U.S. patent application number 12/137646 was filed with the patent office on 2009-02-05 for polycrystalline conducting polymers and precursors thereof having adjustable morphology and properties.
Invention is credited to Marie Angelopoulos, Yun-Hsin Liao, Ravi F. Saraf.
Application Number | 20090032775 12/137646 |
Document ID | / |
Family ID | 46202879 |
Filed Date | 2009-02-05 |
United States Patent
Application |
20090032775 |
Kind Code |
A1 |
Angelopoulos; Marie ; et
al. |
February 5, 2009 |
POLYCRYSTALLINE CONDUCTING POLYMERS AND PRECURSORS THEREOF HAVING
ADJUSTABLE MORPHOLOGY AND PROPERTIES
Abstract
Polycrystalline materials containing crystallies of precursors
to electrically conductive polymers and electrically conductive
polymers are described which have an adjustable high degree of
crystallinity. The intersticial regions between the crystallites
contains amorphous material containing precursors to electrically
conductive polymers and/or electrically conductive polymers. The
degree of crystallinity is achieved by preparing the materials
under conditions which provide a high degree of mobility to the
polymer molecules permitting them to associate with one another to
form a crystalline state. This is preferable achieved by including
additives, such as plasticizers and diluents, to the solution from
which the polycrystalline material is formed. The morphology of the
polycrystalline material is adjustable to modify the properties of
the material such as the degree of crystallinity, crystal grain
size, glass transition temperature, thermal coefficient of
expansion and degree of electrical conductivity. High levels of
electrical conductivity are achieved in in the electrically
conductive polycrystalline materials without stretch orienting the
material. The enhanced electrical conductivity is isotropic as
compared to a stretch oriented film which has isotropic electrical
conductivity.
Inventors: |
Angelopoulos; Marie;
(Cortlandt Manor, NY) ; Liao; Yun-Hsin;
(Tarrytown, NY) ; Saraf; Ravi F.; (Briarcliff
Manor, NY) |
Correspondence
Address: |
Daniel P. Morris;IBM CORPORATION
Intellectual Property Law Dept., P.O. Box 218
Yorktown Heights
NY
10598
US
|
Family ID: |
46202879 |
Appl. No.: |
12/137646 |
Filed: |
June 12, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09727615 |
Dec 1, 2000 |
7404914 |
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12137646 |
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09268527 |
Mar 12, 1999 |
6210606 |
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09727615 |
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08620168 |
Mar 22, 1996 |
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09268527 |
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60007688 |
Nov 29, 1995 |
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Current U.S.
Class: |
252/500 ;
524/130; 524/287; 524/315; 524/320 |
Current CPC
Class: |
Y10T 428/249958
20150401; H01B 1/128 20130101; C08G 61/12 20130101 |
Class at
Publication: |
252/500 ;
524/287; 524/320; 524/315; 524/130 |
International
Class: |
H01B 1/12 20060101
H01B001/12; C08K 5/09 20060101 C08K005/09; C08K 5/10 20060101
C08K005/10; C08K 5/5317 20060101 C08K005/5317 |
Claims
1. A composition of matter comprising: a polycrystalline material
comprising crystallites of polymers with intersticial regions
therebetween; wherein said polymer is a precursor to an
electrically conductive polymer; said intersticial regions between
said crystallites comprising amorphous material comprising an
additive; said additive provides mobility to said polymer to allow
said polymer to associate with one another to achieve said
crystallites; said polycrystalline material is characterized by a
degree of crystallinity and a degree of amorphous regions, said
degree of polycrystallinity and said degree of amorphous regions
are selected by selecting the composition of said additive and the
amount of said additive; and wherein said additive is a plasticizer
selected from the group consisting of: Adipic acid derivatives
Sebacic acid derivatives Azelaic acid derivatives Stearic acid
derivatives Benzoic acid derivatives Diethyl succinate Citric acid
derivatives N-Ethyl o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
2. A composition of matter according to claim 1, wherein said
structure is electrically conductive and has an isotropic
electrical conductivity.
3. A composition of matter according to claim 1, wherein said
polymer is selected from the group consisting of substituted and
unsubstituted polyparaphenylene vinylenes, polyparaphenylenes,
polyanilines, polythiophenes, polyazines, polyfuranes,
polypyrroles, polyselenophenes, poly-p-phenylene sulfides,
polyacetylenes formed from soluble precursors, combinations thereof
and blends thereof with other polymers and copolymers of the
monomers thereof.
4. A composition of matter according to claim 1, wherein said
structure has crystallinity greater than about 25%.
5. A composition of matter comprising: a polycrystalline material
comprising crystallites of polymers with intersticial regions
therebetween; said polymer is a precursor to an electrically
conductive polymer; said intersticial regions comprise an amorphous
material selected from the group consisting of said polymers; said
amorphous material includes an additive; said polycrystalline
material is characterized by a degree of crystallinity and a degree
of amorphous regions, said degree of polycrystallinity and said
degree of amorphous regions are selected by selecting the
composition of said additive and the amount of said additive; and
wherein said additive is a plasticizer selected from the group
consisting of: Adipic acid derivatives Sebacic acid derivatives
Azelaic acid derivatives Stearic acid derivatives Benzoic acid
derivatives Diethyl succinate Citric acid derivatives N-Ethyl
o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
6. A composition of matter according to claim 5, wherein said
polymer is an electrically conductive polymer and said
polycrystalline material has a conductivity which is isotropic.
7. A composition of matter according to claim 5, wherein said
polymer is selected from the group consisting of substituted and
unsubstituted polyparaphenylene vinylenes, polythianophthenes,
polyparaphenylenes, polyanilines, polythiophenes, polyazines,
polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene
sulfides, polyacetylenes formed from soluble precursors,
combinations thereof and blends thereof with other polymers and
copolymers of the monomers thereof.
8. A composition of matter according to claim 1, wherein the amount
of said additive is adjustable.
9. A composition of matter according to claim 8, wherein said
amount is controlled to modify physical properties of said
structure.
10. A composition of matter according to claim 9, wherein said
physical properties are selected from the group consisting of glass
transition temperature, compliance, thermal coefficient of
expansion, modulus, yield and tensile strength, hardness,
density.
11. A composition of matter according to claim 1, wherein said
crystallites have a size greater than about 80 .ANG..
12. A composition of matter according to claim 5, wherein said
crystallites have a size greater than about 80 .ANG..
13. A composition of matter comprising: a polycrystalline material
comprising crystallites of polyaniline with intersticial regions
therebetween; said polyaniline is a precursor to an electrically
conductive polyaniline; said intersticial regions comprise an
amorphous material selected from the group consisting of
polyaniline; said amorphous material includes an additive in an
amount from about 0.001% to about 90% by weight; said
polycrystalline material is characterized by a degree of
crystallinity and a degree of amorphous regions, said degree of
polycrystallinity and said degree of amorphous regions are selected
by selecting the composition of said additive and the amount of
said additive; and wherein said additive is a plasticizer selected
from the group consisting of: Adipic acid derivatives Sebacic acid
derivatives Azelaic acid derivatives Stearic acid derivatives
Benzoic acid derivatives Diethyl succinate Citric acid derivatives
N-Ethyl o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
14. A composition of matter according to claim 1, wherein the
amorphous material in the intersticial regions contains
crosslinks.
15. A composition of matter according to claim 1, wherein the
amorphous material in the intersticial regions are
deaggregated.
16. A composition of matter according to claim 1, wherein the
additive is in an amount for about 0.001% to about 90% by
weight.
17. A structure according to claim 1, wherein said amorphous
regions have crystalline order.
18. A structure according to claim 1, wherein said additive has a
different material composition from said polycrystalline
material.
19. A structure comprising: a surface of a structure selected from
the group consisting of an electrostatic discharge shield, a wire,
a solder, around an electromagnetic interference shield, a
semiconductor device, and a corrodible material; said surface has
disposed thereon a composition of matter comprising crystalline
material comprising crystallites of polymers with intersticial
regions therebetween; wherein said polymer is a precursor to an
electrically conductive polymer; said intersticial regions between
said crystallites comprising amorphous material comprising an
additive; said additive provides mobility to said polymer to allow
said polymer to associate with one another to achieve said
crystallites; said polycrystalline material is characterized by a
degree of crystallinity and a degree of amorphous regions, said
degree of polycrystallinity and said degree of amorphous regions
are selected by selecting the composition of said additive and the
amount of said additive; and wherein said additive is a plasticizer
selected from the group consisting of: Adipic acid derivatives
Sebacic acid derivatives Azelaic acid derivatives Stearic acid
derivatives Benzoic acid derivatives Diethyl succinate Citric acid
derivatives N-Ethyl o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
20. A structure according to claim 19, wherein said structure is
electrically conductive and has an isotropic electrical
conductivity.
21. A structure according to claim 19, wherein said polymer is
selected from the group consisting of substituted and unsubstituted
polyparaphenylene vinylenes, polyparaphenylenes, polyanilines,
polythiophenes, polyazines, polyfuranes, polypyrroles,
polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed
from soluble precursors, combinations thereof and blends thereof
with other polymers and copolymers of the monomers thereof.
22. A structure according to claim 21, wherein said structure has
crystallinity greater than about 25%.
23. A structure comprising: a polycrystalline material comprising
crystallites of polymers with intersticial regions therebetween;
said polymer is a precursor to an electrically conductive polymer;
said intersticial regions comprise an amorphous material selected
from the group consisting of said polymers; said amorphous material
includes an additive; said polycrystalline material is
characterized by a degree of crystallinity and a degree of
amorphous regions, said degree of polycrystallinity and said degree
of amorphous regions are selected by selecting the composition of
said additive and the amount of said additive; and wherein said
additive is a plasticizer selected from the group consisting of:
Adipic acid derivatives Sebacic acid derivatives Azelaic acid
derivatives Stearic acid derivatives Benzoic acid derivatives
Diethyl succinate Citric acid derivatives N-Ethyl
o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
24. A structure according to claim 23, wherein said polymer is an
electrically conductive polymer and said polycrystalline material
has a conductivity which is isotropic.
25. A structure according to claim 23, wherein said polymer is
selected from the group consisting of substituted and unsubstituted
polyparaphenylene vinylenes, polythianophthenes,
polyparaphenylenes, polyanilines, polythiophenes, polyazines,
polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene
sulfides, polyacetylenes formed from soluble precursors,
combinations thereof and blends thereof with other polymers and
copolymers of the monomers thereof.
26. A structure according to claim 23, wherein the amount of said
additive is adjustable.
27. A structure according to claim 26, wherein said amount is
controlled to modify physical properties of said structure.
28. A structure according to claim 27, wherein said physical
properties are selected from the group consisting of glass
transition temperature, compliance, thermal coefficient of
expansion, modulus, yield and tensile strength, hardness,
density.
29. A structure according to claim 23, wherein said crystallites
have a size greater than about 80 .ANG..
30. A structure according to claim 23, wherein said crystallites
have a size greater than about 80 .ANG..
31. A structure comprising: a polycrystalline material comprising
crystallites of polyaniline with intersticial regions therebetween;
said polyaniline is a precursor to an electrically conductive
polyaniline; said intersticial regions comprise an amorphous
material selected from the group consisting of polyaniline; said
amorphous material includes an additive in an amount from about
0.001% to about 90% by weight; said polycrystalline material is
characterized by a degree of crystallinity and a degree of
amorphous regions, said degree of polycrystallinity and said degree
of amorphous regions are selected by selecting the composition of
said additive and the amount of said additive; and wherein said
additive is a plasticizer selected from the group consisting of:
Adipic acid derivatives Sebacic acid derivatives Azelaic acid
derivatives Stearic acid derivatives Benzoic acid derivatives
Diethyl succinate Citric acid derivatives N-Ethyl
o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
32. A structure according to claim 23, wherein the amorphous
material in the intersticial regions contains crosslinks.
33. A structure according to claim 23, wherein the amorphous
material in the intersticial regions are deaggregated.
34. A structure according to claim 23, wherein the additive is in
an amount for about 0.001% to about 90% by weight.
35. A structure comprising: a polycrystalline material comprising
crystallites of polymers with intersticial regions therebetween;
wherein said polymer is a precursor to an electrically conductive
polymer; said intersticial regions between said crystallites
comprising amorphous material comprising an additive; said additive
provides mobility to said polymer to allow said polymer to
associate with one another to achieve said crystallites; said
polycrystalline material is characterized by a degree of
crystallinity and a degree of amorphous regions, said degree of
polycrystallinity and said degree of amorphous regions are selected
by selecting the composition of said additive and the amount of
said additive; and wherein said additive is a plasticizer selected
from the group consisting of: Adipic acid derivatives Sebacic acid
derivatives Azelaic acid derivatives Stearic acid derivatives
Benzoic acid derivatives Diethyl succinate Citric acid derivatives
N-Ethyl o,p-tolusnesulfonamide Dimer acid derivatives
o,p-toluenesulfonanamide Epoxy derivatives Terpentines Fumaric acid
derivatives Terpentine derivatives Glycerol triacetate Siloxanes
Isobutyrate derivatives Polysiloxanes Isophthalic acid derivatives
Ethylene glycols Lauric acid derivatives Polyethylene glycols
Linoleic acid derivative Polyesters Maleic acid derivative Sucrose
derivatives Mellitates Tartaric acid derivative Myristic acid
derivatives Terephthalic acid derivative Oleic acid derivatives
Trimellitic acid derivatives Palmitic acid derivatives Glycol
derivatives Paraffin derivatives Glycolates Phosphoric acid
derivatives poly(alkyl naphthalene)s Phthalic acid derivatives
aliphatic aromatics Leromoll Ricinoleic acid derivatives Phosphonic
acid derivatives Polysilanes.
Description
[0001] This application is a DIV of Ser. No. 09/727,615 (filed on
Dec. 1, 2000), which is a CON of Ser. No. 09/268,527 (filed on Mar.
12, 1999, now U.S. Pat. No. 6,210,606), which application is a CON
of Ser. No. 08/620,168 (filed Mar. 22, 1996, now U.S. Pat. No.
5,932,143), which application claims benefit of 60/007,688 (filed
Nov. 29, 1995).
CROSS REFERENCE TO RELATED APPLICATION
[0002] U.S. patent application Ser. No. 08/620,619, filed Mar. 22,
1996, entitled. "PLASTICIZED, ANTIPLASTICIZED CRYSTALLINE
CONDUCTING POLYMERS AND PRECURSORS THEREOF" now U.S. Pat. No.
5,928,566, and U.S. patent application Ser. No. 08/620,631, filed
Mar. 22, 1996 entitled, "METHODS OF FABRICATING PLASTICIZED,
ANTIPLASTICIZED AND CRYSTALLINE CONDUCTING POLYMERS AND PRECURSORS
THEREOF", now U.S. Pat. No. 5,969,024 the teachings of which are
incorporated herein by reference.
FIELD OF THE INVENTION
[0003] The present invention is directed to polycrystalline
electrically conductive polymer precursors and polycrystalline
conducting polymers having adjustable morphology and
properties.
BACKGROUND
[0004] Electrically conductive organic polymers emerged in the
1970's as a new class of electronic materials. These materials have
the potential of combining the electronic and magnetic properties
of metals with the light weight, processing advantages, and
physical and mechanical properties characteristic of conventional
organic polymers. Examples of electrically conducting polymers are
polyparaphenylene vinylenes, polyparaphenylenes, polyanilines,
polythiophenes, polyazines, polyfuranes, polythianaphthenes
polypyrroles, polyselenophenes, poly-p-phenylene sulfides,
polyacetylenes formed from soluble precursors, combinations thereof
and blends thereof with other polymers and copolymers of the
monomers thereof.
[0005] These polymers are conjugated systems which are made
electrically conducting by doping. The doping reaction can involve
an oxidation, a reduction, a protonation, an alkylation, etc. The
non-doped or non-conducting form of the polymer is referred to
herein as the precursor to the electrically conducting polymer. The
doped or conducting form of the polymer is referred to herein as
the conducting polymer.
[0006] Conducting polymers have potential for a large number of
applications in such areas such as electrostatic charge/discharge
(ESC/ESD) protection, electromagnetic interference (EMI) shielding,
resists, electroplating, corrosion protection of metals, and
ultimately metal replacements, i.e. wiring, plastic microcircuits,
conducting pastes for various interconnection technologies (solder
alternative), etc. Many of the above applications especially those
requiring high current capacity have not yet been realized because
the conductivity of the processible conducting polymers is not yet
adequate for such applications.
[0007] To date, polyacetylene exhibits the highest conductivity of
all the conducting polymers. The reason for this is that
polyacetylene can be synthesized in a highly crystalline form
(crystallinity as high as 90% has been achieved) (as reported in
Macromolecules, 25, 4106, 1992). This highly crystalline
polyacetylene has a conductivity on the order of 10.sup.5 S/cm.
Although this conductivity is comparable to that of copper,
polyacetylene is not technologically applicable because it is a
non-soluble, non-processible, and environmentally unstable polymer.
The polyaniline class of conducting polymers has been shown to be
probably the most suited of such materials for commercial
applications. Great strides have been made in making the material
quite processable. It is environmentally stable and allows chemical
flexibility which in turn allows tailoring of its properties.
Polyaniline coatings have been developed and commercialized for
numerous applications. Devices and batteries have also been
constructed with this material. However, the conductivity of this
class of polymers is generally on the low end of the metallic
regime. The conductivity is on the order of 10.sup.0 S/cm. Some of
the other soluble conducting polymers such as the polythiophenes,
poly-para-phenylenevinylenes exhibit conductivity on the order of
10.sup.2 S/cm. It is therefore desirable to increase the
conductivity of the soluble/processible conducting polymers, in
particular the polyaniline materials.
[0008] The conductivity (a) is dependent on the number of carriers
(n) set by the doping level, the charge on the carriers (q) and on
the interchain and intrachain mobility (.mu.) of the carriers.
.sigma.=nq.mu.
[0009] Generally, n (the number of carriers) in these systems is
maximized and thus, the conductivity is dependent on the mobility
of the carriers. To achieve higher conductivity, the mobility in
these systems needs to be increased. The mobility, in turn, depends
on the morphology of the polymer. The intrachain mobility depends
on tile degree of conjugation along the chain, presence of defects,
and on the chain conformation. The interchain mobility depends on
the interchain interactions, the interchain distance, the degree of
crystallinity, etc. Increasing the crystallinity results in
increased conductivity as examplified by polyacetylene. To date, it
has proven quite difficult to attain polyaniline in a highly
crystalline state. Some crystallinity has been achieved by stretch
orientation or mechanical deformation (A. G. MacDiarmid et al in
Synth. Met. 55-57, 753). In these stretch-oriented systems,
conductivity enhancements have been observed. The conductivity
enhancement was generally that measured parallel to tile stretch
direction. Therefore, the conductivity in these systems is
anisotropic. It is desirable to achieve a method of controlling and
tuning the morphology of polyaniline. It is desirable to achieve a
method of controlling and tuning the degree of crystallinity and
the degree of amorphous regions in polyaniline, which in turn
provides a method of tuning the physical, mechanical, and
electrical properties of polyaniline. It is further desirable to
achieve highly crystalline and crystalline polyaniline and to
achieve this in a simple and useful manner in order to increase the
mobility of the carriers and, therefore, the conductivity of the
polymer. It is also further desirable to achieve isotropic
conductivity, that is conductivity not dependent on direction as
with stretch-oriented polyanilines.
OBJECTS
[0010] It is an object of the present invention to provide a
polycrystalline material containing crystallites of an electrically
conducting polymer precursor and/or electrically conducting polymer
having an adjustable morphology.
[0011] It is an object of the present invention to provide a
polycrystalline material of an electrically conductive polymer
precursor and/or electrically conducting polymer in which the
degree of amorphous and crystalline regions is adjustable.
[0012] It is an object of the present invention to provide a
polycrystalline material of an electrically conducting polymer
precursor and/or electrically conducting polymer having adjustable
physical, mechanical, and electrical properties.
[0013] It is an object of the present invention to provide a
crystalline electrically conducting polymer precursor and
crystalline conducting polymers.
[0014] It is an object of the present invention to provide a highly
crystalline electrically conducting polymer precursor and highly
crystalline conducting polymers.
[0015] It is an object of the present invention to provide a
polycrystalline material of an electrically conducting polymer
precursor and/or crystalline conducting polymers to provide a
highly crystalline material.
[0016] It is another object of the present invention to provide an
electrically conducting polycrystalline material that exhibits
enhanced carrier mobility.
[0017] It is another object of the present invention to provide an
electrically conducting polycrystalline material which exhibits
enhanced conductivity.
[0018] It is another object of the present invention to provide an
electrically conducting polycrystalline material which exhibits
enhanced isotropic conductivity.
[0019] It is another object of the present invention to provide a
plasticization effect in a polycrystalline electrically conducting
polymer precursors and/or electrically conducting polymers.
[0020] It is another object of the present invention to provide a
polycrystalline material having an antiplasticization effect in
electrically conducting polymer precursors and electrically
conducting polymers.
[0021] It is another object of the present invention to provide a
polycrystalline material of a precursor or electrically conducting
polymer containing an additive providing mobility.
[0022] It is another object of the present invention to provide a
polycrystalline material of a precursor or electrically conductive
polymer containing an additive to induce all enhanced degree of
crystallinity.
[0023] It is another object of the present invention to provide a
non-stretch oriented polycrystalline film of a precursor or of an
electrically conductive polymer which has an enhanced degree of
crystallinity.
[0024] It is an object of the present invention to provide a
polycrystalline material of an electrically conducting polymer
precursor and/or electrically conducting polymer having an
increased glass transition temperature.
[0025] It is an object of the present invention to provide an
electrically conducting polymer precursor and electrically
conducting polymer having an decreased glass transition
temperature.
[0026] It is an object of the present invention to provide a
polycrystalline material of an electrically conducting polymer
precursor and electrically conducting polymer having enhanced
mechanical properties.
[0027] It is an object of the present invention to provide a
polycrystalline material of an electrically conducting polymer
precursor and electrically conducting polymer having decrease
mechanical properties.
SUMMARY OF THE INVENTION
[0028] A broad aspect of the present invention is a polycrystalline
material comprising crystallites of a precursor to an electrically
conductive polymer and/or an electrical conductive polymer. The
intersticial regions between the crystallites contain amorphous
material.
[0029] In a more particular aspect of the present invention, the
amorphous regions of the material contain the additive.
DESCRIPTION OF THE DRAWINGS
[0030] Further objects, features, and advantages of the present
invention will become apparent from a consideration of the
following detailed description of the invention when read in
conjunction with the drawings FIG's. in which:
[0031] FIG. 1 is a general formula for polyaniline in the non-doped
or precursor form.
[0032] FIG. 2 is a general formula for a doped conducting
polyaniline.
[0033] FIG. 3 is a general formula for the polysemiquinone radical
cation form of doped conducting polyaniline.
[0034] FIG. 4 is a Gel Permeation Chromatograph (GPC) of
polyaniline base in NMP (0.1%): GPC shows a trimodal
distribution--A very high molecular weight fraction (approx. 12%)
and a major peak having lover molecular weight.
[0035] Curve 5(a) is a Wide Angle-X-Ray Scattering (WAXS) spectrum
for a polyaniline base film processed from NMP. The polymer film is
essentially amorphous. Curve 5(b) is a Wide Angle X-Ray Scattering
spectrum for a polyaniline base film that has stretch-oriented
(I/Io-3.7). This film was derived from a gel. Curve 5(c) is a Wide
Angle-X-Ray Scattering spectrum for a polyaniline-base film
containing 10% poly-co-dimethyl propylamine siloxane. This film is
highly crystalline.
[0036] FIG. 6 is a Schematic diagram of a polycrystalline material
as taught in present invention having crystalline regions (outlined
in (dotted rectangles) with intersticial amorphous regions
[0037] FIG. 7 is a Dynamic Mechanical Thermal Analysis (DMTA) plot
for polyaniline base film cast from NMP. (First Thermal Scan; under
Nitrogen).
[0038] FIG. 8 is a DMTA plot which represents the second thermal
scan for a polyaniline base film cast from NMP; This same film was
previously scanned as shown in FIG. 7. Film Contains no residual
solvent.
[0039] FIG. 9 is a DMTA plot for polyaniline base film cast from
NMP and containing 5% poly-co-dimethyl aminopropyl siloxane (5% N
content). First Thermal Scan.
[0040] FIG. 10 is a DMTA plot for polyaniline base film cast from
NMP and containing 5% poly-co-dimethyl aminopropyl siloxane (5% N
content). Second Thermal Scan (this same film was previously
scanned as shown in FIG. 9) Film Contains no residual solvent.
[0041] FIG. 11 is a GPC for a polyaniline base solution in NMP
containing 5% poly-co-dimethyl aminopropyl siloxane by weight to
polyaniline. The polyaniline was 0.1% in NMP.
DETAILED DESCRIPTION
[0042] The present invention is directed toward electrically
conducting polymer precursors and conducting polymers having
adjustable morphology and in turn adjustable physical, and
electrical properties. The present invention is also directed
toward controlling and enhancing the 3-dimensional order or
crystallinity of conducting polymer precursors and of conducting
polymers. In addition, the present invention is directed towards
enhancing the electrical conductivity of conducting polymers. This
is done by forming an admixture of an electrically conducting
polymer precursor or an electrically conducting polymer with an
additive whereby the additive provides local mobility to the
molecules so as to allow the conducting polymer precursor or
conducting polymer chains to associate with one another and achieve
a highly crystalline state. An example of such an additive is a
plasticizer. A plasticizer is a substance which when added to a
polymer, solvates the polymer and increases its flexibility,
deformability, generally decreases the glass transition temperature
Tg, and generally reduces the tensile modulus. In certain cases,
the addition of a plasticizer may induce antiplasticization, that
is an increase in the modulus or stiffness of the polymer, an
increase in Tg. Herein the additives can provide a plasticization
effect, an antiplasticization effect or both effects.
[0043] Examples of polymers which can be used to practice the
present invention are of substituted and unsubstituted homopolymers
and copolymers of aniline, thiophene, pyrrole, p-phenylene sulfide,
azines, selenophenes, furans, thianaphthenes, phenylene vinylene,
etc. and the substituted and unsubstituted polymers,
polyparaphenylenes, polyparaphenylevevinylenes, polyanilines,
polyazines, polythiophenes, poly-p-phenylene sulfides, polyfuranes,
polypyrroles, polythianaphthenes, polyselenophenes, polyacetylenes
formed from soluble precursors and combinations thereof and
copolymers of monomers thereof. The general formula for these
polymers can be found in U.S. Pat. No. 5,198,153 to Angelopoulos et
al. While the present invention will be described with reference to
a preferred embodiment, it is not limited thereto. It will be
readily apparent to a person of skill in the art how to extend the
teaching herein to other embodiments. One type of polymer which is
useful to practice the present invention is a substituted or
unsubstituted polyaniline or copolymers of polyaniline having
general formula shown in FIG. 1 wherein each R can be H or any
organic or inorganic radical; each R can be the same or different;
wherein each R.sup.1 can be H or any organic or inorganic radical,
each R.sup.1 can be the same or different; x.gtoreq.1; preferable
x.gtoreq.2 and y has a value from 0 to 1. Examples of organic
radicals are alkyl or aryl radicals. Examples of inorganic radicals
are Si and Ge. This list is exemplary only and not limiting. The
most preferred embodiment is emeraldine base form of the
polyaniline wherein y has a value of approximately 0.5. The base
form is the non-doped form of the polymer. The non-doped form of
polyaniline and the non-doped form of the other conducting polymers
is herein referred to as the electrically conducting polymer
precursor.
[0044] In FIG. 2, polyaniline is shown doped with a dopant. In this
form, the polymer is in the conducting form. If the polyaniline
base is exposed to cationic species QA, the nitrogen atoms of the
imine (electron rich) part of the polymer becomes substituted with
the Q+ cation to form an emeraldinie salt as show in FIG. 2. Q+ can
be selected from H+ and organic or inorganic cations, for example,
an alkyl group or a metal.
[0045] QA can be a protic acid where Q hydrogen. When a protic
acid, HA, is used to dope the polyaniline, the nitrogen atoms of
the imine part of the polyaniline are protonated. The emeraldine
base form is greatly stalbilized by resonance effects. The charges
distribute through the nitrogen atoms and aromatic rings making the
imine and amine nitrogens indistinguishable. The actual structure
of the doped form is a delocalized polysemiquinone radical cation
as shown in FIG. 3.
[0046] The emeraldine base form of polyaniline is soluble in
various organic solvents and in various aqueous acid solutions.
Examples or organic solvents are dimethylsulfoxide (DMSO),
dimethylformamide (DMF) and N-methylpyrrolidinone (NMP),
dimethylene propylene urea, tetramethyl urea, etc. This list is
exemplary only and not limiting. Examples of aqueous acid solutions
is 80% acetic acid and 60-88% formic acid. This list is exemplary
only and not limiting.
[0047] Polyaniline base is generally processed by dissolving the
polymer in NMP. These solutions exhibit a bimodal or trimodal
distribution in Gel Permeation Chromatography (GPC) as a result of
aggregation induced by internal hydrogen bonding between chains as
previously described in U.S. patent application Ser. No.
08/370,128, filed on Jan. 9, 1995, the teaching of which is
incorporated herein by reference. The GPC curve for typical
polyaniline base in NMP is shown in FIG. 4.
[0048] Polymers in general can be amorphous, crystalline, or partly
crystalline. In the latter case, the polymer consists of
crystalline phases and amorphous phases. The morphology of a
polymer is very important in determining the polymer's physical,
mechanical, and electronic properties.
[0049] Polyaniline base films processed from NMP either by spin
coating or by solution casting techniques are amorphous as can be
seen in FIG. 5a which depicts the Wide Angle X-Ray Scattering
(WAXS) spectrum for this material. Amorphous diffuse scattering is
observed. Some crystallinity is induced in these films by post
processing mechanical deformation especially if these films are
derived from gels as described by A. G. MacDiarmid et al in Synth.
Met. 55-57, 753 (1993), WAXS of a stretch oriented film having been
stretched (I/Io=3.7.times.) derived from a gel is shown in FIG. 5b.
Some has been induced as compared to the non-stretch oriented films
as evidenced by the defined scattering peaks.
[0050] Doping the amorphous polyaniline base films (those having
structure shown in FIG. 5a) with aqueous hydrochloric acid results
in isotropic conductivity of 1 S/cm. Such films are not
crystalline. Similar doping of stretch oriented films results in
anisotropic conductivity where conductivity on the order of
10.sup.2 S/cm is measured parallel to the stretch direction whereas
conductivity on the order of 10.sup.0 S/cm is measured
perpendicular to the stretch direction. It should also be noted
that some level of crystallinity is lost during the doping process
in these films.
[0051] According to the present invention, the interchain (polymer
chain) registration is increased as compared to a stretch oriented
film.
[0052] FIGS. 7 and 8 show the dynamic mechanical thermal analysis
(DMTA) spectrum for a polyaniline base film processed from NMP
alone. FIG. 7 is the first scan where a Tg of approx. 118 is
observed as a result of the residual NMP which is present in the
film. FIG. 8 is the second thermal scan of the same film. This film
has no residual solvent and a Tg of .congruent.251.degree. C. is
measured for the polyaniline base polymer.
[0053] When an additive such as a plasticizer, such as a
poly-co-dimethyl propylamine siloxane, is added to the polyaniline
base completely different properties and morphology is observed.
The siloxane has a polar amine group which facilitates the
miscibility of the polyaniline base and the plasticizer. The DMTA
of a polyaniline base film cast from NMP and containing 55 by
weight to polyaniline of the poly-co-dimethyl propyl amine siloxane
exhibits a lower Tg on the first thermal scan as compared to
polyaniline base processed from NMP alone (FIG. 9) as a result of
plasticization induced by the siloxane. However, on the second
thermal scan of this film (FIG. 10), the polymer exhibits an
increase in Tg as compared to polyaniline processed from NMP. When
the polysiloxane is added to a solution of polyaniline base, the
siloxane due to the polar amine group can interact with the polymer
chains and disrupt some of the polyaniline interactions with itself
or some of the aggregation. Thus, the polysiloxane first induces
some deaggregation. However, the polysiloxane has multiple amine
sites and thus, it can itself hydrogen bond with multiple
polyaniline base chains and thus, the polysiloxane facilitates the
formation of a cross-linked network. This cross-linked network
accounts for the increased Tg observed in the DMTA. Tg is
characteristic of the amorphous regions of a polymer and in this
case the amorphous regions consist of a cross-linked
polyaniline/polysiloxane network. Thus, the polysiloxane is
inducing an antiplasticization effect in polyaniline base as the Tg
is increased. Generally, plasticizers reduce Tg. GPC data (FIG. 11)
is consistent with this model. The addition of the poly-amino
containing siloxane to a polyaniline base solution in NMP results
in a significant increase in the high molecular weight fractions
depicting the cross-linked network which forms between polyaniline
and the plasticizer.
[0054] In addition to the cross-linked network the siloxane induces
in the amorphous regions, concomitantly it also is found to induce
significant levels of crystallinity in polyaniline base as a result
of the local mobility that it provides. FIG. 5c shows the WAXS for
a polyaniline base film processed from NMP containing 10% of the
poly amino containing siloxane. As can be seen highly crystalline
polyaniline has bee attained. Much higher levels of crystallinity
as compared to FIG. 5b for the stretch oriented films.
[0055] Thus polyaniline by the addition of the siloxane forms a
structure depicted in FIG. 6 where crystalline regions of highly
associated polyaniline chains (outlined by a rectangle) are formed
with intersticial amorphous regions. In most cases, the additive
resides in the amorphous intersticial sites. The degree of
crystallinity (number of crystalline sites) and the size of the
crystalline domains as well as the degree of amorphous regions and
the nature of the amorphous region (aggregated, i.e. cross-linked
or not) can be tuned by the type and amount of additive. In turn,
by controlling the above, the properties of the material can also
be controlled.
[0056] With the poly-co-dimethyl aminopropyl siloxane (5% N
content), loadings ranging from 0.001 to 20% by weight gives highly
crystalline polyaniline. The highly crystalline polyaniline in turn
exhibits increased modulus, stiffness, yield and tensile strengths,
hardness, density and softening points. Thus, the siloxane at these
loadings is having an antiplasticization effect. Above 20% loading,
the crystallinity begins to decrease. As the crystallinity
decreases, the modulus, stiffness, Yield and tensile strengths,
hardness, density and softening points begin to decrease. Thus, the
siloxane at these loadings begins to have a plasticization effect.
The siloxane content becomes high enough that it disrupts the
polyaniline base interactions in the crystalline regions. With the
poly co dimethyl aminopropyl siloxanes having 0.5 and 13% N ratios,
similar trends are observed but the particular amount of siloxane
needed to have a plasticization effect or an antiplasticization
effect varies. Thus, the degree of crystallinity and the degree of
amorphous regions and in turn the properties of polyaniline can be
tuned by the nature of the additive as well as the amount of
additive. Indeed, using the same additive but simply changing the
loading dramatically changes the morphology and in turn the
properties of polyaniline. electronic properties of the polymer are
also impacted. The conductivity of a polyaniline base film cast
from NMP and containing 1% by weight poly-co-dimethyl aminopropyl
siloxane which is doped by aqueous hydrochloric acid is 50 S/cm as
compared to 1 S/cm for a polyaniline film with no plasticizer. This
is isotropic conductivity. The doped film containing the
polysiloxane retains the highly crystalline structure.
[0057] The degree of crystallinity and the degree of amorphous
regions and in turn the physical, mechanical, and electronic
properties can be tuned by the particular additive used and by the
amount of additive. For example, the Tg of polyaniline can be
increased or decreased by the amount and type of additive. The
mechanical properties such as tensile properties, modulus, impact
resistance, etc. can be tuned as described above. The additive can
range from 0.001 to 90% by weight, more preferably from 0.001 to
50% and most preferably from 0.001 to 25%. A list of plasticizers
that can be used to practice the present invention is given in
Table 1. The additive can also be removed from the final film
structure if so desired by appropriate extraction.
SPECIFIC EXAMPLES
[0058] Polyaniline Synthesis Polyaniline is synthesized by the
oxidative polymerization of aniline using ammonium peroxydisulfate
in aqueous hydrochloric acid. The polyaniline hydrochloride
precipitates from solution. The polymer is then neutralized using
aqueous ammonium hydroxide. The neutralized or non-dope polyaniline
base is then filtered, washed and dried. Polyaniline can also be
made by electrochemical oxidative polymerization as taught by W.
Huang, B. Humphrey, and A. G. MacDiarmid, J. Chem. Soc., Faraday
Trans. 1, 82, 2385, 1986.
Polyaniline Base in NMP:
[0059] The polyaniline base powder is readily dissolved in NMP up
to 5% solids. Thin films (on the order of a micron) can be formed
by spin-coating. Thick films are made by solution casting and
drying (70.degree. C. in vacuum oven under a nitrogen purge for 15
hours). These solutions and films have the properties described
above.
Polyaniline Base in NMP/Plasticizer
[0060] a. Polyaniline Base was first dissolved in NMP to 5% solids
and allowed to mix well. A poly-co-dimethyl, aminopropyl siloxane
(N content 5% relative to repeat unit) was dissolved to 5% in NMP.
The siloxane solution was added to the polyaniline base solution.
The resulting admixture was allowed to mix for 12 hours at room
temperature. A number of solutions were made having from 0.001% to
50% siloxane content (by weight relative to polyaniline). Thin
films were spin-coated onto quartz substrates; Thick films were
prepared by solution casting and baking the solutions at 70.degree.
C. in a vacuum oven under a Nitrogen purge for 15 hours). The
solutions and the films have the properties described above.
[0061] b. The same experiment described in (a) was carried out
except that the plasticizer was a poly-co-dimethyl, aminopropyl
siloxane in which the N content was 13%.
[0062] c. The same experiment described in (a) was carried out
except that the plasticizer was a poly-co-dimethyl, aminopropyl
siloxane in which the N content was 0.5%.
[0063] d. The same experiment described in (a) was carried out
except that the plasticizer was polyglycol diacid.
[0064] e. The same experiment described in (a) was carried out
except that the plasticizer was 3,6,9-trioxaundecanedioic acid.
[0065] f. The same experiment described in (a) was carried out
except that the plasticizer was poly(ethylene glycol) tetrahydro
furfuryl ether.
[0066] g. The same experiment described in (a) was carried out
except that the plasticizer was glycerol triacetate.
[0067] h. The same experiment described on (a) was carried out
except the plasticizer was epoxidized soy bean oil.
Polyaniline Base in NMP/m-Cresol/Plasticizer
[0068] The same experiment as described in (a) was carried out
except that polyaniline base and the plasticizer was dissolved in
NMP/m-Cresol mixtures in which m-Cresol ranged from 1 to 99%
Polyaniline Base in m-Cresol/Plasticizer
[0069] The same experiment as described in (a) was carried out
except that the polyaniline base was dissolved in m-Cresol and the
plasticizer was dissolved in m-Cresol.
Polyaniline Base in m-Cresol and in NMP/m-Cresol
[0070] Polyaniline Base was dissolved in m-Cresol and in
NMP/m-Cresol combinations to 5% solids. The m-Cresol in the latter
system being the additive ranged from 1 to 99%. Free-Standing films
were made by solution casting techniques. With increasing m-cresol
content, the polyaniline exhibited a WAXS similar to that shown in
FIG. 5a except that the amorphous scattering peak became somewhat
sharper indicative of some crystallinity. However, this was
significantly less than observed with the siloxane plasticizer.
Doped Polyanilines
[0071] 1. Hydrochloric Acid and/or Methanesulfonic Acid Doped
Films
[0072] Polyaniline base films made as described above were doped by
aqueous acid solutions of hydrochloric or methanesulfonic acid. The
films were immersed in the acid solution for 12 hours for thin
films and 36 hours for the thick films. The conductivity of a
polyaniline base film processed from NMP and doped with these acid
solutions is 1 S/cm The conductivity of a base film processed from
NMP and 1% poly-co-dimethyl, aminopropyl siloxane (5% N content)
was 50 S/cm.
2. Sulfonic Acid Doped Polyanilines
[0073] Polyaniline Base was dissolved in a solvent such as NMP or
NMP/m-Cresol combinations, etc. from 1 to 5% solids. To this
solution was added a dopant such camphorsulfonic acid or
acrylamidopropanesulfonic acid (previously reported in U.S. patent
application Ser. No. 595,853 filed on Feb. 2, 1996). These
solutions were used to spin-coat or solution cast films. In some
experiments, the plasticizer such as the poly-co-dimethyl,
aminopropyl siloxane in a solvent was added to the doped
polyaniline solution. In certain other experiments, the plasticizer
was first added to the pani base solution. The dopant was then
added to the polyaniline solution containing the plasticizer.
[0074] The teaching of the following U.S. patent applications are
incorporated herein by reference:
"CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERS, PRECURSORS THEREOF
AND APPLICATIONS THEREOF", application Ser. No. 595,853, filed Feb.
2, 1996, now U.S. Pat. No. 6,193,909; "METHODS OF FABRICATION OF
CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERS AND PRECURSORS
THEREOF", application Ser. No. 594,680, filed Feb. 2, 1996, now
U.S. Pat. No. 6,030,550; "DEAGGREGATED ELECTRICALLY CONDUCTIVE
POLYMERS AND PRECURSORS THEREOF", application Ser. No. 370,127,
filed Jan. 9, 1995, now U.S. Pat. No. 5,804,100; and "METHODS OF
FABRICATION OF DEAGGREGATED ELECTRICALLY CONDUCTIVE POLYMERS AND
PRECURSORS THEREOF", application Ser. No. 370,128, filed Jan. 9,
1995, now U.S. Pat. No. 6,087,472.
[0075] While the present invention has been shown and described
with respect to a preferred embodiment, it will be understood that
numerous changes, modifications, and improvements will occur to
those skilled in the art without departing from the spirit and
scope of the invention.
TABLE-US-00001 TABLE I PLASTICIZERS ADIPIC ACID DERIVATIVES
Dicapryl adipate Di-(2-ethylhexyl) adipate Di(n-heptyl, n-nonyl)
adipate Diisobutyl adipate Diisodecyl adipate Dinomyl adipate
Di-(tridecyl) adipate AZELAIC ACID DERIVATIVES Di-(2-ethylhexyl
azelate) Diisodecyl azelate Diisoctyl azelate Dimethyl azelate
Di-n-hexyl azelate BENZOIC ACID DERIVATIVES Diethylene glycol
dibenzoate Dipropylene glycol dibenzoate Polyethylene glycol 200
dibenzoate CITRIC ACID DERIVATIVES Acetyl tri-n-butyl citrate
Acetyl triethyl citrate Tri-n-butyl citrate Triethyl citrate DIMER
ACID DERIVATIVES Bis-(2-hydroxyethyl dimerate) EPOXY DERIVATIVES
Epoxidized linseed oil Epoxidized soy bean oil 2-Ethylhexyl
epoxytallate n-Octyl expoxystearate FUMARIC ACID DERIVATIVES
Dibutyl fumarate GLYCEROL DERIVATIVES Glycerol triacetate
ISOBUTYRATE DERIVATIVE 2,2,4-Trimethyl-1,3-pentanediol
Diisobutyrate ISOPHTHALIC ACID DERIVATIVES Di-(2-ethylhexyl)
isophthalate Dimethyl isophthalate Diphenyl isophthalate LAURIC
ACID DERIVATIVES Methyl laurate LINOLEIC ACID DERIVATIVE Methyl
linoleate, 75% MALEIC ACID DERIVATIVES Di-(2-ethylhexyl) maleate
Di-n-butyl maleate MELLITATES Tricapryl trimellitate
Tri-(2-ethylhexyl) trimellitate Triisodecyl trimellitate
Tri-(n-octyl, n-hecyl) trimellitate MYRISTIC ACID DERIVATIVES
Isopropyl myristate OLEIC ACID DERIVATIVES Butyl oleate Glycerol
monooleate Glycerol trioleate Methyl oleate n-Propyl oleate
Tetrahydrofurfuryl oleate PALMITIC ACID DERIVATIVES Isopropyl
plamitate Methyl palmitate PARAFFIN DERIVATIVES Chloroparaffin, 41%
Cl Chloroparaffin, 50% Cl Chloroparaffin, 60% Cl Chloroparaffin,
70% Cl PHOSPHORIC ACID DERIVATIVES 2-Ethylhexyl diphenyl phosphate
isodecyl diphenyl phosphate 4-Butylphenyl diphenyl phosphate
Tri-butoxyethyl phosphate Tributyl phosphate Tricresyl phosphate
Triphenyl phosphate PHTHALIC ACID DERIVATIVES Butyl benzyl
phthalate Butyl octyl phthalate Dicapryl phthalate Dicyclohexyl
phthalate Di-(2-ethylhexyl) phthalate Diethyl phthalate Dihexyl
phthalate Diisobutyl phthalate Diisodecyl phthalate Diisononyl
phthalate Diisooctyl phthalate Dimethyl phthalate Ditridecyl
phthalate Diundecyl phthalate RICINOLEIC ACID DERIVATIVES Butyl
ricinoleate Glyceryl tri(acetyl) ricinoleate) Methyl acetyl
ricinoleate Methyl ricinoleate n-Butyl acetyl ricinoleate Propylene
glycol ricinoleate SEBACIC ACID DERIVATIVES Dibutyl sebacate
Di-(2-ethylhexyl) sebacate Dimethyl sebacate STEARIC ACID
DERIVATIVES Ethylene glycol monostearate Glycerol monostearate
Isopropyl isostearate Methyl stearate n-Butyl stearate Propylene
glycol monostearate SUCCINIC ACID DERIVATIVES Dimethyl succinate
SULFONIC ACID DERIVATIVES N-Ethyl o,p-toluenesulfonamide
o,p-toluenesulfonanamide Polyesters adipic acid polyester Paraplex
G-40 adipic acid polyester Santicizer 334F azelaic acid polyester
Plastolein 9720) azelaic acid polyester Plastolein 9750 sebacic
acid polyester Paraplex G-25 Sucrose derivatives sucrose
acetate-isobutyrate (SAIB) Tartaric acid derivative dibutyl
tartrate Terephthalic acid derivative bis(2-ethylhexyl)
terephthalate (DOTP) Trimellitic acid derivatives
tris(2-ethylhexyl) trimellitate (TOTM) heptyl nonyl trimellitate
heptyl nonyl undecyl trimellitate triisodecyl trimellitate Glycol
derivatives diethylene glycol dipelargonate triethylene glycol di-2
ethylbutyrate poly(ethylene glycol) (200) di-2- ethylhexanoate
Glycolates methyl phthalyl ethyl glycolate butyl phthalyl butyl
glycolate Hydrocarbons hydrogenated terphenyls HB-40 poly(alkyl
naphthalene)s Panaflex aliphatic aromatics Leromoll chlorinated
paraffin (52 wt % Cl), Cerecol S-52 Terpenes and Derivatives
Camphor Hydrogenated methyl ester or rosin Phosphonic Acid
Derivatives Chlorinated Polyphosphanate Siloxanes Polydimethyl
siloxane Polyco-dimetyhyl/propylamine siloxanes with various amount
of propylamine content Polydiphenylsiloxanes Polyco-dimethylphenyl
siloxanes Silanol terminated polysiloxanes Amino terminated
polysiloxanes Epoxy terminated polysiloxanes Carbirol terminated
polysiloxanes Polysiloxanes ##STR00001## Glycols Polyethylene
glycol Poly(ethylene glycol) tetrahydrofurfuryl ether Poly(ethylene
glycol) bis(carboxymethyl) ether 3,6,9-trioxadecanoic acid
3,6,9-trioxaundecanedioic acid Polyglycol diacid
* * * * *