4).sub.4--Y (VIII),
[0063] wherein "X" is selected from the group consisting of
nitrogen and phosphorus; each R.sup.4 is independently selected
from substituted or unsubstituted aliphatic or aromatic radicals,
or substituted or unsubstituted carbocyclic or heterocyclic
radicals as previously described for the corresponding quaternary
onium sulfonic acid salt of formula (I); and Y comprises a
hydroxide, OCOR.sup.5, or OR.sup.5, wherein R.sup.5 comprises a
substituted or unsubstituted aliphatic, carbocyclic or aromatic,
radical. In one embodiment, suitable R.sup.5 groups are selected
from the group consisting of C.sub.1-C.sub.8 linear and branched
alkyl groups. In another embodiment, suitable R.sup.5 groups are
selected from the group consisting of C.sub.6-C.sub.12 aryl groups.
These quaternary ammonium and phosphonium compounds of formula
(VIII) react with a sulfonic acid group to generate the
corresponding quaternary ammonium or phosphonium sulfonate
compounds in the reaction mixture.
[0064] The quaternary compound of formula (VIII) is preferably
selected from the group consisting of tetraethylphosphonium
hydroxide, tetra-n-butylphosphonium hydroxide,
tetra-n-butylammonium hydroxide, tetra-n-octylphosphonium
hydroxide, and tetraphenylphosphonium hydroxide.
[0065] The temperature of the reaction mixture is preferably
maintained in the range from about 10.degree. C. to about
50.degree. C. In one embodiment, the temperature of the reaction
mixture is maintained in the range from about 20.degree. C. to
about 30.degree. C. In another embodiment the reaction is carried
out at an autogenous temperature. The pH of the reaction mixture is
preferably adjusted to about 4 to about 6, with a pH of about 5 to
about 5.5 more preferred.
[0066] Some surfactants are commercially available in the sulfonic
acid forms. For example, Dowfax 3B0 Surfactant is commercially
available in the acid form from Dow Chemical Company. In such cases
commercially available sulfonic acids can be directly reacted with
the quaternary compounds with adjustment of the pH as described
above to furnish the quaternary onium aromatic sulfonate
compound.
[0067] The quaternary onium aromatic sulfonate compound is then
extracted from the product mixture using a suitable solvent.
Suitable solvents include those that selectively dissolve the
quaternary onium sulfonate compound. In some embodiments, suitable
solvents comprise halogenated aliphatic and aromatic compounds,
aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and
mixtures thereof. In a particular embodiment, a suitable solvent
for extraction is chloroform.
[0068] The solvent is then evaporated such that substantially all
of the solvent is removed. In one embodiment, "substantially" means
an amount which is greater than 90 weight percent (wt. %) removed,
in other embodiments, greater than about 98 wt. % removed, in still
other embodiments, greater than about 99 wt. % removed, based on
the weight of solvent used. In still another embodiment, removal of
substantially all the solvent means that no more condensate is
obtained in the evaporation process.
[0069] For example, the method described above can be used for
preparing
benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate
(hereinafter sometimes referred to as Formula (IX)). The method
comprises mixing benzene-1-methoxy-3-(n-pentadecyl)-4,6-disulfonic
acid with a tetra-n-butylphosphonium hydroxide quaternary compound.
The required di-alkali metal salt of
benzene-1-methoxy-3-(n-pentadecyl)-4,6-disulfonic acid can be
prepared by employing a 3-step process starting from
3-pentadecylphenol. O-methylation of an alkali metal salt of
3-(n-pentadecyl)phenol with methyl iodide in a dipolar aprotic
solvent, such as dimethylsulfoxide gives 3-(n-pentadecyl)anisole.
This material is then sulfonated using concentrated sulfuric acid,
oleum, or chlorosulfonic acid to form the disulfonic acid
derivative. When chlorosulfonic acid is used, the product is a
sulfonyl chloride derivative which upon hydrolysis forms the
sulfonic acid. The disulfonic acid is isolated in a pure form as a
di-alkali metal salt since this route helps in separating the
organic impurities present in the sulfonation reaction mixture.
[0070] Another example of the utility of the method described above
is for making an alkylated diphenyloxide
tetrabutylphosphoniumsulfonate compound having the formula (V). The
starting material for making the compound shown in formula (V) is
represented by the formula (X): 23
[0071] wherein "T" is selected from hydrogen and sodium, and "a'"
and R.sup.2 are as described previously. The sodium salts of
formula (X) wherein a' is 1 is, for example commercially available
from Dow Chemical Company under the trade name Dowfax.RTM.
surfactants. The sulfonic acid forms of formula (X), wherein a' is
1, and R.sup.2 is a C.sub.10 or a C.sub.12 alkyl group is, for
example commercially available from Dow Chemical Company.
[0072] A polyorganosiloxane-functionalized aromatic sulfonate
having the formula (VI) can be made by mixing in a suitable
solvent, a hydroxyalkyl-terminated polydimethylsiloxane having the
formula (XI), 24
[0073] wherein "n"" has a value of about 7; a quaternary sulfonate
salt of an aromatic sulfocarboxylic acid having the formula (XII):
25
[0074] wherein R.sup.1 and "X" are as previously described, and a
catalyst. The resulting mixture is then preferably heated with
stirring for a suitable duration to effect an esterification
reaction and form the desired product. To effect complete reaction,
the reaction mixture is then preferably heated to a temperature of
about 50.degree. C. to about a refluxing temperature of the
reaction mixture, more preferably, to a temperature of about
70.degree. C. to about 90.degree. C., and even more preferably to a
temperature of about 50.degree. C. to about 70.degree. C. The
duration of heating is preferably from about 8 hours to about 30
hours, with about 12 hours to about 26 hours more preferred, and
from about 18 hours to about 24 hours even more preferred.
[0075] The catalyst composition comprises at least one carbodiimide
compound of the formula (XIII):
R.sup.6--N.dbd.C.dbd.N--R.sup.6 (XIII),
[0076] wherein R.sup.6 is independently selected from monovalent
alkyl and aryl, substituted and unsubstituted radicals;
1-hydroxybenzotriazole, and at least one nitrogen base selected
from the group consisting of tertiary amines of the formula
(R.sup.7).sub.3N, where R.sup.7 is independently selected from
C.sub.1-C.sub.8 linear and branched alkyl groups; and heterocyclic
nitrogen bases. In one embodiment, the heterocyclic nitrogen base
that can be used include, but are not limited to substituted and
unsubstituted pyridines, imidazoles, and pyrrolidines. Any mixture
of the foregoing list of tertiary amines and heterocyclic bases can
also be used for the esterification reaction. In a particular
embodiment, the carbodiimide compound is at least one selected from
the group consisting of 1,3-dicyclohexylcarbodiimide,
1-[3-(dimethylamino)propyl]-3-ethylcarbo- diimide hydrochloride,
and 1,3-diisopropylcarbodiimide.
[0077] The solvent for the esterification reaction comprises
C.sub.1-C.sub.4 nitriles, dichloromethane, 1,2-dichloroethane,
chlorobenzene, dichlorobenzene, and chlorotoluenes. Acetonitrile is
a preferred solvent for this reaction since it can be easily
removed by evaporation and facilitates product isolation.
[0078] In another exemplary embodiment, the quaternary sulfonate
salt of a sulfocarboxylic acid used is represented by formula (XII)
in which R.sup.1 is an n-butyl group, and "X" is selected from the
group consisting of phosphorus and nitrogen.
[0079] In another exemplary embodiment of the method, the
preparation of the bis(tetrabutylphosphonium)
polyorganosiloxane-functionalized aromatic sulfonate formula (VI)
as previously shown, preferably comprises the use of a solvent
selected from the group consisting of C.sub.1-C.sub.4 nitriles,
dichloromethane, 1,2-dichloroethane, chlorobenzene,
dichlorobenzene, and chlorotoluenes. Acetonitrile is a preferred
solvent for this reaction. Product formation is accomplished by
heating the reaction mixture, whereby the temperature is maintained
from about 50.degree. C. to the refluxing temperature of the
reaction mixture, and more preferably, from about 50.degree. C. to
about 85.degree. C.
[0080] The quaternary aromatic onium sulfonate compounds may have
surface migratory aptitude that can aid in dissipation of localized
static charge accumulated on a polymer surface. These compounds
possess a polar, hydrophilic onium sulfonate group, and a
non-polar, hydrophobic moiety. While not wanting to be bound by
theory, it is believed that the polar group attracts ambient
moisture to form a layer of water molecules on the polymer surface.
These water molecules in turn are hydrogen bonded to each other.
Dissipation of the localized surface charge occurs through this
hydrogen-bonded layer of water molecules, thus leading to
antistatic activity.
[0081] The quaternary aromatic onium sulfonate compounds can be
incorporated into polymers, particularly thermoplastic polymers,
together with other additives during the molding process to afford
antistatic polymer molding compositions without adversely affecting
the transparency properties. Such polymer molding compositions are
commercially valuable for preparing antistatic articles. In many
embodiments, the articles that can be prepared using the above
polymer molding compositions are those comprising forward lighting
assemblies, automotive headlamp lenses, fog lamp lenses, ophthalmic
devices, printer devices, and display panel devices for appliances.
Examples of thermoplastic molding compositions include those
comprising aromatic polycarbonate, polyestercarbonate,
polyphenylene sulfide, polyetherimide, polyester, polyphenylene
ether, polyphenylene ether/styrene polymer blends, polyamide,
polyketone, acrylonitrile-butadiene-styrene copolymer,
styrene-acrylonitrile copolymer, polyolefin, blends thereof, and
blends thereof with other materials, such as glass.
[0082] Numerous approaches can be used for incorporating the
quaternary aromatic onium sulfonate compounds into thermoplastic
polymers. For example, a dry blending process includes preparing
the polymer molding composition by mixing all of the components
prior to subjecting the mixture to a molding process for
fabricating the articles. The various components may include the
polymer resin (powder, pellets, or the like), the quaternary
aromatic onium sulfonate compounds and various additives such as,
but not limited to, antioxidants, thermal stabilizers, ultraviolet
stabilizers, processing agents, mold release agents, fillers, flame
retardants, and the like.
[0083] Another method for incorporating the quaternary aromatic
onium sulfonate compounds into thermoplastic polymers comprises
combining the ingredients, including at least one and/or antidust
additives discussed above, with at least one polymer in a melt
processing equipment. Depending upon the nature of the antistatic
additive, a solvent may be optionally added to aid in mixing with
the rest of the feed mixture. In some embodiments, the processing
machine may have a devolatilization system to effectively remove
volatiles such as the optional solvent during the processing step.
Any melt processing equipment may be employed and those skilled in
the art may choose appropriate equipment without undue
experimentation depending upon such factors as the type of polymer
to be processed. In various embodiments suitable melt processing
equipment includes, but is not limited to, extruders, kneaders,
roll-mills and similar equipment. The method of molding the above
molding compositions may include at least one step of injection
molding, sheet molding, thermoforming, and/or blow molding.
[0084] In another embodiment, molding may be accomplished using a
molten feed stream, instead of a powder and/or pellet form of the
thermoplastic polymer component. This option is advantageous in a
polymer production facility, wherein the final product exiting the
polymerization process is in a neat molten state. Thus, the molten
polymer is directly fed into a molding machine together with the
quaternary aromatic onium sulfonate compound, together with other
desired processing additives.
[0085] In addition to employing the compositions in molding and
blow molding processes, the antistatic compositions described
herein are useful for coating articles and for preparing fibers.
The fibers can then be employed for manufacture of fabric and the
like.
[0086] In the examples to follow, the following procedures were
employed.
[0087] Glass transition temperatures (hereinafter referred to as
T.sub.g) were measured using a Perkin Elmer Model TGA-7
Thermogravimetric Analyzer. Percent transmission (hereinafter
referred to as "% T"), yellowness index (hereinafter referred to as
"YI"), and percent haze (hereinafter referred to as "% Haze") were
measured using Pacific Scientific.RTM. Model XL-835 colorimeter.
The percent change in melt viscosity ratio (hereinafter referred to
as "% .DELTA.MVR") was measured using a Gottfert.RTM. Rheograph
2002 instrument. Heat distortion temperature (hereinafter referred
to as "HDT") is a measure of the heat deflection temperature under
a load and was measured in accordance with procedure defined by ISO
75. The Vicat softening temperature (hereinafter referred to as
"VICAT") is the temperature at which a plastic starts to soften
rapidly and was measured in accordance with procedure defined by
ISO 306.
[0088] Tulsion T-42 MP (H.sup.+), an acidic gel type ion exchange
resin was purchased from Thermax Limited, India. The resin had
moisture content of about 50-52% and an exchange capacity of about
1.8 milliequivalents of H.sup.+ per unit volume of resin in the wet
state (about 4.9 milliequivalents of H.sup.+ per unit volume of
resin in the dry state). The Dowfax.RTM. surfactants were procured
from Dow Chemical Company.
EXAMPLE 1
[0089] In this example,
benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabuty- lphosphonium
sulfonate (formula (IX)) was prepared.
[0090] Into a 2-liter round-bottomed flask was placed 500
milliliters (ml) of dimethyl sulfoxide, 100 grams (g) of
3-(n-pentadecyl)phenol (0.33 mol), and 73.55 g of potassium
hydroxide (1.31 mol). To this mixture, 93.5 g of methyl iodide (
0.66 mol) was added drop wise with stirring at room temperature.
After the addition, the reaction mixture was stirred for a further
6 hours. Then the reaction mixture was poured into deionized water
(1.5 liters). The organic material was extracted by addition of
diethyl ether. The diethyl ether layer was separated, washed with
water, dried over anhydrous sodium sulfate, and finally evaporated
to afford the crude product as a viscous fluid. This material was
purified by silica gel column chromatography using petroleum ether
as the eluent to furnish 3-(n-pentadecyl)anisole (104.6 g, 97% of
theoretical yield) having a melting range of 27-28.degree. C.
[0091] Into a 500 ml round-bottomed flask fitted with a magnetic
stirring bar and a dropping funnel was added
3-(n-pentadecyl)anisole (56 g, 0.18 mol). The contents of the flask
were chilled in a cooling bath. Concentrated sulfuric acid (46.5 g,
0.48 mol) was added drop wise over a period of about 30 minutes
with stirring so as to maintain an internal temperature of about
10.degree. C. After all the sulfuric acid had been added, the
cooling bath was removed, and the reaction mixture was heated to
maintain a temperature of about 70.degree. C. for about 6 hours.
Then the mixture was cooled to room temperature and poured into
ice-cold deionized water (500 ml) with stirring. The mixture was
extracted with ethyl acetate (3.times.100 ml) to remove unreacted
3-(n-pentadecyl)anisole as an ethyl acetate solution. The aqueous
layer was neutralized with sodium bicarbonate and cooled to about
10.degree. C. for about 3 hours. The precipitated sodium sulfate
was filtered off, and the filtrate was diluted with n-butanol (500
ml). The n-butanol solution was concentrated on a rotary evaporator
under reduced pressure. Methanol (500 ml) was added to the residual
material whereupon some more sodium sulfate precipitated out which
was removed by filtration. The process of adding methanol,
concentration under reduced pressure, subsequent addition of more
methanol, and filtration was done two more times to ensure complete
removal of sodium sulfate. The filtrate resulting finally was
evaporated under reduced pressure to furnish crude disodium salt of
benzene-1-methoxy-3-(n-pentadecyl)-4,6-disulfonic acid. This
material was washed with hot ethanol (3.times.300 ml) to remove
colored impurities.
[0092] The clarified disodium salt from above was dissolved in
deionized water and the solution was passed through a column packed
with Tulsion H.sup.+ ion exchange resin (previously purified by
washing with hot distilled water). The eluate from the column was
collected and treated with tetra-n-butylphosphonium hydroxide (used
as a 40% aqueous solution) until the pH of the reaction mixture was
about 5.6. The reaction mixture was extracted with chloroform (500
ml); the chloroform solution was washed with deionized water, and
dried over anhydrous sodium sulfate. Removal of the chloroform on a
rotary evaporator, followed by drying under high vacuum using an
oil pump afforded the product as a pale yellow viscous liquid.
Proton NMR spectrum of the material showed that it was the desired
product.
EXAMPLE 2
[0093] In this example, alkylated diphenyloxide
tetrabutylphosphoniumsulfo- nates of formula (XIV) with R.sup.2
groups having varying alkyl chain lengths (A, B, C, and D) were
prepared. 26
[0094] The alkylated diphenyloxide sulfonic acids that were
commercially available were reacted with tetra-n-butylphosphonium
hydroxide as follows.
[0095] A solution of tetra-n-butylphosphonium hydroxide (40%
aqueous solution) was added drop wise to the appropriate alkylated
diphenyloxide sulfonic acid (50 g), dissolved in about 200 ml of
deionized water, with stirring at room temperature until the pH of
the reaction mixture indicated a value of about 5.5. The reactions
were monitored using a pH meter. The reaction mixture was extracted
with dichloromethane (250 ml), and the dichloromethane layer was
separated, washed three times with water, dried over anhydrous
sodium sulfate, and evaporated to furnish the desired product. The
data is shown in Table 1.
[0096] In those cases where the sodium salts of the alkylated
diphenyloxide sulfonic acids were available, they were first
converted to the corresponding sulfonic acid derivatives by
treatment with an acidic ion exchange resin, such as Tulsion
H.sup.+ ion exchange resin, using the same procedure as described
above for making the compound having formula (IX).
[0097] In this manner, the alkylated diphenyloxide sulfonate
compounds (XIV-A), (XIV-B), (XIV-C), and (XIV-D) were prepared by
starting from the corresponding C.sub.6, C.sub.10, C.sub.12, and
C.sub.16 alkylated diphenyl oxide sodium sulfonic acids,
respectively.
1TABLE 1 Alkyl group in the starting Moles of Weight of alkylated
diphenyloxide Molecular SO.sub.3H present TBPH (40% sulfonic acids
weight in 50 g of acid solution) used C.sub.6 430 0.23 151 C.sub.10
498 0.20 139 C.sub.12 524 0.19 132 C.sub.16 596 0.17 116
EXAMPLE 3
[0098] This example describes the synthesis of a
bis(tetrabutylphosphonium- ) polyorganosiloxane-functionalized
aromatic sulfonate compound (formula VI).
[0099] In a 1-liter beaker was placed 4-sulfobenzoic acid (20.2 g,
0.1 mol), and added deionized water (200 ml) to dissolve the
material. To this solution was added 40% aqueous solution of
tetra-n-butylphosphonium hydroxide (69 g, 0.1 mol). The solid that
precipitated out was isolated by filtration using a sintered
funnel, and washed several times with deionized water. The salt was
then crystallized from tetrahydrofuran to give pure
4-(tetra-n-butylphosphoniumsulfonato)benzoic acid (m.p. 182.degree.
C.-184.degree. C.; 32.20 g, 70% of theoretical yield). Proton NMR
spectrum of the material verified the purity of the above
intermediate product.
[0100] Into a 500 ml three-necked round bottom flask fitted with a
magnetic stirring bar, a dropping funnel and a reflux condenser
were taken allyl alcohol (117 g, 2.01 mol) and
chlorotrimethylsilane (1 ml). To this mixture maintained at ambient
temperature was added 1, 1, 1, 3, 3, 3-hexamethyldisilazane (160.0
g, 0.99 mol) drop wise with magnetic stirring. After completion of
the addition, the reaction mixture was heated under reflux for
about 6 hours. Fractional distillation of the mixture furnished 227
g (88% of theoretical yield) of the intermediate product,
allyloxytrimethylsilane having a boiling range from about
100.degree. C. to about 101.degree. C.
[0101] Into a 500 ml three-necked round bottom flask equipped with
a magnetic stirring bar, a reflux condenser, and a dropping funnel
was placed hydride-terminated polydimethyl siloxane (purchased from
Aldrich; number average molecular weight (M.sub.n)=580; 158.0 g,
0.27 mol) and 8 wt % solution of hydrogen hexachloroplatinate (1.5
ml). The mixture was heated to 60.degree. C. and
allyloxytrimethylsilane (77 g, 0.59 mol) was added drop wise over a
period of about 1.5 hours. After the addition, the contents of the
reaction flask was slowly heated to about 120.degree. C. and held
at that temperature for about 3 hours. Excess
allyloxytrimethylsilane was then removed by distillation. The
reaction mixture was cooled to room temperature and suction
filtered through a Celite-magnesium sulfate-Celite bed to furnish
176.0 g, (77.20% of theoretical yield) of
bis(trimethylsilyloxypropyl)-terminated poly (dimethylsiloxane) as
a viscous oily product.
[0102] Into a 500 ml round bottom flask fitted with a magnetic
stirring bar was taken bis(trimethylsilyloxypropyl)-terminated poly
(dimethylsiloxane) prepared above (170.0 g) and 300 ml of a
solution of hydrochloric acid (prepared by diluting 85 ml of 35%
hydrochloric acid with 215 ml of tetrahydrofuran). The resulting
mixture was stirred at room temperature for about 6 h and then
diluted with diethyl ether (1000 ml). The ether solution was washed
with aqueous sodium bicarbonate solution (4.times.200 ml), followed
by washing with brine (2.times.200 ml). The ether solution was
separated, dried over anhydrous sodium sulfate, filtered, and
concentrated on a rotary evaporator. The residual oily product was
distilled under reduced pressure. The fraction having a boiling
range from about 65.degree. C. to about 80.degree. C. at about 0.06
mm Hg was collected. In this manner, 96 g of the desired
bis(hydroxypropyl)-terminated poly(dimethylsiloxane) product was
obtained. NMR analysis of the product indicated the material had a
number average molecular weight (M.sub.n) of about 770.
[0103] Into a 100 ml round bottom flask fitted with a magnetic
stirring bar was placed the
4-(tetra-n-butylphosphoniumsulfonato)benzoic acid prepared as
described above (1.0 g, 2.2 mmol), bis(hydroxypropyl)-termina- ted
poly(dimethylsiloxane) (0.77 g, 1 mmol),
1-[3-(dimethylamino)propyl]-3- -ethylcarbodiimide hydrochloride
(0.77 g, 4 mmol), triethylamine (0.51 g, 5 mmol),
1-hydroxybenzotriazole (0.68 g, 5 mmol), and acetonitrile (20 ml).
The resulting mixture was heated under reflux for about 24 h. After
cooling the reaction mixture to room temperature, acetonitrile was
removed under reduced pressure, and the residual material was
dissolved in dichloromethane. The dichloromethane solution was
successively washed with aqueous sodium bicarbonate solution,
brine, water, dried over anhydrous sodium sulfate, filtered, and
concentrated on a rotary evaporator to furnish the crude product as
a viscous oily material. This material was purified using silica
gel column chromatography. Initially, ethyl acetate was used as the
eluent to remove any unreacted bis(hydroxypropyl)-terminated
poly(dimethylsiloxane). Then methanol was used as the eluent to
isolate the desired product bis(tetrabutylphosphoni- um)
polyorganosiloxane-functionalized aromatic sulfonate (VI) (1.42 g,
75% of theoretical yield). Proton NMR spectrum of the material
indicated that pure product had been isolated.
EXAMPLE 4
[0104] In this example, an aromatic polycarbonate resin was
melt-blended with the appropriate amount of the anti-static agent
as indicated below. The aromatic polycarbonate resin used in the
examples was a BPA homopolycarbonate resin having an intrinsic
viscosity of about 0.46 deciliters per gram as measured in
dichloromethane at 20.degree. C. The molding mixture also contained
2.7 grams of silicone oil mold release agent per kilogram of
molding mixture and 3.9 grams of stabilizers per kilogram of
molding mixture, the addition of which are not believed to affect
the antistatic properties. The molding mixture was molded in a 25
mm twin-screw extruder using an operating temperature of about
285.degree. C. After being extruded through a die orifice, the
resulting strands were quenched in water and cut into pellets,
which were dried at about 120.degree. C. for about 2 hours (h). The
dried pellets were injection molded using a single screw
injection-molding machine to produce 10 centimeters (cm) square
plaques having a thickness of about 2.5 millimeters (mm). The
maximum temperature for the injection-molding barrel was about
285.degree. C.
[0105] The plaques required for carrying out the static decay tests
were obtained from the larger plaques prepared above. Each plaque
used for the static decay test measured about 78 mm.times.58
mm.times.2.5 mm. Prior to the test, the plaques were conditioned at
a temperature of about 23.degree. C. and a relative humidity of
about 50% for about three days. The static decay tests were carried
out on these plaques using a Static Honestineter, Model S-5109
instrument manufactured by Shishido Electrostatic Ltd. The applied
voltage was cut-off when the surface charge attained a fixed value
of about 3 kilovolts. Subsequently, the decay of surface charge was
followed with time with a detector. The static half decay time
(indicated by "T.sub.1/2") represents the time at which the surface
charge reached a value that was half the initial value. The above
procedure was repeated for a control experiment where no antistatic
additive was added. Table 2 refers to measurements made with
plaques containing 25.6 mmol of the antistatic additive per
kilogram of the polycarbonate. Table 3 refers to measurements made
with plaques containing 1.5 weight percent of the antistatic
additive relative to weight of the polycarbonate taken. "NA" in the
tables means "not available".
2TABLE 2 Formula of Antistatic % .DELTA.MVR compound T.sub.1/2
(sec) % T YI Haze (%) HDT VICAT (IX) 16.6 88.6 6.23 4.76 33.1 117.4
137.7 (XIV-D) 114.7 NA NA NA 36.3 123.1 141.4 (VI) 9.0 NA NA NA
155.05 112.5 131.4 None* >>1500 90 NA NA NA 150 *Control
[0106]
3TABLE 3 Formula of Antistatic .DELTA.MVR compound T.sub.1/2 (sec)
% T YI % Haze (%) Tg (.degree. C.) (XIV-A) 200 NA NA NA 87.8 145.4
(XIV-B) 200 79.0 12 77.8 103.4 145.2 (XIV-C) 127.0 NA NA NA 133.4
144.4 None* >>1500 90 NA NA NA 150 *Control
[0107] The results in Table 2 and Table 3 show that the antistatic
compounds represented exhibit significant reduction in static decay
properties compared to the control without an antistatic compound.
In addition to the reduction in static decay, the polymer
compositions comprising the aforementioned antistatic compounds
maintain the polymers inherent physical properties, such as, for
example, glass transition temperature.
[0108] While the disclosure has been illustrated and described in
typical embodiments, it is not intended to be limited to the
details shown, since various modifications and substitutions can be
made without departing in any way from the spirit of the present
invention. As such, further modifications and equivalents of the
disclosure herein disclosed may occur to persons skilled in the art
using no more than routine experimentation, and all such
modifications and equivalents are believed to be within the spirit
and scope of the disclosure as defined by the following claims. All
Patents cited herein are incorporated herein by reference.
* * * * *