Polymeric arylamine silane compounds and imaging members incorporating same

Electrophotographic imaging members are disclosed which incorporate a charge transport layer comprising an arylamine/siloxane polymer.

BACKGROUND OF THE INVENTION 
This invention relates to arylamine compounds, particularly to polymeric 
tertiary arylamine compounds and electrophotographic imaging members and 
processes utilizing such polymeric tertiary arylamine compounds. 
In the art of electrophotography an electrophotographic plate comprising a 
photoconductive insulating layer on a conductive layer is imaged by first 
uniformly electrostatically charging the surface of the photoconductive 
insulating layer. The plate is then exposed to a pattern of activating 
electromagnetic radiation such as illuminated areas of the photoconductive 
insulating layer. The plate is then exposed to a light, which selectively 
dissipates the charge in the illuminated areas of the photoconductive 
insulating layer while leaving behind an electrostatic latent image in the 
non-illuminated areas. This electrostatic latent image may then be 
developed to form a visible image by depositing finely divided 
electroscopic toner particles on the surface of the photoconductive 
insulating layer. The resulting visible toner image can be transferred to 
a suitable receiving member such as paper. This imaging process may be 
repeated many times with reusable photoconductive insulating layers. 
As more advanced, higher speed electrophotographic copiers, duplicators and 
printers were developed, degradation of image quality was encountered 
during cycling. Moreover, complex, highly sophisticated, duplicating and 
printing systems operating at high speeds have placed stringent 
requirements including narrow operating limits on photoreceptors. For 
example, the numerous layers found in many modern photoconductive imaging 
members must be highly flexible, adhere well to adjacent layers, and 
exhibit predictable electrical characteristics within narrow operating 
limits to provide excellent toner images over many thousands of cycles. 
There is also a great current need for long-lasting, flexible 
photoreceptors in compact imaging machines that employ small diameter 
support rollers for photoreceptor belt systems compressed into a very 
confined space. Small diameter support rollers are also highly desirable 
for simple, reliable copy paper stripping systems which utilize the beam 
strength of the copy paper to automatically remove copy paper sheets from 
the surface of a photoreceptor belt after toner image transfer. However, 
small diameter rollers, e.g. less than about 0.75 inch (19 mm) diameter, 
raise the threshold of mechanical of mechanical performance criteria for 
photoreceptors to such a high level that spontaneous photoreceptor belt 
material failure becomes a frequent event for flexible belt 
photoreceptors. 
One type of multilayered photoreceptor that has been employed as a belt in 
electrophotographic imaging systems comprises a substrate, a conductive 
layer, a charge blocking layer, a charge generating layer, and a charge 
transport layer. The charge transport layer often comprises an activating 
small molecule dispersed or dissolved in a polymeric film forming binder. 
Generally, the polymeric film forming binder in the transport layer is 
electrically inactive by itself and becomes electrically active when it 
contains the activating small molecule. The expression "electrically 
active" means that the material is capable of supporting the injection of 
either the hole or electrophotogenerated charge carrier from the material 
in the charge generating layer and is capable of allowing the transport of 
these charge carriers through the electrically active layer in order to 
discharge a surface charge on the active layer. The multilayered type of 
photoreceptor may also comprise additional layers such as an anti-curl 
backing layer, an adhesive layer, and an overcoating layer. 
DESCRIPTION OF PRIOR ART 
U.S. Pat. No. 4,818,650 discloses an electrostatic imaging member 
comprising a polymeric amine compound. The patent does not describe 
polymeric amine compounds linked by siloxane linkages. 
U.S. Pat. No. 4,725,518 discloses a charge transport layer comprising an 
aromatic amine compound. The patent does not describe polymeric amine 
compounds linked by siloxane linkages. 
U.S. Pat. No. 4,806,444 discloses an electrostatic imaging member 
comprising a polymeric amine compound linked by an --O--CO--O-- group. The 
patent does not describe polymeric amine compounds linked by siloxane 
linkages. 
SUMMARY OF THE INVENTION 
It is, therefore, an object of the present invention to provide an improved 
polymeric tertiary arylamine compound or a photoresponsive member 
containing the polymeric compound which overcome at least some of the 
above-noted disadvantages. 
It is yet another object of the present invention to provide an improved 
electrophotographic member which exhibits greater resistance to cracking 
and crazing induced by repetitive mechanical flexing. 
It is still another object of the present invention to provide a 
photoconductive imaging member which eliminates component crystallization. 
It is a further object of the present invention to provide an 
electrophotographic imaging member which retains stable electrical 
properties during cycling. 
It is yet another object of the present invention to provide an improved 
electrophotographic member which resists abrasion when exposed to blade 
cleaning devices. 
It is a further object of the present invention to provide an improved 
photoconductive imaging member which exhibits resistance to residual toner 
build-up subsequent to mechanical cleaning. 
Some of the foregoing objects and others are accomplished in accordance 
with the present invention by providing a polymeric arylamine siloxane 
compound represented by the formula: 
##STR1## 
wherein A is a tertiary arylamine moiety, R is a substituted or 
unsubstituted alkyl, alkenyl or aryl group, R' is a substituted or 
unsubstituted alkyl, alkenyl or aryl group, m is an integer from about 5 
to about 5,000, and n is an integer from 1 to 6 (preferably from 1 to 3). 
The tertiary arylamine moiety is derived from and is a residue of a 
precursor tertiary arylamine compound used in the reaction forming the 
polymer. Preferred compounds of the present invention are those of the 
formula: 
##STR2## 
wherein R, R', m and n are as specified above. Other such compounds 
according to the present invention are of similar formula but with 
substitution on the tertiary arylamine moiety resulting from the use of an 
arylamine other than 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine to 
make such compounds. 
Some of the foregoing objects and others are also accomplished in 
accordance with the present invention by providing a polymeric arylamine 
siloxane compound formed by the reaction of a tertiary aryl amine, such as 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
the like, with a silane of the general formula: 
##STR3## 
wherein R is a substituted or unsubstituted alkyl, alkenyl or aryl group, 
R' is a substituted or unsubstituted alkyl, alkenyl or aryl group, and n 
is an integer from 1 to 6 (preferably from 1 to 3). Mixtures of two or 
more silanes of this formula may also be reacted with the arylamine 
compound to form compounds of the present invention. The arylamine 
compound and silane can also be reacted in the presence of additional 
aromatic monomers, such as bisphenols and the like. 
The polymeric arylamine siloxane of this invention is used in an 
electrophotographic imaging member comprising a substrate, a charge 
generating layer, and a hole transport layer where at least the charge 
generating layer or hole transport layer contains the polymeric arylamine 
siloxane described above. 
A photoconductive imaging member of this invention may be prepared by 
providing a substrate having an electrically conductive surface, applying 
a charge generation layer on the substrate, and applying a charge 
transport layer on the charge generating level. Suitable substrates and 
charge generation layers are known to those skilled in the art. Detailed 
examples of suitable substrates and charge generation layers are disclosed 
in U.S. Pat. No. 4,818,650, the entire disclosure of this patent being 
incorporated herein by reference. A charge blocking layer may also be used 
between the substrate and the charge generating layer. Detailed examples 
of suitable blocking layers are disclosed in U.S. Pat. No. 4,818,650, the 
entire disclosure of this patent being incorporated herein by reference. 
The thickness of the substrate layer and blocking layer will depend on 
numerous factors including economical ones. Those skilled in the art will 
know acceptable ranges for the thickness of the layers. More detailed 
examples of the desired thickness of the substrate layer are also 
disclosed in U.S. Pat. No. 4,818,650, the entire disclosure of this patent 
being incorporated herein by reference. More detailed examples of the 
desired thickness of the blocking layer are also disclosed in U.S. Pat. 
No. 4,818,650, 4,291,110, 4,338,387, 4,286,033, the entire disclosure of 
each patent being incorporated herein by reference. 
Any suitable photogenerating layer may be applied to the blocking layer, 
which can then be overcoated with the charge transport layer. Those 
skilled in the art may overcoat the layer as detailed in U.S. Pat. No. 
4,818,650. Examples of photogenerating layers include inorganic 
photoconductive particles such as amorphous selenium, trigonal selenium, 
and selenium alloys as described in U.S. Pat. No. 4,818,650. 
The photogenerating composition or pigment may be employed in an inactive 
or active binder resin. Typical inactive binder resins include 
polycarbonates, polyesters, polyurethanes, polystyrenes, polysulfones, 
polyamides, polyethersulfones, polyethylenes, polypropylenes, 
polybutadienes, polyarylsulfones, polyarylethers, polyphenylene sulfides 
and others described in U.S. Pat. No. 3,121,006, the entire disclosure of 
which is incorporated by reference herein. The most common active 
transport resin is polyvinylcarbazole. 
The photogenerating composition or pigment may be present in the resinous 
binder composition in various amounts, generally, however, from about 5 
percent by volume to about 90 percent by volume of the photogenerating 
pigment is dispersed in about 10 percent by volume to about 95 percent by 
volume of the resinous binder, and preferably from about 20 percent by 
volume to about 30 percent by volume of the photogenerating pigment is 
dispersed in about 70 percent by volume to about 80 percent by volume of 
the resinous binder composition. In one embodiment about 8 percent by 
volume of the photogenerating pigment is dispersed in about 92 percent by 
volume of the resinous binder composition. 
For embodiments in which the photogenerating layers do not contain a 
resinous binder, the photogenerating layer may comprise any suitable, well 
known homogeneous photogenerating material. Typical homogeneous 
photogenerating materials include inorganic photoconductive compounds such 
as amorphous selenium, selenium alloys selected such as 
selenium-tellurium, selenium-tellurium-arsenic, and selenium arsenide and 
organic material such as chlorindium phthalocyanine, chloraluminum 
phthalocyanine, vanadyl phthalocyanine, and the like. 
The photogenerating layer containing photoconductive compositions and/or 
pigments and the resinous binder material generally ranges in thickness of 
from about 0.1 micrometer to about 5.0 micrometers, and preferably has a 
thickness of from about 0.3 micrometer to about 3 micrometers. The 
photogenerating layer thickness is related to binder content. Higher 
binder content compositions generally require thicker layers for 
photogeneration. Thickness outside these ranges can be selected providing 
the objectives of the present invention are achieved. 
The active charge transport layer comprises a polymeric arylamine of this 
invention capable of supporting the injection of photogenerated holes from 
the charge generation layer and allowing the transport of these holes 
through the transport layer to selectively discharge the surface charge. 
When the photogenerating layer is sandwiched between the conductive layer 
and the active charge transport layer, the transport layer not only serves 
to transport holes, but also protects the photoconductive layer from 
abrasion or chemical attack and therefore extends the operating life of 
the electrophotographic imaging member. The charge transport layer should 
exhibit negligible, if any, discharge when exposed to a wavelength of 
light useful in xerography (e.g. 4000 angstroms to 9000 angstroms). 
Therefore, the charge transport layer is substantially transparent to 
radiation in a region in which the photoconductor is to be used. Thus, the 
active charge transport layer is a substantially non-photoconductive 
material which supports the injection of photogenerated holes from the 
generation layer. The active transport layer is normally transparent when 
exposure is effected through the active layer to ensure that most of the 
incident radiation is utilized by the underlying charge carrier generator 
layer for efficient photogeneration. When used with a transparent 
substrate, imagewise exposure may be accomplished through the substrate 
will all light passing through the substrate. In this case, the active 
transport material need not be transmitting in the wavelength region of 
use. The charge transport layer in conjunction with the generation layer 
in the instant invention is a material which is an insulator to the extent 
that an electrostatic charge placed on the transport layer is not 
conducted in the absence of illumination. 
Part or all of the transport material comprising a hole transporting small 
molecule in an inactive binder to be employed in the transport layer may 
be replaced by the active materials of this invention described above 
comprising a polymeric arylamine film forming material. Any polymeric 
arylamine moieties should be free from electron withdrawing substituents 
such as NO.sub.2 groups, CN groups, &gt;C.dbd.O and the like. The hole 
transporting small molecule-inactive resin binder composition may be 
entirely replaced with 100 percent of a polymeric arylamine compound of 
this invention. 
Any suitable solvent may be employed to apply the transport layer material 
to the underlying layer. Typical solvents include methylene chloride, 
toluene, tetrahydrofuran, and the like. Toluene solvent is a particularly 
desirable component of the charge transport layer coating mixture for 
adequate dissolving of all the components. 
Any suitable and conventional technique may be utilized to mix and 
thereafter apply the charge transport layer coating mixture to the 
underlying surface, e.g. charge generating layer. Typical applications 
techniques include spraying, dip coating, roll coating, wire wound rod 
coating, and the like. Drying of the deposited coating may be effected by 
any suitable conventional technique such as oven drying, infrared 
radiation drying, air drying and the like. 
Generally, the thickness of the hole transport layer is between about 5 to 
about 100 micrometers, but thicknesses outside this range can also be 
used. The hole transport layer should be an insulator to the extent that 
the electrostatic charge placed on the hole transport layer is not 
conducted in the absence of illumination at a rate sufficient to prevent 
formation and retention of an electrostatic latent image thereon. In 
general, the ration of the thickness of the hole transport layer to the 
charge generator layer is preferably maintained from about 2:1 to 200:1 
and in some instances as great as 400:1. 
Optionally, an electrically active overcoat layer may also be utilized to 
improve resistance to abrasion. In some cases a back coating may be 
applied to the side opposite the photoreceptor to provide flatness and/or 
abrasion resistance. These backcoating layers may comprise organic 
polymers or inorganic polymers that are electrically insulating or 
slightly semi-conductive. 
The electrophotographic member of the present invention containing the 
electrically active polymeric arylamine as at least the generator or 
transport layer may be employed in any suitable and conventional 
electrophotographic imaging process which utilizes charging prior to image 
exposure to activating electromagnetic radiation. Conventional positive or 
reversal development techniques may be employed to form a marking material 
image on the imaging surface of the electrophotographic imaging member of 
this invention. Thus, by applying a suitable electrical bias and selecting 
toner having the appropriate polarity of electrical charge, one may form a 
toner image in the negatively charged areas or discharged areas on the 
imaging surface of the electrophotographic member of the present 
invention. More specifically, for positive development, charged toner 
particles of one polarity are attracted to the oppositely charged 
electrostatic areas of the imaging surface and for reversal development, 
charged toner particles are attracted to the discharged areas of the 
imaging surface. Where the transport layer of this invention is sandwiched 
between a photogenerating layer and a conductive surface, a positive 
polarity charge is normally applied prior to imagewise exposure to 
activating electromagnetic radiation. Where the photogenerating layer of 
this invention is sandwiched between a transport layer and a conductive 
surface, a negative polarity charge is normally applied prior to imagewise 
exposure to activating electromagnetic radiation. 
The electrophotographic member of the present invention exhibits greater 
resistance to cracking, crazing, and will not crystallize or phase 
separate during cycling, when the polyarylamine compounds comprise 100% of 
the hole transport layer. 
The invention will now be described in detail with respect to the specific 
preferred embodiments thereof, it being understood that these examples are 
intended to be illustrative only and that the invention is not intended to 
be limited to the materials, conditions, process parameters and the like 
recited herein. All parts and percentage are by weight unless otherwise 
indicated.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
The invention will now be described in detail with respect to the specific 
preferred embodiments thereof, it being understood that these examples are 
intended to be illustrative only and that the invention is not intended to 
be limited to the materials, conditions, process parameters and the like 
recited herein. 
Preferred polymeric arylamines of this invention have a molecular weight 
from about 20,000 to 200,000 and more preferably from about 60,000 to 
180,000. The most preferred weight is determined by the solubility of the 
polymer in solvents of choice for photoreceptors as well as the solution 
viscosity at a given weight. 
Typical hydroxy tertiary arylamine compound useful in practicing the 
present invention include 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'diamine; 
N,N-bis(4-(hydroxyphenyl)-m-toluidine; 
bis-N-(3-hydroxyphenyl)-N-phenyl-4-aminophenyl)-methane; 
bis(N-(4-hydroxyphenyl)-N-phenyl)-4-aminophenyl]-isopropylidene; 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)[1,1"-terphenyl]-4,4"diamine; 
9-ethyl-3.6-bis]N-phenyl-N-3(3-hydroxyphenyl)-aminocarbiazole; 
1,4-bis(N-phenyl-N-(3-hydroxyphenyl)phenylenediamine; and the like. 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine is 
particularly preferred. Other arylamine compounds include those disclosed 
in U.S. Pat. Nos. 4,806,443, 4,806,444 and 4,818,650, the disclosures of 
which are incorporated herein by reference. 
Representative hydroxy arylamine compounds may be prepared by hydrolyzing 
an alkoxy arylamine. A typical process for preparing alkoxy arylamines is 
disclosed in Example 1 of U.S. Pat. No. 4,588,666 to Stolka, et al., the 
entire disclosure of this patent being incorporated herein by reference. 
In accordance with the procedure of Example 1 in U.S. Pat. No. 4,588,666, 
N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine may be 
synthesized from iodoanisole to achieve a yield of 90 percent, m.p. 
120.degree.-125.degree. C. 
N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine was 
prepared, for example from the 
N,N'-di(3-methoxyphenyl)-N,N'-diphenyl-[1,1-biphenyl]4,4'diamine by 
placing into a two liter three-necked round bottom flask, equipped with a 
mechanical stirrer and an argon gas inlet, 137.5 grams 
N.N'-diphenyl-N,N'-bis(3-methoxyphenyl)-[1,1'-biphenyl]-4,4'diamine (0.25 
moles), 223.5 gms anhydrous sodium iodide (1.5 moles) and 500 milliliters 
warm sulfolane (distilled). The contents of the flask are heated to 
120.degree. C. then cooled to 60.degree.-75.degree. C. Five milliliters of 
D. I. water is added dropwise, followed by 190.5 milliliters of 
trimethyl-chlorosilane (1.5 moles). The contents are allowed to heat at 
60.degree. to 75.degree. C. for six hours. HPLC analysis is utilized to 
determine when the reaction is complete. The contents of the flask is 
poured into a 3 liter Erlenmeyer flask containing 1.5 liter of deionized 
water. The water layer is decanted and the dark oily residue taken up into 
500 milliliters methanol. The methanol solution is extracted with two 400 
milliliter portions of hexane to remove the hexamethyldisiloxane 
by-products. The methanol solution was rotoevaporated to remove the 
solvents. The residue is taken up into 500 milliliters of acetone and 
then precipitated into 1.5 liters deionized water. The off-white solid is 
filtered and then washed with deionized water and dried in vacuo. The 
crude N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)[1,1'-biphenyl]-4,4'-diamine 
is placed into a two liter round-bottom flask containing a magnetic 
stirrer and one liter toluene. Fifty gms. Florisil.RTM. (Florisil is a 
registered trademark of Floridin Co.) is added to the flask and allowed to 
stir for two hours. The dark Florisil.RTM. is filtered off, leaving a pale 
yellow toluene solution. The toluene is roto-evaporated to yield a pale 
yellow viscous oil. The oily product is dissolved in 400 milliliters 
acetone then diluted with 400 milliliters heptane and allowed to 
crystallize. The colorless crystals were filtered. Additional product is 
obtained by roto-evaporating the acetone from the filtrate. 
Preferred silanes include dimethyldichlorosilane, diethyldichlorosilane, 
methylvinyl-dichlorosilane, 1,1,4,4-tetramethyl-1,4-dichlorodisilethylene, 
1,2-dichlorotetramethyldisiloxane, methyltrichlorosilane, 
phenylmethyldichlorosilane, 1,7-dichlorooctamethyltetrasiloxane, 
1,5-dichlorohexamethyltrisiloxane and the like. 
An organic amine may be used in the reaction. Typical materials include 
amine halogen acceptors and pyridine is generally preferred. 
EXAMPLE I 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
Dimethyldichlorosilane 
The reaction vessel was constructed using a 500 ml. 3-necked Morton flask, 
a mechanical stirrer, a thermometer, a water condenser, a dropping burette 
and an electric heating mantle. The reaction vessel was charged with 10.4 
grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 2.8 grams of (CH.sub.3).sub.2 SiCl.sub.2 (0.022 moles) and 7 
cc of dry toluene. 
Using external heating and vigorous agitation, the kettle contents was 
heated to approximately 50.degree. to 60.degree. C. At 58.degree. C. the 
feed was added slowly and dropwise over the span of approximately 10 
minutes. No external heat was used after the addition of the feed because 
the exothermic reaction maintained the temperature at approximately 
62.degree. C. After addition of the feed was complete, the reaction 
mixture was heated externally for approximately 15 minutes at 
approximately 60.degree. C. 
When the contents of the reaction vessel reached 30.degree. C., 100 cc of 
water and 100 cc of toluene were added and the mixture was stirred well. 
The contents of the reaction vessel were then transferred to a separatory 
funnel where the bottom water layer was removed. Then 100 cc of 2% 
HCl/H.sub.2 O was added to the funnel and the contents were shaken well. 
The water layer was removed and the step was repeated. Then 100 cc of 2% 
NaHCO.sub.3 /H.sub.2 O was added and the contents were stirred. The water 
layer was removed and the step was repeated. The contents were washed 
twice with 100 cc portions of H.sub.2 O. The solvent/polymer layer was 
then removed, dried with Na.sub.2 SO.sub.4, and filtered. Yield=10.0 
grams. 
EXAMPLE II 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine, 
Bis-Phenol A and Dimethyldichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 8.0 grams of dry Et.sub.3 N, 6.2 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine 
(0.012 moles), 50 cc of dry toluene, and 1.8 grams of bis-phenol A (about 
0.008 moles). The feed was comprised of 2.8 grams of (CH.sub.3).sub.2 
SiCl.sub.2 (0.022 moles) and 7 cc of dry toluene. 
Using external heating and vigorous agitation, the kettle contents was 
heated to approximately 60.degree. C. At 55.degree. C. the feed was added 
slowly and dropwise over the span of approximately 50 minutes. After 
addition of the feed was complete, the reaction mixture was heated 
externally for approximately 15 to 20 minutes at approximately 50.degree. 
to 60.degree. C. The contents were washed as in Example I to neutral pH. 
The contents were then dried over Na.sub.2 SO.sub.4, and filtered. 
The polymer solution obtained after filtration was recharged into the 
reaction vessel and 1.0 gram of (CH.sub.3).sub.2 SiCl.sub.2 was added over 
the span of one hour. The contents were cooled and transferred to a 
separatory funnel where the contents were washed 3 times with 100 cc 
portions of H.sub.2 O, separated, dried over Na2SO4, and filtered. The 
filtered product was then precipitated into methanol and filtered. The 
solids were dried in a vacuum overnight at 50.degree. C. Yield=5.5 grams. 
EXAMPLE III 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,5-Dichlorohexamethyltrisiloxane and Dimethyldichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The first 
feed was comprised of 1.1 grams of 1,5 dichlorohexamethyltrisiloxane 
(about 0.004 moles) and 2.0 grams of dry toluene. The second feed was 
comprised of 2.3 grams (0.018 moles) of Me.sub.2 SiCl.sub.2 and 7.0 grams 
of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the first feed was 
added slowly and dropwise over the span of approximately 10 minutes. After 
addition of the first feed was complete, the reaction mixture was heated 
externally for approximately 15 minutes at approximately 74.degree. C. The 
reaction was then cooled to 60.degree. C. and the second feed was added 
dropwise. After addition of the second feed was complete, the reaction 
mixture was heated externally for approximately 15 minutes at 
approximately 60.degree. C. The reaction was cooled to room temperature 
where the contents were precipitated into 1500 ml of MeOH. A stringy 
elastomeric precipitate formed and was filtered through coarse glass frit. 
The filtrate was washed with MeOH and n-hexane. The solid was then dried 
at 45.degree.-50.degree. C. for 16 hours. The resulting solid was slightly 
turbid. 
The dried solid was then resolvated in 75 cc of dry toluene. A celite 
filter aid was added and the solution was vacuum filtered through coarse 
glass frit. The filtrate was precipitated in 1500 ml n-heptane. The 
resulting polymer cake was washed with MeOH and vacuum dried for 3 hours 
at 50.degree. C. The resulting solid was now transparent. Yield=9.5 grams. 
Mol. wt. data: M.sub.N =38,323, M.sub.W =115,971, disp. 3.03. 
EXAMPLE IV 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine, 
Bis-Phenol A, 1,5-Dichlorohexamethyltrisiloxane and Dimethyldichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 8.3 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine 
(0.016 moles), 0.9 grams of bis-phenol A (BPA) (0.004 moles), 50 cc of dry 
toluene, and 5.0 grams of dry pyridine. The first feed was comprised of 
1.4 grams of 1,5 -dichlorohexamethyltrisiloxane (about 0.005 moles) and 
2.0 grams of dry toluene. The second feed was comprised of 2.2 grams of 
Me.sub.2 SiCl.sub.2 (0.017 moles) and 7.0 grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the first feed was 
added slowly and dropwise over the span of approximately 10 minutes. After 
addition of the first feed was complete, the reaction mixture was heated 
externally for approximately 15 minutes at approximately 75.degree. C. The 
reaction was then cooled to 65.degree. C. and the second feed was added 
dropwise. After 20 minutes, the addition of the second feed was complete 
and the reaction mixture was heated externally for approximately 15 
minutes at approximately 65.degree. C. The reaction was cooled to room 
temperature where the contents were vacuum filtered through a coarse glass 
frit. The filtrate was precipitated into 1000 cc of heptane and stirred 
for 1 hour. The solution was then filtered through a coarse glass frit and 
the solid was vacuum dried at 50.degree. C. for three hours. Yield=9.2 
grams. Mol. wt. data: M.sub.N =21,339, M.sub.W =45,140, disp.= 2.12. 
EXAMPLE V 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine, 
Dimethyldichlorosilane and Methyltrichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The first 
feed was comprised of 2.8 grams of Me.sub.2 SiCl.sub.2, and 7.0 grams of 
dry toluene. The second feed was comprised of 0.05 grams of MeSiCl.sub.3 
in 1.0 grams of dry toluene. 
The kettle charge was stirred at room temperature until dissolved. The feed 
was added while stirring vigorously. After addition of the feed was 
complete, the reaction mixture rose to 34.degree. C. because it was 
exothermic. The reaction mixture was then heated externally for 
approximately 30 minutes at approximately 50.degree. C. The reaction was 
then cooled to room temperature. The solution was filtered through a 
coarse glass frit and returned to the kettle. While stirring the mixture 
at 25.degree. C. 0.05 grams of MeSiCl.sub.3 in 1.0 grams of toluene was 
added. After 15 minutes the reaction mixture was then heated externally 
for approximately 15 minutes at approximately 50.degree. C. The reaction 
was then cooled to room temperature and the solution was filtered through 
a coarse glass frit. The solution was then stirred for 1 hour in 1500 cc 
of n-hexane, washed with MeOH, and filtered through a coarse glass frit. 
The remaining solid was vacuum dried at 60.degree. C. for 16 hours. 
Yield=10.2 grams. Mol. wt. data: M.sub.N =53,866, M.sub.W =239,958, 
disp.=4.45. 
EXAMPLE VI 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine, 
Dimethyldichlorosilane and Methyltrichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 2.7 grams of Me.sub.2 SiCl.sub.2 (0.021 moles), 0.1 grams of 
MeSiCl.sub.3 (0.0007 moles), and 8.0 grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 50.degree. to 60.degree. C. At 50.degree. C. the 
feed was added slowly and dropwise over the span of approximately 20 
minutes. After addition of the feed was complete, the reaction mixture was 
heated externally for approximately 60 minutes at approximately 55.degree. 
C. and was stirred vigorously. 
The reaction was cooled to room temperature. The solution was filtered 
through a coarse glass frit and returned to the kettle. The solution was 
then stirred for 1 hour in 1500 cc of n-hexane, washed with MeOH, and 
filtered through a coarse glass frit. The remaining solid was vacuum dried 
at 50.degree.-55.degree. C. overnight. Yield=9.8 grams. Mol. wt. data: 
M.sub.N =13,664, M.sub.W =51,377, disp.=3.76. 
EXAMPLE VII 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine, 
1,5-Dichlorohexamethyltrisiloxane and Methyltrichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 5.5 grams of 1,5-dichlorohexamethyltrisiloxane (0.02 moles) 
and 5.0 grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the feed was added 
slowly and dropwise over the span of approximately 35 minutes. After 
addition of the feed was complete, the reaction mixture was heated 
externally for approximately 60 minutes at approximately 70.degree. C. and 
was stirred vigorously. 
The reaction was then cooled to room temperature. At 25.degree. C., 0.05 
grams of MeSiCl.sub.3 was added and heated to 50.degree. C. After 15 
minutes an additional 0.05 grams of MeSiCl.sub.3 was added and heated at 
50.degree. C. for 15 minutes. The solution was cooled to room temperature, 
filtered through a coarse glass frit and precipitated in 1500 cc of 
methanol. The solution was vacuum filtered through a coarse glass frit. 
The remaining solid was vacuum dried at 50.degree. C. for 3.0 hours. 
Yield=9.6 grams. Mol. wt. data: M.sub.N =22,268, M.sub.W =64,435, 
disp.=2.89. 
EXAMPLE VIII 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,7-Dichlorooctamethyltetrasiloxane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 7.0 grams of 1,7-dichlorooctamethyltetrasiloxane (0.02 moles) 
and 7.0 grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the feed was added 
slowly and dropwise over the span of approximately 35 minutes. The 
contents then were maintained at 75.degree. C. for one hour. The reaction 
was then cooled to 50.degree. C., and 0.1 grams of MeSiCl.sub.3 in 1.0 
gram of toluene was added and heated to 50.degree.-55.degree. C. and 
stirred for 15 minutes. 
The contents were cooled to room temperature, filtered and precipitated 
into 1500 cc methanol. The precipitate was then vacuum overnight at 
55.degree. C. Yield=10.0 grams. Mol. wt. data: M.sub.N =30,156, M.sub.W 
=86,774, disp.=2.88. 
EXAMPLE IX 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,1,4,4-Tetramethyl-1,4-dichlorodisilethylene 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 4.3 grams of 1,1,4,4-tetramethyl-1,4-dichlorodisilethylene 
(0.02 moles) and 7.0 grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the feed was added 
slowly and dropwise over the span of approximately 30 minutes. The 
contents then were maintained at 75.degree. C. for one hour. The reaction 
was cooled to 50.degree. C., and 0.1 grams of MeSiCl.sub.3 in 1.0 gram of 
toluene was added and heated to 50.degree.-55.degree. C. and stirred for 
15 minutes. 
The contents were cooled to room temperature, filtered and precipitated 
into 1500 cc MeOH. The precipitate was then vacuum dried overnight at 
55.degree. C. Yield=11.5 grams. Mol. wt. data: M.sub.N =6,723, M.sub.W 
=30,139, disp.=4.48. 
EXAMPLE X 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,7-Dichlorooctamethyltetrasiloxane and Phenylmethyldichlorosilane 
The reaction vessel was constructed as in example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The feed was 
comprised of 5.6 grams of 1,7-dichlorooctamethyltetrasiloxane (0.016 
moles), 0.8 grams of phenylmethyldichlorosilane (0.004 moles) and 7.0 
grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the feed was added 
slowly and dropwise over the span of approximately 40 minutes. The 
contents then were maintained at 75.degree. C. for one hour. The reaction 
was then cooled to about 50.degree.-55.degree. C. At 55.degree. C., 0.1 
grams of MeSiCl.sub.3 in 1.0 grams of toluene was added and heated to 
50.degree.-55.degree. C. and stirred for 15 minutes. 
The contents were cooled to room temperature, filtered through a coarse 
glass frit and precipitated into 1500 cc MeOH. The precipitate was then 
vacuum dried overnight at 50.degree. C. Yield=13.2 grams. 
EXAMPLE XI 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,7-Dichlorooctamethyltetrasiloxane and Dimethyldichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1,1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The first 
feed was comprised of 3.5 grams of 1,7-dichlorooctamethyltetrasiloxane 
(about 0.01 moles) and 7.0 grams of dry toluene. The second feed was 
comprised of 1.6 grams of dimethyldichlorosilane (0.012 moles) and 3.0 
grams of dry toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the first feed was 
added slowly and dropwise over the span of approximately 20 minutes. The 
contents then were maintained at 75.degree. C. for 20 minutes. The 
reaction was then cooled to 50.degree. C. At 50.degree. C. the second feed 
was added slowly and dropwise over the span of approximately 10 minutes. 
The contents then were maintained at 50.degree. C. for 15 minutes. The 
contents were cooled to room temperature, filtered through #2 Whatman 
paper, and precipitated into 1500 cc MeOH. The precipitate was then vacuum 
dried at 50.degree. C. for three hours. Yield=10.6 grams. Mol. wt. data: 
M.sub.N =23,988, M.sub.W =64,439, disp.=2.69. 
EXAMPLE XII 
Transport Polymer Preparation Using 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine and 
1,7-Dichlorooctamethyltetrasiloxane and Dimethyldichlorosilane 
The reaction vessel was constructed as in Example I. The reaction vessel 
was charged with 10.4 grams of 
N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1-1'-biphenyl)-4,4'-diamine (0.02 
moles), 50 cc of dry toluene, and 5.0 grams of dry pyridine. The first 
feed was comprised of 3.5 grams of 1,7-dichlorooctamethyltetrasiloxane 
(0.01 moles) and 7.0 grams of dry toluene. The second feed was comprised 
of 1.8 grams of dimethyldichlorosilane (0.014 moles) and 3.0 grams of dry 
toluene. 
Using external heating and vigorous agitation, the kettle contents were 
heated to approximately 75.degree. C. At 75.degree. C. the first feed was 
added slowly and dropwise over the span of approximately 25 minutes. The 
contents then were maintained at 75.degree. C. for 15 minutes. The 
reaction was then cooled to 50.degree. C. At 50.degree. C. the second feed 
was added slowly and dropwise over the span of approximately 20 minutes. 
The contents were maintained at 50.degree. C. for 15 minutes. 
The contents were cooled to room temperature, filtered through #2 Whatman 
paper, and precipitated into 1500 cc MeOH. The precipitate solution was 
stirred for one hour and then filtered through a coarse glass frit. The 
polymer cake was washed with MeOH several times. The polymer cake was then 
vacuum dried at 50.degree. C. for 16 hours. Yield=12.3 grams. Mol. wt. 
data: M.sub.N =34,482, M.sub.W =78,131, disp.=2.27.