U.S. patent application number 15/288301 was filed with the patent office on 2017-01-26 for periodic structured organic films.
The applicant listed for this patent is XEROX CORPORATION. Invention is credited to Adrien P. Cote, Matthew A. Heuft.
Application Number | 20170022338 15/288301 |
Document ID | / |
Family ID | 45096432 |
Filed Date | 2017-01-26 |
United States Patent
Application |
20170022338 |
Kind Code |
A1 |
Cote; Adrien P. ; et
al. |
January 26, 2017 |
PERIODIC STRUCTURED ORGANIC FILMS
Abstract
An ordered structured organic film comprising a plurality of
segments and a plurality of linkers arranged as a covalent organic
framework, wherein the structured organic film may be a
multi-segment thick structured organic film.
Inventors: |
Cote; Adrien P.; (Kitchener,
CA) ; Heuft; Matthew A.; (Oakville, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
XEROX CORPORATION |
Norwalk |
CT |
US |
|
|
Family ID: |
45096432 |
Appl. No.: |
15/288301 |
Filed: |
October 7, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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12815688 |
Jun 15, 2010 |
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15288301 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 2377/00 20130101;
C08G 18/3281 20130101; C09D 179/02 20130101; C08J 2367/00 20130101;
C08J 2377/06 20130101; C08J 5/18 20130101; C08J 2375/00 20130101;
C08J 2369/00 20130101; C08J 2379/02 20130101; C09D 175/04 20130101;
C08G 18/751 20130101; Y10T 428/24777 20150115; C09D 177/06
20130101; C08G 18/7614 20130101; C09D 177/00 20130101; B05D 3/065
20130101; C09D 169/00 20130101; C09D 167/00 20130101; C08G 18/329
20130101 |
International
Class: |
C08J 5/18 20060101
C08J005/18; C09D 169/00 20060101 C09D169/00; B05D 3/06 20060101
B05D003/06; C09D 167/00 20060101 C09D167/00; C09D 177/06 20060101
C09D177/06; C09D 175/04 20060101 C09D175/04; C09D 179/02 20060101
C09D179/02; C09D 177/00 20060101 C09D177/00 |
Claims
1. A process for preparing a structured organic film (SOF)
comprising: (a) preparing a liquid-containing reaction mixture
comprising: a first solvent, a second solvent, and a plurality of
molecular building blocks each of the plurality of molecular
building blocks being either a segment or linker; (b) forming a
pre-SOF from the plurality of molecular building blocks; (c)
depositing the formed pre-SOF as a wet film on a substrate; and (d)
promoting a change of the wet film to a dry film comprising the SOF
as a covalent organic framework (COF), wherein at a macroscopic
level the covalent organic framework is a film; wherein the SOF is
periodic as determined by two-dimensional X-ray scattering.
2. The process of claim 1, wherein the at least one of the
molecular building blocks comprises at least one atom that is not
carbon.
3. The process of claim 1, wherein forming the pre-SOF comprises
heating.
4. The process of claim 1, wherein forming the pre-SOF comprises
irradiating with UV radiation.
5. The process of claim 1, further comprising removing the SOF from
the substrate to obtain a free-standing SOF.
6. The process of claim 5, further comprising processing the
free-standing SOF into a roll.
7. The process of claim 1, further comprising cutting and seaming
the SOF into a belt.
8. The process of claim 1, comprising repeating the steps in SOF
formation one or more times, wherein the substrate at each
iteration is a prior fabricated SOF.
9. The process of claim 1, wherein promoting a change of the wet
film to a dry film comprising the SOF comprises heating to remove
the first solvent, the second solvent, or both.
10. The process of claim 1, wherein a catalyst is used in forming
the pre-SOF.
11. The process of claim 1, wherein the wet film has a viscosity of
about 50 cps to about 1000 cps.
12. A process for preparing a structured organic film (SOF)
comprising: (a) preparing a liquid-containing reaction mixture
comprising: a first solvent, a second solvent, and a plurality of
molecular building blocks each of the plurality of molecular
building blocks being either a segment or linker; (b) forming a
pre-SOF from the plurality of molecular building blocks; (c)
depositing the formed pre-SOF as a wet film on a substrate, wherein
the substrate is a prior fabricated SOF; and (d) promoting a change
of the wet film to a dry film comprising the SOF as a covalent
organic framework (COF), wherein at a macroscopic level the
covalent organic framework is a film; wherein the SOF is periodic
as determined by two-dimensional X-ray
13. The process of claim 12, wherein the at least one of the
molecular building blocks comprises at least one atom that is not
carbon.
14. The process of claim 12, wherein forming the pre-SOF comprises
heating.
15. The process of claim 12, wherein forming the pre-SOF comprises
irradiating with UV radiation.
16. The process of claim 12, further comprising removing the SOF
from the substrate to obtain a free-standing SOF.
17. The process of claim 16, further comprising processing the
free-standing SOF into a roll.
18. The process of claim 12, further comprising cutting and seaming
the SOF into a belt.
19. The process of claim 12, wherein promoting a change of the wet
film to a dry film comprising the SOF comprises heating to remove
the first solvent, the second solvent, or both.
20. The process of claim 12, wherein a catalyst is used in forming
the pre-SOF.
Description
[0001] This application is a divisional application of U.S. patent
application Ser. No. 12/815,688, the disclosure of which is totally
incorporated herein by reference in its entirety.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0002] Commonly assigned U.S. patent application Ser. Nos.
12/716,524; 12/716,449; 12/716,706; 12/716,324; 12/716,686; and
Ser. No. 12/716,571, entitled "Structured Organic Films,"
"Structured Organic Films Having an Added Functionality," "Mixed
Solvent Process for Preparing Structured Organic Films," "Composite
Structured Organic Films," "Process For Preparing Structured
Organic Films (SOFs) Via a Pre-SOF," "Electronic Devices Comprising
Structured Organic Films," respectively, the disclosures of which
are totally incorporated herein by reference in their entireties,
describe structured organic films, methods for preparing structured
organic films and applications of structured organic films.
BACKGROUND OF THE INVENTION
[0003] Materials whose chemical structures are comprised of
molecules linked by covalent bonds into extended structures may be
placed into two classes: (1) polymers and cross-linked polymers,
and (2) covalent organic frameworks (also known as covalently
linked organic networks).
[0004] The first class, polymers and cross-linked polymers, is
typically embodied by polymerization of molecular monomers to form
long linear chains of covalently-bonded molecules. Polymer
chemistry processes can allow for polymerized chains to, in turn,
or concomitantly, become `cross-linked.` The nature of polymer
chemistry offers poor control over the molecular-level structure of
the formed material, i.e. the organization of polymer chains and
the patterning of molecular monomers between chains is mostly
random. Nearly all polymers are amorphous, save for some linear
polymers that efficiently pack as ordered rods. Some polymer
materials, notably block co-polymers, can possess regions of order
within their bulk. In the two preceding cases the patterning of
polymer chains is not by design, any ordering at the
molecular-level is a consequence of the natural intermolecular
packing tendencies.
[0005] The second class, covalent organic frameworks (COFs), differ
from the first class (polymers/cross-linked polymers) in that COFs
are intended to be highly patterned. In COF chemistry molecular
components are called molecular building blocks rather than
monomers. During COF synthesis molecular building blocks react to
form two- or three-dimensional networks. Consequently, molecular
building blocks are patterned throughout COF materials and
molecular building blocks are linked to each other through strong
covalent bonds.
[0006] COFs developed thus far are typically powders with high
porosity and are materials with exceptionally low density. COFs can
store near-record amounts of argon and nitrogen. While these
conventional COFs are useful, there is a need, addressed by
embodiments of the present invention, for new materials that offer
advantages over conventional COFs in terms of enhanced
characteristics.
SUMMARY OF THE DISCLOSURE
[0007] There is provided in embodiments an ordered (periodic)
structured organic film comprising a plurality of segments and a
plurality of linkers arranged as a covalent organic framework,
wherein at a macroscopic level the covalent organic framework is a
film.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Other aspects of the present disclosure will become apparent
as the following description proceeds and upon reference to the
following figures which represent illustrative embodiments:
[0009] FIG. 1 is a graphic representation that compares the Fourier
transform infrared spectral of the products of control experiments
mixtures, wherein only
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
is added to the liquid reaction mixture (top), wherein only
benzene-1,4-dimethanol is added to the liquid reaction mixture
(middle), and wherein the necessary components needed to form a
patterned Type 2 SOF are included into the liquid reaction mixture
(bottom).
[0010] FIG. 2 is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising
N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine segments, p-xylyl
segments, and ether linkers.
[0011] FIG. 3 is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising
N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine segments, n-hexyl
segments, and ether linkers.
[0012] FIG. 4 is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising
N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine segments,
4,4'-(cyclohexane-1,1-diyl)diphenyl, and ether linkers.
[0013] FIG. 5 is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising of
triphenylamine segments and ether linkers.
[0014] FIG. 6 is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising triphenylamine
segments, benzene segments, and imine linkers.
[0015] FIG. 7. is a graphic representation of a Fourier transform
infrared spectrum of a free standing SOF comprising triphenylamine
segments, and imine linkers.
[0016] FIG. 8 is a graphic representation of two-dimensional X-ray
scattering data for the SOFs produced in Examples 26 and 54.
DETAILED DESCRIPTION
[0017] "Structured organic film" (SOF) is a new term introduced by
the present disclosure to refer to a COF that is a film at a
macroscopic level. The term "SOF" refers to a covalent organic
framework (COF) that is a film at a macroscopic level. The phrase
"macroscopic level" refers, for example, to the naked eye view of
the present SOFs. Although COFs are a network at the "microscopic
level" or "molecular level" (requiring use of powerful magnifying
equipment or as assessed using scattering methods), the present SOF
is fundamentally different at the "macroscopic level" because the
film is for instance orders of magnitude larger in coverage than a
microscopic level COF network. SOFs described herein have
macroscopic morphologies much different than typical COFs
previously synthesized. COFs previously synthesized were typically
obtained as polycrystalline or particulate powders wherein the
powder is a collection of at least thousands of particles
(crystals) where each particle (crystal) can have dimensions
ranging from nanometers to millimeters. The shape of the particles
can range from plates, spheres, cubes, blocks, prisms, etc. The
composition of each particle (crystal) is the same throughout the
entire particle while at the edges, or surfaces of the particle, is
where the segments of the covalently-linked framework terminate.
The SOFs described herein are not collections of particles.
Instead, the SOFs of the present disclosure are at the macroscopic
level substantially defect-free SOFs or defect-free SOFs having
continuous covalent organic frameworks that can extend over larger
length scales such as for instance much greater than a millimeter
to lengths such as a meter and, in theory, as much as hundreds of
meters. It will also be appreciated that SOFs tend to have large
aspect ratios where typically two dimensions of a SOF will be much
larger than the third. SOFs have markedly fewer macroscopic edges
and disconnected external surfaces than a collection of COF
particles.
[0018] In embodiments, a "substantially defect-free SOF" or
"defect-free SOF" may be formed from a reaction mixture deposited
on the surface of an underlying substrate. The term "substantially
defect-free SOF" refers, for example, to an SOF that may or may not
be removed from the underlying substrate on which it was formed and
contains substantially no pinholes, pores or gaps greater than the
distance between the cores of two adjacent segments per square cm;
such as, for example, less than 10 pinholes, pores or gaps greater
than about 250 nanometers in diameter per cm.sup.2, or less than 5
pinholes, pores or gaps greater than about 100 nanometers in
diameter per cm.sup.2. The term "defect-free SOF" refers, for
example, to an SOF that may or may not be removed from the
underlying substrate on which it was formed and contains no
pinholes, pores or gaps greater than the distance between the cores
of two adjacent segments per micron, such as no pinholes, pores or
gaps greater than about 100 Angstroms in diameter per micron.sup.2,
or no pinholes, pores or gaps greater than about 50 Angstroms in
diameter per micron.sup.2, or no pinholes, pores or gaps greater
than about 20 Angstroms in diameter per micron.sup.2.
[0019] In embodiments, the SOF comprises at least one atom of an
element that is not carbon, such at least one atom selected from
the group consisting of hydrogen, oxygen, nitrogen, silicon,
phosphorous, selenium, fluorine, boron, and sulfur. In further
embodiments, the SOF is a boroxine-, borazine-, borosilicate-, and
boronate ester-free SOF.
[0020] Molecular Building Block
[0021] The SOFs of the present disclosure comprise molecular
building blocks having a segment (S) and functional groups (Fg).
Molecular building blocks require at least two functional groups
(x.gtoreq.2) and may comprise a single type or two or more types of
functional groups. Functional groups are the reactive chemical
moieties of molecular building blocks that participate in a
chemical reaction to link together segments during the SOF forming
process. A segment is the portion of the molecular building block
that supports functional groups and comprises all atoms that are
not associated with functional groups. Further, the composition of
a molecular building block segment remains unchanged after SOF
formation.
[0022] Functional Group
[0023] Functional groups are the reactive chemical moieties of
molecular building blocks that participate in a chemical reaction
to link together segments during the SOF forming process.
Functional groups may be composed of a single atom, or functional
groups may be composed of more than one atom. The atomic
compositions of functional groups are those compositions normally
associated with reactive moieties in chemical compounds.
Non-limiting examples of functional groups include halogens,
alcohols, ethers, ketones, carboxylic acids, esters, carbonates,
amines, amides, imines, ureas, aldehydes, isocyanates, tosylates,
alkenes, alkynes and the like.
[0024] Molecular building blocks contain a plurality of chemical
moieties, but only a subset of these chemical moieties are intended
to be functional groups during the SOF forming process. Whether or
not a chemical moiety is considered a functional group depends on
the reaction conditions selected for the SOF forming process.
Functional groups (Fg) denote a chemical moiety that is a reactive
moiety, that is, a functional group during the SOF forming
process.
[0025] In the SOF forming process the composition of a functional
group will be altered through the loss of atoms, the gain of atoms,
or both the loss and the gain of atoms; or, the functional group
may be lost altogether. In the SOF, atoms previously associated
with functional groups become associated with linker groups, which
are the chemical moieties that join together segments. Functional
groups have characteristic chemistries and those of ordinary skill
in the art can generally recognize in the present molecular
building blocks the atom(s) that constitute functional group(s). It
should be noted that an atom or grouping of atoms that are
identified as part of the molecular building block functional group
may be preserved in the linker group of the SOF. Linker groups are
described below.
[0026] Segment
[0027] A segment is the portion of the molecular building block
that supports functional groups and comprises all atoms that are
not associated with functional groups. Further, the composition of
a molecular building block segment remains unchanged after SOF
formation. In embodiments, the SOF may contain a first segment
having a structure the same as or different from a second segment.
In other embodiments, the structures of the first and/or second
segments may be the same as or different from a third segment,
forth segment, fifth segment, etc. A segment is also the portion of
the molecular building block that can provide an inclined property.
Inclined properties are described later in the embodiments.
[0028] In specific embodiments, the segment of the SOF comprises at
least one atom of an element that is not carbon, such at least one
atom selected from the group consisting of hydrogen, oxygen,
nitrogen, silicon, phosphorous, selenium, fluorine, boron, and
sulfur.
[0029] A description of various exemplary molecular building
blocks, linkers, SOF types, strategies to synthesize a specific SOF
type with exemplary chemical structures, building blocks whose
symmetrical elements are outlined, and classes of exemplary
molecular entities and examples of members of each class that may
serve as molecular building blocks for SOFs are detailed in U.S.
patent application Ser. Nos. 12/716,524; 12/716,449; 12/716,706;
12/716,324; 12/716,686; and 12/716,571, entitled "Structured
Organic Films," "Structured Organic Films Having an Added
Functionality," "Mixed Solvent Process for Preparing Structured
Organic Films," "Composite Structured Organic Films," "Process For
Preparing Structured Organic Films (SOFs) Via a Pre-SOF,"
"Electronic Devices Comprising Structured Organic Films," the
disclosures of which are totally incorporated herein by reference
in their entireties.
[0030] Metrical Parameters of SOFs
[0031] SOFs have any suitable aspect ratio. In embodiments, SOFs
have aspect ratios for instance greater than about 30:1 or greater
than about 50:1, or greater than about 70:1, or greater than about
100:1, such as about 1000:1. The aspect ratio of a SOF is defined
as the ratio of its average width or diameter (that is, the
dimension next largest to its thickness) to its average thickness
(that is, its shortest dimension). The term `aspect ratio,` as used
here, is not bound by theory. The longest dimension of a SOF is its
length and it is not considered in the calculation of SOF aspect
ratio.
[0032] Generally, SOFs have widths and lengths, or diameters
greater than about 500 micrometers, such as about 10 mm, or 30 mm.
The SOFs have the following illustrative thicknesses: about 10
Angstroms to about 250 Angstroms, such as about 20 Angstroms to
about 200 Angstroms, for a mono-segment thick layer and about 20 nm
to about 5 mm, about 50 nm to about 10 mm for a multi-segment thick
layer.
[0033] SOF dimensions may be measured using a variety of tools and
methods. For a dimension about 1 micrometer or less, scanning
electron microscopy is the preferred method. For a dimension about
1 micrometer or greater, a micrometer (or ruler) is the preferred
method.
[0034] Multilayer SOFs
[0035] A SOF may comprise a single layer or a plurality of layers
(that is, two, three or more layers). SOFs that are comprised of a
plurality of layers may be physically joined (e.g., dipole and
hydrogen bond) or chemically joined. Physically attached layers are
characterized by weaker interlayer interactions or adhesion;
therefore physically attached layers may be susceptible to
delamination from each other. Chemically attached layers are
expected to have chemical bonds (e.g., covalent or ionic bonds) or
have numerous physical or intermolecular (supramolecular)
entanglements that strongly link adjacent layers.
[0036] Therefore, delamination of chemically attached layers is
much more difficult. Chemical attachments between layers may be
detected using spectroscopic methods such as focusing infrared or
Raman spectroscopy, or with other methods having spatial resolution
that can detect chemical species precisely at interfaces. In cases
where chemical attachments between layers are different chemical
species than those within the layers themselves it is possible to
detect these attachments with sensitive bulk analyses such as
solid-state nuclear magnetic resonance spectroscopy or by using
other bulk analytical methods.
[0037] In the embodiments, the SOF may be a single layer
(mono-segment thick or multi-segment thick) or multiple layers
(each layer being mono-segment thick or multi-segment thick).
"Thickness" refers, for example, to the smallest dimension of the
film. As discussed above, in a SOF, segments are molecular units
that are covalently bonded through linkers to generate the
molecular framework of the film. The thickness of the film may also
be defined in terms of the number of segments that is counted along
that axis of the film when viewing the cross-section of the film. A
"monolayer" SOF is the simplest case and refers, for example, to
where a film is one segment thick. A SOF where two or more segments
exist along this axis is referred to as a "multi-segment" thick
SOF.
[0038] An exemplary method for preparing physically attached
multilayer SOFs includes: (1) forming a base SOF layer that may be
cured by a first curing cycle, and (2) forming upon the base layer
a second reactive wet layer followed by a second curing cycle and,
if desired, repeating the second step to form a third layer, a
forth layer and so on. The physically stacked multilayer SOFs may
have thicknesses greater than about 20 Angstroms such as, for
example, the following illustrative thicknesses: about 20 Angstroms
to about 10 cm, such as about 1 nm to about 10 mm, or about 0.1 mm
Angstroms to about 5 mm. In principle there is no limit with this
process to the number of layers that may be physically stacked.
[0039] In embodiments, a multilayer SOF is formed by a method for
preparing chemically attached multilayer SOFs by: (1) forming a
base SOF layer having functional groups present on the surface (or
dangling functional groups) from a first reactive wet layer, and
(2) forming upon the base layer a second SOF layer from a second
reactive wet layer that comprises molecular building blocks with
functional groups capable of reacting with the dangling functional
groups on the surface of the base SOF layer. In further
embodiments, a capped SOF may serve as the base layer in which the
functional groups present that were not suitable or complementary
to participate in the specific chemical reaction to link together
segments during the base layer SOF forming process may be available
for reacting with the molecular building blocks of the second layer
to from an chemically bonded multilayer SOF. If desired, the
formulation used to form the second SOF layer should comprise
molecular building blocks with functional groups capable of
reacting with the functional groups from the base layer as well as
additional functional groups that will allow for a third layer to
be chemically attached to the second layer. The chemically stacked
multilayer SOFs may have thicknesses greater than about 20
Angstroms such as, for example, the following illustrative
thicknesses: about 20 Angstroms to about 10 cm, such as about 1 nm
to about 10 mm, or about 0.1 mm Angstroms to about 5 mm. In
principle there is no limit with this process to the number of
layers that may be chemically stacked.
[0040] In embodiments, the method for preparing chemically attached
multilayer SOFs comprises promoting chemical attachment of a second
SOF onto an existing SOF (base layer) by using a small excess of
one molecular building block (when more than one molecular building
block is present) during the process used to form the SOF (base
layer) whereby the functional groups present on this molecular
building block will be present on the base layer surface. The
surface of base layer may be treated with an agent to enhance the
reactivity of the functional groups or to create an increased
number of functional groups.
[0041] In an embodiment the dangling functional groups or chemical
moieties present on the surface of an SOF or capped SOF may be
altered to increase the propensity for covalent attachment (or,
alternatively, to disfavor covalent attachment) of particular
classes of molecules or individual molecules, such as SOFs, to a
base layer or any additional substrate or SOF layer. For example,
the surface of a base layer, such as an SOF layer, which may
contain reactive dangling functional groups, may be rendered
pacified through surface treatment with a capping chemical group.
For example, a SOF layer having dangling hydroxyl alcohol groups
may be pacified by treatment with trimethylsiylchloride thereby
capping hydroxyl groups as stable trimethylsilylethers.
Alternatively, the surface of base layer may be treated with a
non-chemically bonding agent, such as a wax, to block reaction with
dangling functional groups from subsequent layers.
[0042] Molecular Building Block Symmetry
[0043] Molecular building block symmetry relates to the positioning
of functional groups (Fgs) around the periphery of the molecular
building block segments. Without being bound by chemical or
mathematical theory, a symmetric molecular building block is one
where positioning of Fgs may be associated with the ends of a rod,
vertexes of a regular geometric shape, or the vertexes of a
distorted rod or distorted geometric shape. For example, the most
symmetric option for molecular building blocks containing four Fgs
are those whose Fgs overlay with the corners of a square or the
apexes of a tetrahedron.
[0044] Use of symmetrical building blocks is practiced in
embodiments of the present disclosure for two reasons: (1) the
patterning of molecular building blocks may be better anticipated
because the linking of regular shapes is a better understood
process in reticular chemistry, and (2) the complete reaction
between molecular building blocks is facilitated because for less
symmetric building blocks errant conformations/orientations may be
adopted which can possibly initiate numerous linking defects within
SOFs.
[0045] In embodiments, a Type 1 SOF contains segments, which are
not located at the edges of the SOF, that are connected by linkers
to at least three other segments. For example, in embodiments the
SOF comprises at least one symmetrical building block selected from
the group consisting of ideal triangular building blocks, distorted
triangular building blocks, ideal tetrahedral building blocks,
distorted tetrahedral building blocks, ideal square building
blocks, and distorted square building blocks. In embodiments, Type
2 and 3 SOF contains at least one segment type, which are not
located at the edges of the SOF, that are connected by linkers to
at least three other segments. For example, in embodiments the SOF
comprises at least one symmetrical building block selected from the
group consisting of ideal triangular building blocks, distorted
triangular building blocks, ideal tetrahedral building blocks,
distorted tetrahedral building blocks, ideal square building
blocks, and distorted square building blocks.
[0046] Practice of Linking Chemistry
[0047] In embodiments linking chemistry may occur wherein the
reaction between functional groups produces a volatile byproduct
that may be largely evaporated or expunged from the SOF during or
after the film forming process or wherein no byproduct is formed.
Linking chemistry may be selected to achieve a SOF for applications
where the presence of linking chemistry byproducts is not desired.
Linking chemistry reactions may include, for example, condensation,
addition/elimination, and addition reactions, such as, for example,
those that produce esters, imines, ethers, carbonates, urethanes,
amides, acetals, and silyl ethers.
[0048] In embodiments the linking chemistry via a reaction between
function groups producing a non-volatile byproduct that largely
remains incorporated within the SOF after the film forming process.
Linking chemistry in embodiments may be selected to achieve a SOF
for applications where the presence of linking chemistry byproducts
does not impact the properties or for applications where the
presence of linking chemistry byproducts may alter the properties
of a SOF (such as, for example, the electroactive, hydrophobic or
hydrophilic nature of the SOF). Linking chemistry reactions may
include, for example, substitution, metathesis, and metal catalyzed
coupling reactions, such as those that produce carbon-carbon
bonds.
[0049] For all linking chemistry the ability to control the rate
and extent of reaction between building blocks via the chemistry
between building block functional groups is an important aspect of
the present disclosure. Reasons for controlling the rate and extent
of reaction may include adapting the film forming process for
different coating methods and tuning the microscopic arrangement of
building blocks to achieve a periodic SOF, as defined in earlier
embodiments.
[0050] Innate Properties of COFs
[0051] COFs have innate properties such as high thermal stability
(typically higher than 400.degree. C. under atmospheric
conditions); poor solubility in organic solvents (chemical
stability), and porosity (capable of reversible guest uptake). In
embodiments, SOFs may also possess these innate properties.
[0052] Added Functionality of SOFs
[0053] Added functionality denotes a property that is not inherent
to conventional COFs and may occur by the selection of molecular
building blocks wherein the molecular compositions provide the
added functionality in the resultant SOF. Added functionality may
arise upon assembly of molecular building blocks having an
"inclined property" for that added functionality. Added
functionality may also arise upon assembly of molecular building
blocks having no "inclined property" for that added functionality
but the resulting SOF has the added functionality as a consequence
of linking segments (S) and linkers into a SOF. Furthermore,
emergence of added functionality may arise from the combined effect
of using molecular building blocks bearing an "inclined property"
for that added functionality whose inclined property is modified or
enhanced upon linking together the segments and linkers into a
SOF.
[0054] An Inclined Property of a Molecular Building Block
[0055] The term "inclined property" of a molecular building block
refers, for example, to a property known to exist for certain
molecular compositions or a property that is reasonably
identifiable by a person skilled in art upon inspection of the
molecular composition of a segment. As used herein, the terms
"inclined property" and "added functionality" refer to the same
general property (e.g., hydrophobic, electroactive, etc.) but
"inclined property" is used in the context of the molecular
building block and "added functionality" is used in the context of
the SOF.
[0056] The hydrophobic (superhydrophobic), hydrophilic, lipophobic
(superlipophobic), lipophilic, photochromic and/or electroactive
(conductor, semiconductor, charge transport material) nature of an
SOF are some examples of the properties that may represent an
"added functionality" of an SOF. These and other added
functionalities may arise from the inclined properties of the
molecular building blocks or may arise from building blocks that do
not have the respective added functionality that is observed in the
SOF.
[0057] The term hydrophobic (superhydrophobic) refers, for example,
to the property of repelling water, or other polar species such as
methanol, it also means an inability to absorb water and/or to
swell as a result. Furthermore, hydrophobic implies an inability to
form strong hydrogen bonds to water or other hydrogen bonding
species. Hydrophobic materials are typically characterized by
having water contact angles greater than 90.degree. and
superhydrophobic materials have water contact angles greater than
150.degree. as measured using a contact angle goniometer or related
device.
[0058] The term hydrophilic refers, for example, to the property of
attracting, adsorbing, or absorbing water or other polar species,
or a surface that is easily wetted by such species. Hydrophilic
materials are typically characterized by having less than
20.degree. water contact angle as measured using a contact angle
goniometer or related device. Hydrophilicity may also be
characterized by swelling of a material by water or other polar
species, or a material that can diffuse or transport water, or
other polar species, through itself. Hydrophilicity, is further
characterized by being able to form strong or numerous hydrogen
bonds to water or other hydrogen bonding species.
[0059] The term lipophobic (oleophobic) refers, for example, to the
property of repelling oil or other non-polar species such as
alkanes, fats, and waxes. Lipophobic materials are typically
characterized by having oil contact angles greater than 90.degree.
as measured using a contact angle goniometer or related device.
[0060] The term lipophilic (oleophilic) refers, for example, to the
property attracting oil or other non-polar species such as alkanes,
fats, and waxes or a surface that is easily wetted by such species.
Lipophilic materials are typically characterized by having a low to
nil oil contact angle as measured using, for example, a contact
angle goniometer. Lipophilicity can also be characterized by
swelling of a material by hexane or other non-polar liquids.
[0061] The term photochromic refers, for example, to the ability to
demonstrate reversible color changes when exposed to
electromagnetic radiation. SOF compositions containing photochromic
molecules may be prepared and demonstrate reversible color changes
when exposed to electromagnetic radiation. These SOFs may have the
added functionality of photochromism. The robustness of
photochromic SOFs may enable their use in many applications, such
as photochromic SOFs for erasable paper, and light responsive films
for window tinting/shading and eye wear. SOF compositions may
contain any suitable photochromic molecule, such as a difunctional
photochromic molecules as SOF molecular building blocks (chemically
bound into SOF structure), a monofunctional photochromic molecules
as SOF capping units (chemically bound into SOF structure, or
unfunctionalized photochromic molecules in an SOF composite (not
chemically bound into SOF structure). Photochromic SOFs may change
color upon exposure to selected wavelengths of light and the color
change may be reversible.
[0062] SOF compositions containing photochromic molecules that
chemically bond to the SOF structure are exceptionally chemically
and mechanically robust photochromic materials. Such photochromic
SOF materials demonstrate many superior properties, such as high
number of reversible color change processes, to available polymeric
alternatives.
[0063] The term electroactive refers, for example, to the property
to transport electrical charge (electrons and/or holes).
Electroactive materials include conductors, semiconductors, and
charge transport materials. Conductors are defined as materials
that readily transport electrical charge in the presence of a
potential difference. Semiconductors are defined as materials do
not inherently conduct charge but may become conductive in the
presence of a potential difference and an applied stimuli, such as,
for example, an electric field, electromagnetic radiation, heat,
and the like. Charge transport materials are defined as materials
that can transport charge when charge is injected from another
material such as, for example, a dye, pigment, or metal in the
presence of a potential difference.
[0064] Conductors may be further defined as materials that give a
signal using a potentiometer from about 0.1 to about 10.sup.7
S/cm.
[0065] Semiconductors may be further defined as materials that give
a signal using a potentiometer from about 10.sup.-6 to about
10.sup.4 S/cm in the presence of applied stimuli such as, for
example an electric field, electromagnetic radiation, heat, and the
like. Alternatively, semiconductors may be defined as materials
having electron and/or hole mobility measured using time-of-flight
techniques in the range of 10.sup.-10 to about 10.sup.6
cm.sup.2V.sup.-1s.sup.-1 when exposed to applied stimuli such as,
for example an electric field, electromagnetic radiation, heat, and
the like.
[0066] Charge transport materials may be further defined as
materials that have electron and/or hole mobility measured using
time-of-flight techniques in the range of 10.sup.-10 to about
10.sup.6 cm.sup.2V.sup.-1s.sup.-1. It should be noted that under
some circumstances charge transport materials may be also
classified as semiconductors.
[0067] SOFs with hydrophobic added functionality may be prepared by
using molecular building blocks with inclined hydrophobic
properties and/or have a rough, textured, or porous surface on the
sub-micron to micron scale. A paper describing materials having a
rough, textured, or porous surface on the sub-micron to micron
scale being hydrophobic was authored by Cassie and Baxter (Cassie,
A. B. D.; Baxter, S. Trans. Faraday Soc., 1944, 40, 546).
[0068] Molecular building blocks comprising or bearing
highly-fluorinated segments have inclined hydrophobic properties
and may lead to SOFs with hydrophobic added functionality.
Highly-fluorinated segments are defined as the number of fluorine
atoms present on the segment(s) divided by the number of hydrogen
atoms present on the segment(s) being greater than one. Fluorinated
segments, which are not highly-fluorinated segments may also lead
to SOFs with hydrophobic added functionality.
[0069] The above-mentioned fluorinated segments may include, for
example, tetrafluorohydroquinone, perfluoroadipic acid hydrate,
4,4'-(hexafluoroisopropylidene)diphthalic anhydride,
4,4'-(hexafluoroisopropylidene)diphenol, and the like.
[0070] SOFs having a rough, textured, or porous surface on the
sub-micron to micron scale may also be hydrophobic. The rough,
textured, or porous SOF surface can result from dangling functional
groups present on the film surface or from the structure of the
SOF. The type of pattern and degree of patterning depends on the
geometry of the molecular building blocks and the linking chemistry
efficiency. The feature size that leads to surface roughness or
texture is from about 100 nm to about 10 .mu.m, such as from about
500 nm to about 5 .mu.m.
[0071] SOFs with hydrophilic added functionality may be prepared by
using molecular building blocks with inclined hydrophilic
properties and/or comprising polar linking groups.
[0072] Molecular building blocks comprising segments bearing polar
substituents have inclined hydrophilic properties and may lead to
SOFs with hydrophilic added functionality. The term polar
substituents refers, for example, to substituents that can form
hydrogen bonds with water and include, for example, hydroxyl,
amino, ammonium, and carbonyl (such as ketone, carboxylic acid,
ester, amide, carbonate, urea).
[0073] SOFs with electroactive added functionality may be prepared
by using molecular building blocks with inclined electroactive
properties and/or be electroactive resulting from the assembly of
conjugated segments and linkers. The following sections describe
molecular building blocks with inclined hole transport properties,
inclined electron transport properties, and inclined semiconductor
properties.
[0074] SOFs with hole transport added functionality may be obtained
by selecting segment cores such as, for example, triarylamines,
hydrazones (U.S. Pat. No. 7,202,002 B2 to Tokarski et al.), and
enamines (U.S. Pat. No. 7,416,824 B2 to Kondoh et al.) with the
following general structures:
##STR00001##
The segment core comprising a triarylamine being represented by the
following general formula:
##STR00002##
wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 each
independently represents a substituted or unsubstituted aryl group,
or Ar.sup.5 independently represents a substituted or unsubstituted
arylene group, and k represents 0 or 1, wherein at least two of
Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 comprises a Fg
(previously defined). Ar.sup.5 may be further defined as, for
example, a substituted phenyl ring, substituted/unsubstituted
phenylene, substituted/unsubstituted monovalently linked aromatic
rings such as biphenyl, terphenyl, and the like, or
substituted/unsubstituted fused aromatic rings such as naphthyl,
anthranyl, phenanthryl, and the like.
[0075] Segment cores comprising arylamines with hole transport
added functionality include, for example, aryl amines such as
triphenylamine, N,N,N',N'-tetraphenyl-(1,1'-biphenyl)-4,4'-diamine,
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine,
N,N'-bis(4-butylphenyl)-N,N'-diphenyl-[p-terphenyl]-4,4''-diamine;
hydrazones such as N-phenyl-N-methyl-3-(9-ethyl)carbazyl hydrazone
and 4-diethyl amino benzaldehyde-1,2-diphenyl hydrazone; and
oxadiazoles such as
2,5-bis(4-N,N-diethylaminophenyl)-1,2,4-oxadiazole, stilbenes, and
the like.
[0076] Molecular building blocks comprising triarylamine core
segments with inclined hole transport properties may be derived
from the list of chemical structures including, for example, those
listed below:
##STR00003## ##STR00004## ##STR00005##
[0077] The segment core comprising a hydrazone being represented by
the following general formula:
##STR00006##
wherein Ar.sup.1, Ar.sup.2, and Ar.sup.3 each independently
represents an aryl group optionally containing one or more
substituents, and R represents a hydrogen atom, an aryl group, or
an alkyl group optionally containing a substituent; wherein at
least two of Ar.sup.1, Ar.sup.2, and Ar.sup.3 comprises a Fg
(previously defined); and a related oxadiazole being represented by
the following general formula:
##STR00007##
wherein Ar and Ar.sup.1 each independently represent an aryl group
that comprises a Fg (previously defined).
[0078] Molecular building blocks comprising hydrazone and
oxadiazole core segments with inclined hole transport properties
may be derived from the list of chemical structures including, for
example, those listed below:
##STR00008## ##STR00009##
[0079] The segment core comprising an enamine being represented by
the following general formula:
##STR00010##
wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, and Ar.sup.4 each
independently represents an aryl group that optionally contains one
or more substituents or a heterocyclic group that optionally
contains one or more substituents, and R represents a hydrogen
atom, an aryl group, or an alkyl group optionally containing a
substituent; wherein at least two of Ar.sup.1, Ar.sup.2, Ar.sup.3,
and Ar.sup.4 comprises a Fg (previously defined).
[0080] Molecular building blocks comprising enamine core segments
with inclined hole transport properties may be derived from the
list of chemical structures including, for example, those listed
below:
##STR00011## ##STR00012##
[0081] SOFs with electron transport added functionality may be
obtained by selecting segment cores comprising, for example,
nitrofluorenones, 9-fluorenylidene malonitriles, diphenoquinones,
and naphthalenetetracarboxylic diimides with the following general
structures:
##STR00013##
It should be noted that the carbonyl groups of diphenylquinones
could also act as Fgs in the SOF forming process.
[0082] SOFs with semiconductor added functionality may be obtained
by selecting segment cores such as, for example, acenes,
thiophenes/oligothiophenes/fused thiophenes, perylene bisimides, or
tetrathiofulvalenes, and derivatives thereof with the following
general structures:
##STR00014##
[0083] The SOF may be a p-type semiconductor, n-type semiconductor
or ambipolar semiconductor. The SOF semiconductor type depends on
the nature of the molecular building blocks. Molecular building
blocks that possess an electron donating property such as alkyl,
alkoxy, aryl, and amino groups, when present in the SOF, may render
the SOF a p-type semiconductor. Alternatively, molecular building
blocks that are electron withdrawing such as cyano, nitro, fluoro,
fluorinated alkyl, and fluorinated aryl groups may render the SOF
into the n-type semiconductor.
[0084] Molecular building blocks comprising acene core segments
with inclined semiconductor properties may be derived from the list
of chemical structures including, for example, those listed
below:
##STR00015##
[0085] Molecular building blocks comprising
thiophene/oligothiophene/fused thiophene core segments with
inclined semiconductor properties may be derived from the list of
chemical structures including, for example, those listed below:
##STR00016##
[0086] Examples of molecular building blocks comprising perylene
bisimide core segments with inclined semiconductor properties may
be derived from the chemical structure below:
##STR00017##
[0087] Molecular building blocks comprising tetrathiofulvalene core
segments with inclined semiconductor properties may be derived from
the list of chemical structures including, for example, those
listed below:
##STR00018##
wherein Ar each independently represents an aryl group that
optionally contains one or more substituents or a heterocyclic
group that optionally contains one or more substituents.
[0088] Similarly, the electroactivity of SOFs prepared by these
molecular building blocks will depend on the nature of the
segments, nature of the linkers, and how the segments are
orientated within the SOF. Linkers that favor preferred
orientations of the segment moieties in the SOF are expected to
lead to higher electroactivity.
[0089] Process for Preparing an Ordered Structured Organic Film
[0090] The process for making ordered SOFs typically comprises a
number of activities or steps (set forth below) that may be
performed in any suitable sequence or where two or more activities
are performed simultaneously or in close proximity in time:
A process for preparing a ordered (periodic) structured organic
film comprising: (a) preparing a liquid-containing reaction mixture
comprising a plurality of molecular building blocks each comprising
a segment and a number of functional groups; (b) depositing the
reaction mixture as a wet film; (c) promoting a change of the wet
film including the molecular building blocks to a dry film
comprising the SOF comprising a plurality of the segments and a
plurality of linkers arranged as a covalent organic framework,
wherein at a macroscopic level the covalent organic framework is a
film; (d) optionally removing the SOF from the coating substrate to
obtain a free-standing SOF; (e) optionally processing the
free-standing SOF into a roll; (f) optionally cutting and seaming
the SOF into a belt; and (g) optionally performing the above SOF
formation process(es) upon an SOF (which was prepared by the above
SOF formation process(es)) as a substrate for subsequent SOF
formation process(es).
[0091] The above activities or steps may be conducted at
atmospheric, super atmospheric, or subatmospheric pressure. The
term "atmospheric pressure" as used herein refers to a pressure of
about 760 torr. The term "super atmospheric" refers to pressures
greater than atmospheric pressure, but less than 20 atm. The term
"subatmospheric pressure" refers to pressures less than atmospheric
pressure. In an embodiment, the activities or steps may be
conducted at or near atmospheric pressure. Generally, pressures of
from about 0.1 atm to about 2 atm, such as from about 0.5 atm to
about 1.5 atm, or 0.8 atm to about 1.2 atm may be conveniently
employed.
[0092] Process Action A: Preparation of the Liquid-Containing
Reaction Mixture
[0093] The reaction mixture comprises a plurality of molecular
building blocks that are dissolved, suspended, or mixed in a
liquid. The plurality of molecular building blocks may be of one
type or two or more types. When one or more of the molecular
building blocks is a liquid, the use of an additional liquid is
optional. Catalysts may optionally be added to the reaction mixture
to enable SOF formation or modify the kinetics of SOF formation
during Action C described above. Additives or secondary components
may optionally be added to the reaction mixture to alter the
physical properties of the resulting SOF.
[0094] The reaction mixture components (molecular building blocks,
optionally a liquid, optionally catalysts, and optionally
additives) are combined in a vessel. The order of addition of the
reaction mixture components may vary; however, typically the
catalyst is added last. In particular embodiments, the molecular
building blocks are heated in the liquid in the absence of the
catalyst to aid the dissolution of the molecular building blocks.
The reaction mixture may also be mixed, stirred, milled, or the
like, to ensure even distribution of the formulation components
prior to depositing the reaction mixture as a wet film.
[0095] In embodiments, the reaction mixture may be heated prior to
being deposited as a wet film. This may aid the dissolution of one
or more of the molecular building blocks and/or increase the
viscosity of the reaction mixture by the partial reaction of the
reaction mixture prior to depositing the wet layer. This approach
may be used to increase the loading of the molecular building
blocks in the reaction mixture.
[0096] In particular embodiments, the reaction mixture needs to
have a viscosity that will support the deposited wet layer.
Reaction mixture viscosities range from about 10 to about 50,000
cps, such as from about 25 to about 25,000 cps or from about 50 to
about 1000 cps.
[0097] The molecular building block loading or "loading" in the
reaction mixture is defined as the total weight of the molecular
building blocks and optionally the catalysts divided by the total
weight of the reaction mixture. Building block loadings may range
from about 3 to 100%, such as from about 5 to about 50%, or from
about 15 to about 40%. In the case where a liquid molecular
building block is used as the only liquid component of the reaction
mixture (i.e. no additional liquid is used), the building block
loading would be about 100%.
[0098] In embodiments, the reaction mixture comprises a plurality
of molecular building blocks that are dissolved, suspended, or
mixed in a liquid. The plurality of molecular building blocks may
be of one type or two or more types. When one or more of the
molecular building blocks is a liquid, the use of an additional
liquid is optional.
[0099] Catalysts may optionally be added to the reaction mixture to
enable pre-SOF formation and/or modify the kinetics of SOF
formation during Action C described above. The term "pre-SOF" may
refer to, for example, at least two molecular building blocks that
have reacted and have a molecular weight higher than the starting
molecular building block and contain multiple functional groups
capable of undergoing further reactions with functional groups of
other building blocks or pre-SOFs to obtain a SOF, which may be a
substantially defect-free or defect-free SOF, and/or the
`activation` of molecular building block functional groups that
imparts enhanced or modified reactivity for the film forming
process. Activation may include dissociation of a functional group
moiety, pre-association with a catalyst, association with a solvent
molecule, liquid, second solvent, second liquid, secondary
component, or with any entity that modifies functional group
reactivity. In embodiments, pre-SOF formation may include the
reaction between molecular building blocks or the `activation` of
molecular building block functional groups, or a combination of the
two. The formation of the "pre-SOF" may be achieved by in a number
of ways, such as heating the reaction mixture, exposure of the
reaction mixture to UV radiation, or any other means of partially
reacting the molecular building blocks and/or activating functional
groups in the reaction mixture prior to deposition of the wet layer
on the substrate. Additives or secondary components may optionally
be added to the reaction mixture to alter the physical properties
of the resulting SOF.
[0100] The reaction mixture components (molecular building blocks,
optionally a liquid, optionally catalysts, and optionally
additives) are combined in a vessel. The order of addition of the
reaction mixture components may vary; however, typically when a
process for preparing a SOF includes a pre-SOF or formation of a
pre-SOF, the catalyst, when present, may be added to the reaction
mixture before depositing the reaction mixture as a wet film. In
embodiments, the molecular building blocks may be reacted
actinically, thermally, chemically or by any other means with or
without the presence of a catalyst to obtain a pre-SOF. The pre-SOF
and the molecular building blocks formed in the absence of catalyst
may be may be heated in the liquid in the absence of the catalyst
to aid the dissolution of the molecular building blocks and
pre-SOFs. In embodiments, the pre-SOF and the molecular building
blocks formed in the presence of catalyst may be may be heated at a
temperature that does not cause significant further reaction of the
molecular building blocks and/or the pre-SOFs to aid the
dissolution of the molecular building blocks and pre-SOFs. The
reaction mixture may also be mixed, stirred, milled, or the like,
to ensure even distribution of the formulation components prior to
depositing the reaction mixture as a wet film.
[0101] In embodiments, the reaction mixture may be heated prior to
being deposited as a wet film. This may aid the dissolution of one
or more of the molecular building blocks and/or increase the
viscosity of the reaction mixture by the partial reaction of the
reaction mixture prior to depositing the wet layer to form
pre-SOFs. For example, the weight percent of molecular building
blocks in the reaction mixture that are incorporated into
pre-reacted molecular building blocks pre-SOFs may be less than
20%, such as about 15% to about 1%, or 10% to about 5%. In
embodiments, the molecular weight of the 95% pre-SOF molecules is
less than 5,000 daltons, such as 2,500 daltons, or 1,000 daltons.
The preparation of pre-SOFs may be used to increase the loading of
the molecular building blocks in the reaction mixture.
[0102] In the case of pre-SOF formation via functional group
activation, the molar percentage of functional groups that are
activated may be less than 50%, such as about 30% to about 10%, or
about 10% to about 5%.
[0103] In embodiments, the two methods of pre-SOF formation
(pre-SOF formation by the reaction between molecular building
blocks or pre-SOF formation by the `activation` of molecular
building block functional groups) may occur in combination and the
molecular building blocks incorporated into pre-SOF structures may
contain activated functional groups. In embodiments, pre-SOF
formation by the reaction between molecular building blocks and
pre-SOF formation by the `activation` of molecular building block
functional groups may occur simultaneously.
[0104] In embodiments, the duration of pre-SOF formation lasts
about 10 seconds to about 48 hours, such as about 30 seconds to
about 12 hours, or about 1 minute to 6 hours.
[0105] In particular embodiments, the reaction mixture needs to
have a viscosity that will support the deposited wet layer.
Reaction mixture viscosities range from about 10 to about 50,000
cps, such as from about 25 to about 25,000 cps or from about 50 to
about 1000 cps.
[0106] The molecular building block loading or "loading" in the
reaction mixture is defined as the total weight of the molecular
building blocks and optionally the catalysts divided by the total
weight of the reaction mixture. Building block loadings may range
from about 3 to 100%, such as from about 5 to about 50%, or from
about 15 to about 40%. In the case where a liquid molecular
building block is used as the only liquid component of the reaction
mixture (i.e. no additional liquid is used), the building block
loading would be about 100%.
[0107] In embodiments, the pre-SOF may be made from building blocks
with one or more of the added functionality selected from the group
consisting of hydrophobic added functionality, superhydrophobic
added functionality, hydrophilic added functionality, lipophobic
added functionality, superlipophobic added functionality,
lipophilic added functionality, photochromic added functionality,
and electroactive added functionality. In embodiments, the inclined
property of the molecular building blocks is the same as the added
functionality of the pre-SOF. In embodiments, the added
functionality of the SOF is not an inclined property of the
molecular building blocks.
[0108] Liquids used in the reaction mixture may be pure liquids,
such as solvents, and/or solvent mixtures. Liquids are used to
dissolve or suspend the molecular building blocks and
catalyst/modifiers in the reaction mixture. Liquid selection is
generally based on balancing the solubility/dispersion of the
molecular building blocks and a particular building block loading,
the viscosity of the reaction mixture, and the boiling point of the
liquid, which impacts the promotion of the wet layer to the dry
SOF. Suitable liquids may have boiling points from about 30 to
about 300.degree. C., such as from about 65.degree. C. to about
250.degree. C., or from about 100.degree. C. to about 180.degree.
C.
[0109] Liquids can include molecule classes such as alkanes
(hexane, heptane, octane, nonane, decane, cyclohexane,
cycloheptane, cyclooctane, decalin); mixed alkanes (hexanes,
heptanes); branched alkanes (isooctane); aromatic compounds
(toluene, o-, m-, p-xylene, mesitylene, nitrobenzene, benzonitrile,
butylbenzene, aniline); ethers (benzyl ethyl ether, butyl ether,
isoamyl ether, propyl ether); cyclic ethers (tetrahydrofuran,
dioxane), esters (ethyl acetate, butyl acetate, butyl butyrate,
ethoxyethyl acetate, ethyl propionate, phenyl acetate, methyl
benzoate); ketones (acetone, methyl ethyl ketone, methyl
isobutylketone, diethyl ketone, chloroacetone, 2-heptanone), cyclic
ketones (cyclopentanone, cyclohexanone), amines (1.degree.,
2.degree., or 3.degree. amines such as butylamine,
diisopropylamine, triethylamine, diisoproylethylamine; pyridine);
amides (dimethylformamide, N-methylpyrolidinone,
N,N-dimethylformamide); alcohols (methanol, ethanol, n-,
i-propanol, n-, t-butanol, 1-methoxy-2-propanol, hexanol,
cyclohexanol, 3-pentanol, benzyl alcohol); nitriles (acetonitrile,
benzonitrile, butyronitrile), halogenated aromatics (chlorobenzene,
dichlorobenzene, hexafluorobenzene), halogenated alkanes
(dichloromethane, chloroform, dichloroethylene, tetrachloroethane);
and water.
[0110] Mixed liquids comprising a first solvent, second solvent,
third solvent, and so forth may also be used in the reaction
mixture. Two or more liquids may be used to aid the
dissolution/dispersion of the molecular building blocks; and/or
increase the molecular building block loading; and/or allow a
stable wet film to be deposited by aiding the wetting of the
substrate and deposition instrument; and/or modulate the promotion
of the wet layer to the dry SOF. In embodiments, the second solvent
is a solvent whose boiling point or vapor-pressure curve or
affinity for the molecular building blocks differs from that of the
first solvent. In embodiments, a first solvent has a boiling point
higher than that of the second solvent. In embodiments, the second
solvent has a boiling point equal to or less than about 130.degree.
C., such as a boiling point equal to or less than about 100.degree.
C., for example in the range of from about 30.degree. C. to about
100.degree. C., or in the range of from about 40.degree. C. to
about 90.degree. C., or about 50.degree. C. to about 80.degree.
C.
[0111] In embodiments, the first solvent, or higher boiling point
solvent, has a boiling point equal to or greater than about
65.degree. C., such as in the range of from about 80.degree. C. to
about 300.degree. C., or in the range of from about 100.degree. C.
to about 250.degree. C., or about 100.degree. C. to about
180.degree. C. The higher boiling point solvent may include, for
example, the following (the value in parentheses is the boiling
point of the compound): hydrocarbon solvents such as amylbenzene
(202.degree. C.), isopropylbenzene (152.degree. C.),
1,2-diethylbenzene (183.degree. C.), 1,3-diethylbenzene
(181.degree. C.), 1,4-diethylbenzene (184.degree. C.),
cyclohexylbenzene (239.degree. C.), dipentene (177.degree. C.),
2,6-dimethylnaphthalene (262.degree. C.), p-cymene (177.degree.
C.), camphor oil (160-185.degree. C.), solvent naphtha
(110-200.degree. C.), cis-decalin (196.degree. C.), trans-decalin
(187.degree. C.), decane (174.degree. C.), tetralin (207.degree.
C.), turpentine oil (153-175.degree. C.), kerosene (200-245.degree.
C.), dodecane (216.degree. C.), dodecylbenzene (branched), and so
forth; ketone and aldehyde solvents such as acetophenone
(201.7.degree. C.), isophorone (215.3.degree. C.), phorone
(198-199.degree. C.), methylcyclohexanone (169.0-170.5.degree. C.),
methyl n-heptyl ketone (195.3.degree. C.), and so forth; ester
solvents such as diethyl phthalate (296.1.degree. C.), benzyl
acetate (215.5.degree. C.), .gamma.-butyrolactone (204.degree. C.),
dibutyl oxalate (240.degree. C.), 2-ethylhexyl acetate
(198.6.degree. C.), ethyl benzoate (213.2.degree. C.), benzyl
formate (203.degree. C.), and so forth; diethyl sulfate
(208.degree. C.), sulfolane (285.degree. C.), and halohydrocarbon
solvents; etherified hydrocarbon solvents; alcohol solvents;
ether/acetal solvents; polyhydric alcohol solvents; carboxylic
anhydride solvents; phenolic solvents; water; and silicone
solvents.
[0112] The ratio of the mixed liquids may be established by one
skilled in the art. The ratio of liquids a binary mixed liquid may
be from about 1:1 to about 99:1, such as from about 1:10 to about
10:1, or about 1:5 to about 5:1, by volume. When n liquids are
used, with n ranging from about 3 to about 6, the amount of each
liquid ranges from about 1% to about 95% such that the sum of each
liquid contribution equals 100%.
[0113] In embodiments, the mixed liquid comprises at least a first
and a second solvent with different boiling points. In further
embodiments, the difference in boiling point between the first and
the second solvent may be from about nil to about 150.degree. C.,
such as from nil to about 50.degree. C. For example, the boiling
point of the first solvent may exceed the boiling point of the
second solvent by about 1.degree. C. to about 100.degree. C., such
as by about 5.degree. C. to about 100.degree. C., or by about
10.degree. C. to about 50.degree. C. The mixed liquid may comprise
at least a first and a second solvent with different vapor
pressures, such as combinations of high vapor pressure solvents
and/or low vapor pressure solvents. The term "high vapor pressure
solvent" refers to, for example, a solvent having a vapor pressure
of at least about 1 kPa, such as about 2 kPa, or about 5 kPa. The
term "low vapor pressure solvent" refers to, for example, a solvent
having a vapor pressure of less than about 1 kPa, such as about 0.9
kPa, or about 0.5 kPa. In embodiments, the first solvent may be a
low vapor pressure solvent such as, for example, terpineol,
diethylene glycol, ethylene glycol, hexylene glycol,
N-methyl-2-pyrrolidone, and tri(ethylene glycol) dimethyl ether. A
high vapor pressure solvent allows rapid removal of the solvent by
drying and/or evaporation at temperatures below the boiling point.
High vapor pressure solvents may include, for example, acetone,
tetrahydrofuran, toluene, xylene, ethanol, methanol, 2-butanone and
water.
[0114] In embodiments where mixed liquids comprising a first
solvent, second solvent, third solvent, and so forth are used in
the reaction mixture, promoting the change of the wet film and
forming the dry SOF may comprise, for example, heating the wet film
to a temperature above the boiling point of the reaction mixture to
form the dry SOF film; or heating the wet film to a temperature
above the boiling point of the second solvent (below the
temperature of the boiling point of the first solvent) in order to
remove the second solvent while substantially leaving the first
solvent and then after substantially removing the second solvent,
removing the first solvent by heating the resulting composition at
a temperature either above or below the boiling point of the first
solvent to form the dry SOF film; or heating the wet film below the
boiling point of the second solvent in order to remove the second
solvent (which is a high vapor pressure solvent) while
substantially leaving the first solvent and, after removing the
second solvent, removing the first solvent by heating the resulting
composition at a temperature either above or below the boiling
point of the first solvent to form the dry SOF film.
[0115] The term "substantially removing" refers to, for example,
the removal of at least 90% of the respective solvent, such as
about 95% of the respective solvent. The term "substantially
leaving" refers to, for example, the removal of no more than 2% of
the respective solvent, such as removal of no more than 1% of the
respective solvent.
[0116] These mixed liquids may be used to slow or speed up the rate
of conversion of the wet layer to the SOF in order to manipulate
the characteristics of the SOFs. For example, in condensation and
addition/elimination linking chemistries, liquids such as water,
1.degree., 2.degree., or 3.degree. alcohols (such as methanol,
ethanol, propanol, isopropanol, butanol, 1-methoxy-2-propanol,
tert-butanol) may be used.
[0117] Optionally a catalyst may be present in the reaction mixture
to assist the promotion of the wet layer to the dry SOF. Selection
and use of the optional catalyst depends on the functional groups
on the molecular building blocks. Catalysts may be homogeneous
(dissolved) or heterogeneous (undissolved or partially dissolved)
and include Bronsted acids (HCl(aq), acetic acid, p-toluenesulfonic
acid, amine-protected p-toluenesulfonic acid such as pyrridium
p-toluenesulfonate, trifluoroacetic acid); Lewis acids (boron
trifluoroetherate, aluminum trichloride); Bronsted bases (metal
hydroxides such as sodium hydroxide, lithium hydroxide, potassium
hydroxide; 1.degree., 2.degree., or 3.degree. amines such as
butylamine, diisopropylamine, triethylamine, diisoproylethylamine);
Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze);
metal salts (FeCl.sub.3, AuCl.sub.3); and metal complexes (ligated
palladium complexes, ligated ruthenium catalysts). Typical catalyst
loading ranges from about 0.01% to about 25%, such as from about
0.1% to about 5% of the molecular building block loading in the
reaction mixture. The catalyst may or may not be present in the
final SOF composition.
[0118] Optionally additives or secondary components may be present
in the reaction mixture and wet layer. Such additives or secondary
components may also be integrated into a dry SOF. Additives or
secondary components can be homogeneous or heterogeneous in the
reaction mixture and wet layer or in a dry SOF. The terms
"additive" or "secondary component," refer, for example, to atoms
or molecules that are not covalently bound in the SOF, but are
randomly distributed in the composition. Additives may be used to
alter the physical properties of the SOF such as electrical
properties (conductivity, semiconductivity, electron transport,
hole transport), surface energy (hydrophobicity, hydrophilicity),
tensile strength, thermal conductivity, impact modifiers,
reinforcing fibers, antiblocking agents, lubricants, antistatic
agents, coupling agents, wetting agents, antifogging agents, flame
retardants, ultraviolet stabilizers, antioxidants, biocides, dyes,
pigments, odorants, deodorants, nucleating agents and the like.
[0119] Process Action B: Depositing the Reaction Mixture as a Wet
Film
[0120] The reaction mixture may be applied as a wet film to a
variety of substrates using a number of liquid deposition
techniques. The thickness of the SOF is dependant on the thickness
of the wet film and the molecular building block loading in the
reaction mixture. The thickness of the wet film is dependent on the
viscosity of the reaction mixture and the method used to deposit
the reaction mixture as a wet film.
Substrates include, for example, polymers, papers, metals and metal
alloys, doped and undoped forms of elements from Groups III-VI of
the periodic table, metal oxides, metal chalcogenides, and
previously prepared SOF films. Examples of polymer film substrates
include polyesters, polyolefins, polycarbonates, polystyrenes,
polyvinylchloride, block and random copolymers thereof, and the
like. Examples of metallic surfaces include metallized polymers,
metal foils, metal plates; mixed material substrates such as metals
patterned or deposited on polymer, semiconductor, metal oxide, or
glass substrates. Examples of substrates comprised of doped and
undoped elements from Groups III-VI of the periodic table include,
aluminum, silicon, silicon n-doped with phosphorous, silicon
p-doped with boron, tin, gallium arsenide, lead, gallium indium
phosphide, and indium. Examples of metal oxides include silicon
dioxide, titanium dioxide, indium tin oxide, tin dioxide, selenium
dioxide, and alumina. Examples of metal chalcogenides include
cadmium sulfide, cadmium telluride, and zinc selenide.
Additionally, it is appreciated that chemically treated or
mechanically modified forms of the above substrates remain within
the scope of surfaces which may be coated with the reaction
mixture.
[0121] In embodiments, the substrate may be composed of, for
example, silicon, glass plate, plastic film or sheet. For
structurally flexible devices, a plastic substrate such as
polyester, polycarbonate, polyimide sheets and the like may be
used. The thickness of the substrate may be from around 10
micrometers to over 10 millimeters with an exemplary thickness
being from about 50 to about 100 micrometers, especially for a
flexible plastic substrate, and from about 1 to about 10
millimeters for a rigid substrate such as glass or silicon.
[0122] The reaction mixture may be applied to the substrate using a
number of liquid deposition techniques including, for example, spin
coating, blade coating, web coating, dip coating, cup coating, rod
coating, screen printing, ink jet printing, spray coating, stamping
and the like. The method used to deposit the wet layer depends on
the nature, size, and shape of the substrate and the desired wet
layer thickness. The thickness of the wet layer can range from
about 10 nm to about 5 mm, such as from about 100 nm to about 1 mm,
or from about 1 .mu.m to about 500 .mu.m.
[0123] Process Action C: Promoting the Change of Wet Film to the
Dry SOF
[0124] The term "promoting" refers, for example, to any suitable
technique to facilitate a reaction of the molecular building
blocks. In the case where a liquid needs to be removed to form the
dry film, "promoting" also refers to removal of the liquid.
Reaction of the molecular building blocks and removal of the liquid
can occur sequentially or concurrently.
[0125] In embodiments, the term "promoting" may also refer, for
example, to any suitable technique to facilitate a reaction of the
molecular building blocks and/or pre-SOFs, such as a chemical
reaction of the functional groups of the building blocks and/or
pre-SOFs. Reaction of the molecular building blocks and/or pre-SOFs
and removal of the liquid can occur sequentially or
concurrently.
[0126] In certain embodiments, the liquid is also one of the
molecular building blocks and is incorporated into the SOF. The
term "dry SOF" refers, for example, to substantially dry films such
as, for example, a substantially dry SOF may have a liquid content
less than about 5% by weight of the SOF, or a liquid content less
than about 2% by weight of the SOF.
[0127] Promoting the wet layer to form a dry SOF may be
accomplished by any suitable technique. Promoting the wet layer to
form a dry SOF typically involves thermal treatment including, for
example, oven drying, infrared radiation (IR), and the like with
temperatures ranging from 40 to 350.degree. C. and from 60 to
200.degree. C. and from 85 to 160.degree. C. The total heating time
can range from about four seconds to about 24 hours, such as from
one minute to 120 minutes, or from three minutes to 60 minutes.
[0128] IR promotion of the wet layer to the COF film may be
achieved using an IR heater module mounted over a belt transport
system. Various types of IR emitters may be used, such as carbon IR
emitters or short wave IR emitters (available from Heraerus).
Additional exemplary information regarding carbon IR emitters or
short wave IR emitters is summarized in the following Table.
TABLE-US-00001 Number of Module Power IR lamp Peak Wavelength lamps
(kW) Carbon 2.0 micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron
3 - twin tube 4.5
[0129] Process Action D: Optionally Removing the SOF from the
Coating Substrate to Obtain a Free-Standing SOF
[0130] In embodiments, a free-standing SOF is desired.
Free-standing SOFs may be obtained when an appropriate low adhesion
substrate is used to support the deposition of the wet layer.
Appropriate substrates that have low adhesion to the SOF may
include, for example, metal foils, metalized polymer substrates,
release papers and SOFs, such as SOFs prepared with a surface that
has been altered to have a low adhesion or a decreased propensity
for adhesion or attachment. Removal of the SOF from the supporting
substrate may be achieved in a number of ways by someone skilled in
the art. For example, removal of the SOF from the substrate may
occur by starting from a corner or edge of the film and optionally
assisted by passing the substrate and SOF over a curved
surface.
[0131] Process Action E: Optionally Processing the Free-Standing
SOF into a Roll
[0132] Optionally, a free-standing SOF or a SOF supported by a
flexible substrate may be processed into a roll. The SOF may be
processed into a roll for storage, handling, and a variety of other
purposes. The starting curvature of the roll is selected such that
the SOF is not distorted or cracked during the rolling process.
[0133] Process Action F: Optionally Cutting and Seaming the SOF
into a Shape, Such as a Belt
[0134] The method for cutting and seaming the SOF is similar to
that described in U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995
(for polymer films), the disclosure of which is herein totally
incorporated by reference. An SOF belt may be fabricated from a
single SOF, a multi layer SOF or an SOF sheet cut from a web. Such
sheets may be rectangular in shape or any particular shape as
desired. All sides of the SOF(s) may be of the same length, or one
pair of parallel sides may be longer than the other pair of
parallel sides. The SOF(s) may be fabricated into shapes, such as a
belt by overlap joining the opposite marginal end regions of the
SOF sheet. A seam is typically produced in the overlapping marginal
end regions at the point of joining. Joining may be affected by any
suitable means. Typical joining techniques include, for example,
welding (including ultrasonic), gluing, taping, pressure heat
fusing and the like. Methods, such as ultrasonic welding, are
desirable general methods of joining flexible sheets because of
their speed, cleanliness (no solvents) and production of a thin and
narrow seam.
[0135] Process Action G: Optionally Using a SOF as a Substrate for
Subsequent SOF Formation Processes
[0136] A SOF may be used as a substrate in the SOF forming process
to afford a multi-layered structured organic film. The layers of a
multi-layered SOF may be chemically bound in or in physical
contact. Chemically bound, multi-layered SOFs are formed when
functional groups present on the substrate SOF surface can react
with the molecular building blocks present in the deposited wet
layer used to form the second structured organic film layer.
Multi-layered SOFs in physical contact may not chemically bound to
one another.
[0137] A SOF substrate may optionally be chemically treated prior
to the deposition of the wet layer to enable or promote chemical
attachment of a second SOF layer to form a multi-layered structured
organic film.
[0138] Alternatively, a SOF substrate may optionally be chemically
treated prior to the deposition of the wet layer to disable
chemical attachment of a second SOF layer (surface pacification) to
form a physical contact multi-layered SOF.
[0139] Other methods, such as lamination of two or more SOFs, may
also be used to prepare physically contacted multi-layered
SOFs.
EXAMPLES
[0140] A number of examples of the process used to make SOFs are
set forth herein and are illustrative of the different
compositions, conditions, techniques that may be utilized.
Identified within each example are the nominal actions associated
with this activity. The sequence and number of actions along with
operational parameters, such as temperature, time, coating method,
and the like, are not limited by the following examples. All
proportions are by weight unless otherwise indicated. The term "rt"
refers, for example, to temperatures ranging from about 20.degree.
C. to about 25.degree. C. Mechanical measurements were measured on
a TA Instruments DMA Q800 dynamic mechanical analyzer using methods
standard in the art. Differential scanning calorimetery was
measured on a TA Instruments DSC 2910 differential scanning
calorimeter using methods standard in the art. Thermal gravimetric
analysis was measured on a TA Instruments TGA 2950 thermal
gravimetric analyzer using methods standard in the art. FT-IR
spectra was measured on a Nicolet Magna 550 spectrometer using
methods standard in the art. Thickness measurements <1 micron
were measured on a Dektak 6m Surface Profiler. Surface energies
were measured on a Fibro DAT 1100 (Sweden) contact angle instrument
using methods standard in the art. Unless otherwise noted, the SOFs
produced in the following examples were either defect-free SOFs or
substantially defect-free SOFs.
[0141] The SOFs coated onto Mylar were delaminated by immersion in
a room temperature water bath. After soaking for 10 minutes the SOF
film generally detached from Mylar substrate. This process is most
efficient with a SOF coated onto substrates known to have high
surface energy (polar), such as glass, mica, salt, and the
like.
[0142] Given the examples below it will be apparent, that the
compositions prepared by the methods of the present disclosure may
be practiced with many types of components and may have many
different uses in accordance with the disclosure above and as
pointed out hereinafter.
[0143] Embodiment of a Patterned SOF Composition
[0144] An embodiment of the disclosure is to attain a SOF wherein
the microscopic arrangement of segments is patterned. The term
"patterning" refers, for example, to the sequence in which segments
are linked together. A patterned SOF would therefore embody a
composition wherein, for example, segment A is only connected to
segment B, and conversely, segment B is only connected to segment
A. Further, a system wherein only one segment exists, say segment
A, is employed is will be patterned because A is intended to only
react with A. In principle a patterned SOF may be achieved using
any number of segment types. The patterning of segments may be
controlled by using molecular building blocks whose functional
group reactivity is intended to compliment a partner molecular
building block and wherein the likelihood of a molecular building
block to react with itself is minimized. The aforementioned
strategy to segment patterning is non-limiting. Instances where a
specific strategy to control patterning has not been deliberately
implemented are also embodied herein.
[0145] A patterned film may be detected using spectroscopic
techniques that are capable of assessing the successful formation
of linking groups in a SOF. Such spectroscopies include, for
example, Fourier-transfer infrared spectroscopy, Raman
spectroscopy, and solid-state nuclear magnetic resonance
spectroscopy. Upon acquiring a data by a spectroscopic technique
from a sample, the absence of signals from functional groups on
building blocks and the emergence of signals from linking groups
indicate the reaction between building blocks and the concomitant
patterning and formation of an SOF.
[0146] Different degrees of patterning are also embodied. Full
patterning of a SOF will be detected by the complete absence of
spectroscopic signals from building block functional groups. Also
embodied are SOFs having lowered degrees of patterning wherein
domains of patterning exist within the SOF. SOFs with domains of
patterning, when measured spectroscopically, will produce signals
from building block functional groups which remain unmodified at
the periphery of a patterned domain.
[0147] It is appreciated that a very low degree of patterning is
associated with inefficient reaction between building blocks and
the inability to form a film. Therefore, successful implementation
of the process of the present disclosure requires appreciable
patterning between building blocks within the SOF. The degree of
necessary patterning to form a SOF is variable and can depend on
the chosen building blocks and desired linking groups. The minimum
degree of patterning required is that required to form a film using
the process described herein, and may be quantified as formation of
about 20% or more of the intended linking groups, such as about 40%
or more of the intended linking groups or about 50% or more of the
intended linking groups; the nominal degree of patterning embodied
by the present disclosure is formation of about 60% of the intended
linking group, such as formation of about 100% of the intended
linking groups. Formation of linking groups may be detected
spectroscopically as described earlier in the embodiments.
[0148] Production of a Patterned SOF
[0149] The following experiments demonstrate the development of a
patterned SOF. The activity described below is non-limiting as it
will be apparent that many types of approaches may be used to
generate patterning in a SOF.
[0150] EXAMPLE 1 describes the synthesis of a Type 2 SOF wherein
components are combined such that etherification linking chemistry
is promoted between two building blocks. The presence of an acid
catalyst and a heating action yield a SOF with the method described
in EXAMPLE 1.
Example 1
Type 2 SOF
[0151] (Action A) Preparation of the Liquid Containing Reaction
Mixture.
[0152] The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.47
g, 3.4 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.12 g, 1.7 mmol)], and 17.9 g of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane. To the filtered solution was added an acid catalyst
delivered as 0.31 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture.
[0153] (Action B) Deposition of Reaction Mixture as a Wet Film.
[0154] The reaction mixture was applied to the reflective side of a
metalized (TiZr) MYLAR.TM. substrate using a constant velocity draw
down coater outfitted with a bird bar having an 8 mil gap.
[0155] (Action C) Promotion of the Change of the Wet Film to a Dry
SOF.
[0156] The metalized MYLAR.TM. substrate supporting the wet layer
was rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness ranging from about 3-6 microns, which may
be delaminated from the substrate as a single free-standing SOF.
The color of the SOF was green. The Fourier-transform infrared
spectrum of a portion of this SOF is provided in FIG. 1.
[0157] To demonstrate that the SOF prepared in EXAMPLE 1 comprises
segments from the employed molecular building blocks that are
patterned within the SOF, three control experiments were conducted.
Namely, three liquid reaction mixtures were prepared using the same
procedure as set forth in Action A in EXAMPLE 1; however, each of
these three formulations were modified as follows: [0158] (Control
reaction mixture 1; Example 2) the building block
benzene-1,4-dimethanol was not included. [0159] (Control reaction
mixture 2; Example 3) the building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
was not included. [0160] (Control reaction mixture 3; Example 4)
the catalyst p-toluenesulfonic acid was not included
[0161] The full descriptions of the SOF forming process for the
above described control experiments are detailed in EXAMPLES 2-4
below.
Example 2
Control Experiment Wherein the Building Block
Benzene-1,4-Dimethanol was not Included
[0162] (Action A) Preparation of the Liquid Containing Reaction
Mixture.
[0163] The following were combined: the building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.12 g, 1.7 mmol)], and 17.9 g of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane. To the filtered solution was added an acid catalyst
delivered as 0.31 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture.
[0164] (Action B) Deposition of Reaction Mixture as a Wet Film.
[0165] The reaction mixture was applied to the reflective side of a
metalized (TiZr) MYLAR.TM. substrate using a constant velocity draw
down coater outfitted with a bird bar having an 8 mil gap.
[0166] (Action C) Attempted Promotion of the Change of the Wet Film
to a Dry SOF.
[0167] The metalized MYLAR.TM. substrate supporting the wet layer
was rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions did not
provide a film. Instead, a precipitated powder of the building
block was deposited onto the substrate.
Example 3
(Control Experiment Wherein the Building Block
N4,N4,N4',N4'-Tetrakis(4-(Methoxymethyl)Phenyl)Biphenyl-4,4'-Diamine
was not Included)
[0168] (Action A) Preparation of the Liquid Containing Reaction
Mixture.
[0169] The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.47
g, 3.4 mmol)] and 17.9 g of 1-methoxy-2-propanol. The mixture was
shaken and heated to 60.degree. C. until a homogenous solution
resulted. Upon cooling to room temperature, the solution was
filtered through a 0.45 micron PTFE membrane. To the filtered
solution was added an acid catalyst delivered as 0.31 g of a 10 wt
% solution of p-toluenesulfonic acid in 1-methoxy-2-propanol to
yield the liquid containing reaction mixture.
[0170] (Action B) Deposition of Reaction Mixture as a Wet Film.
[0171] The reaction mixture was applied to the reflective side of a
metalized (TiZr) MYLAR.TM. substrate using a constant velocity draw
down coater outfitted with a bird bar having an 8 mil gap.
[0172] (Action C) Attempted Promotion of the Change of the Wet Film
to a Dry SOF.
[0173] The metalized MYLAR.TM. substrate supporting the wet layer
was rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions did not
provide a film. Instead, a precipitated powder of the building
block was deposited onto the substrate.
Example 4
Control Experiment Wherein the Acid Catalyst p-Toluenesulfonic Acid
was not Included
[0174] (Action A) Preparation of the liquid containing reaction
mixture. The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.47
g, 3.4 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.12 g, 1.7 mmol)], and 17.9 g of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane to yield the liquid containing reaction mixture.
[0175] (Action B) Deposition of Reaction Mixture as a Wet Film.
[0176] The reaction mixture was applied to the reflective side of a
metalized (TiZr) MYLAR.TM. substrate using a constant velocity draw
down coater outfitted with a bird bar having an 8 mil gap.
[0177] (Action C) Attempted Promotion of the Change of the Wet Film
to a Dry SOF.
[0178] The metalized MYLAR.TM. substrate supporting the wet layer
was rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions did not
provide a film. Instead, a precipitated powder of the building
blocks was deposited onto the substrate.
[0179] As described in EXAMPLES 2-4, each of the three control
reaction mixtures were subjected to Action B and Action C as
outlined in EXAMPLE 1. However, in all cases a SOF did not form;
the building blocks simply precipitated on the substrate. It is
concluded from these results that building blocks cannot react with
themselves under the stated processing conditions nor can the
building blocks react in the absence of a promoter
(p-toluenesulfonic acid). Therefore, the activity described in
EXAMPLE 1 is one wherein building blocks (benzene-1,4-dimethanol
and
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine)
can only react with each other when promoted to do so. A patterned
SOF results when the segments p-xylyl and
N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine connect only with
each other. The Fourier-transform infrared spectrum, compared to
that of the products of the control experiments (FIG. 2) of the SOF
shows absence of functional groups (notably the absence of the
hydroxyl band from the benzene-1,4-dimethanol) from the starting
materials and further supports that the connectivity between
segments has proceed as described above. Also, the complete absence
of the hydroxyl band in the spectrum for the SOF indicates that the
patterning is to a very high degree.
[0180] Described below are further Examples of defect-free SOFs
and/or substantially defect-free SOFs prepared in accordance with
the present disclosure. In the following examples (Action A) is the
preparation of the liquid containing reaction mixture; (Action B)
is the deposition of reaction mixture as a wet film; and (Action C)
is the promotion of the change of the wet film to a dry SOF.
Example 5
Type 2 SOF
[0181] (Action A) The following were combined: the building block
benzene-1,3,5-trimethanol [segment=benzene-1,3,5-trimethyl;
Fg=hydroxyl (--OH); (0.2 g, 1.2 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (0.59 g, 0.8 mmol)], and 8.95 g of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane. To the filtered solution was added an acid catalyst
delivered as 0.16 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture. (Action B) The reaction mixture was applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
an 20 mil gap. (Action C) The metalized MYLAR.TM. substrate
supporting the wet layer was rapidly transferred to an actively
vented oven preheated to 130.degree. C. and left to heat for 40
min. These actions provided a SOF having a thickness ranging from
about 2-4 microns that could be delaminated from the substrate as a
single free-standing SOF. The color of the SOF was green.
Example 6
Type 2 SOF
[0182] (Action A) The following were combined: the building block
1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (--OH); (0.21 g, 1.8
mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (0.58 g, 0.87 mmol)], and 8.95 g of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane. To the filtered solution was added an acid catalyst
delivered as 0.16 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture. (Action B) The reaction mixture was applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 20 mil gap. (Action C) The metalized MYLAR.TM. substrate
supporting the wet layer was rapidly transferred to an actively
vented oven preheated to 130.degree. C. and left to heat for 40
min. These actions provided a SOF having a thickness ranging from
about 4-5 microns that could be delaminated from the substrate as a
single free standing SOF. The color of the SOF was green. The
Fourier-transform infrared spectrum of a portion of this SOF is
provided in FIG. 3.
Example 7
Type 2 SOF
[0183] (Action A) The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.64
g, 4.6 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.54 g, 2.3 mmol)], and 7.51 g of
1,4-dioxane. The mixture was shaken and heated to 60.degree. C.
until a homogenous solution resulted, which was then filtered
through a 0.45 micron PTFE membrane. To the filtered solution was
added an acid catalyst delivered as 0.28 g of a 10 wt % solution of
p-toluenesulfonic acid in 1,4-dioxane to yield the liquid
containing reaction mixture. (Action B) The reaction mixture was
applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having an 10 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer was rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 4 min. These actions provided a SOF having a thickness ranging
from about 8-12 microns that could be delaminated from substrate as
a single free-standing film. The color of the SOF was green.
Example 8
Type 2 SOF
[0184] (Action A) The following were combined: the building block
1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (--OH); (0.57 g, 4.8
mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.61 g, 2.42 mmol)], and 7.51 g of
1,4-dioxane. The mixture was shaken and heated to 60.degree. C.
until a homogenous solution resulted. Upon cooling to rt, the
solution was filtered through a 0.45 micron PTFE membrane. To the
filtered solution was added an acid catalyst delivered as 0.22 g of
a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to
yield the liquid containing reaction mixture. (Action B) The
reaction mixture was applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having a 10 mil gap. (Action C)
The metalized MYLAR.TM. substrate supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness ranging from about 12-20 microns that
could be delaminated from the substrate as a single free-standing
film. The color of the SOF was green.
Example 9
Type 2 SOF
[0185] (Action A) The following were combined: the building block
4,4'-(cyclohexane-1,1-diyl)diphenol
[segment=4,4'-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (--OH);
(0.97 g, 6 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.21 g, 1.8 mmol)], and 7.51 g of
1,4-dioxane. The mixture was shaken and heated to 60.degree. C.
until a homogenous solution resulted. Upon cooling to rt, the
solution was filtered through a 0.45 micron PTFE membrane. To the
filtered solution was added an acid catalyst delivered as 0.22 g of
a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to
yield the liquid containing reaction mixture. (Action B) The
reaction mixture was applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having a 10 mil gap. (Action C)
The metalized MYLAR.TM. substrate supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness ranging from about 12-20 microns that
could be delaminated from the substrate as a single free-standing
film. The color of the SOF was green. The Fourier-transform
infrared spectrum of SOF is provided in FIG. 4.
Example 10
Type 2 SOF
[0186] (Action A) The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.52
g, 3.8 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.26 g, 1.9 mmol)], and 6.3 g of
1,4-dioxane and 1.57 g of n-butyl acetate. The mixture was shaken
and heated to 60.degree. C. until a homogenous solution resulted,
which was then filtered through a 0.45 micron PTFE membrane. To the
filtered solution was added an acid catalyst delivered as 0.28 g of
a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to
yield the liquid containing reaction mixture. (Action B) The
reaction mixture was applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having an 10 mil gap. (Action C)
The metalized MYLAR.TM. substrate supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 4 min. These actions provided a
SOF having a thickness of 7-10 microns that could be delaminated
from substrate as a single free-standing film. The color of the SOF
was green.
Example 11
Type 2 SOF
[0187] (Action A) Same as EXAMPLE 7. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was rapidly transferred to an actively vented
oven preheated to 120.degree. C. and left to heat for 20 min. These
actions provided a uniformly coated multilayer device wherein the
SOF had a thickness ranging from about 9-10 microns.
Example 12
Type 2 SOF
[0188] (Action A) The following were combined: the building block
benzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (--OH); (0.52
g, 3.8 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.26 g, 1.9 mmol)], and 6.3 g of
1,4-dioxane and 1.57 g of methyl isobutyl ketone. The mixture was
shaken and heated to 60.degree. C. until a homogenous solution
resulted, which was then filtered through a 0.45 micron PTFE
membrane. To the filtered solution was added an acid catalyst
delivered as 0.28 g of a 10 wt % solution of p-toluenesulfonic acid
in 1,4-dioxane to yield the liquid containing reaction mixture.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having an 10 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 130.degree. C. and left to heat for 4 min. These actions
provided a SOF having a thickness ranging from about 7-10 microns
that could be delaminated from substrate as a single free-standing
film. The color of the SOF was green.
Example 13
Type 2 SOF
[0189] (Action A) The following were combined: the building block
1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (--OH); (0.47 g, 4.0
mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.31 g, 2.0 mmol)], 6.3 g of
1,4-dioxane, and 1.57 g of n-butyl acetate. The mixture was shaken
and heated to 60.degree. C. until a homogenous solution resulted.
Upon cooling to room temperature, the solution was filtered through
a 0.45 micron PTFE membrane. To the filtered solution was added an
acid catalyst delivered as 0.22 g of a 10 wt % solution of
p-toluenesulfonic acid in 1,4-dioxane to yield the liquid
containing reaction mixture. (Action B) The reaction mixture was
applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having a 10 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer was rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 40 min. These actions provided a SOF having a thickness ranging
from about 8-12 microns that could be delaminated from the
substrate as a single free-standing film. The color of the SOF was
green.
Example 14
Type 2 SOF
[0190] (Action A) Same as EXAMPLE 10. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was rapidly transferred to an actively vented
oven preheated to 120.degree. C. and left to heat for 20 min. These
actions provided a uniformly coated multilayer device wherein the
SOF had a thickness ranging from about 9-10 microns.
Example 15
Type 2 SOF
[0191] (Action A) The following were combined: the building block
1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (--OH); (0.47 g, 4.0
mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (1.31 g, 2.0 mmol)], 6.3 g of
1,4-dioxane, and 1.57 g of methyl isobutyl ketone. The mixture was
shaken and heated to 60.degree. C. until a homogenous solution
resulted. Upon cooling to room temperature, the solution was
filtered through a 0.45 micron PTFE membrane. To the filtered
solution was added an acid catalyst delivered as 0.22 g of a 10 wt
% solution of p-toluenesulfonic acid in 1,4-dioxane to yield the
liquid containing reaction mixture. (Action B) The reaction mixture
was applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having a 10 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer was rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 40 min. These actions provided a SOF having a thickness ranging
from about 8-12 microns that could be delaminated from the
substrate as a single free-standing film. The color of the SOF was
green.
Example 16
Type 2 SOF
[0192] (Action A) The following were combined: the building block
4,4'-(cyclohexane-1,1-diyl)diphenol
[segment=4,4'-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (--OH);
(0.8 g)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (0.8 g, 1.5 mmol)], 1,4-dioxane,
and 1.57 g of n-butyl acetate. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
rt, the solution was filtered through a 0.45 micron PTFE membrane.
To the filtered solution was added an acid catalyst delivered as
0.22 g of a 10 wt % solution of p-toluenesulfonic acid in
1,4-dioxane to yield the liquid containing reaction mixture.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having a 10 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 130.degree. C. and left to heat for 40 min. These actions
provided SOF having a thickness of about 12 microns that could be
delaminated from the substrate as a single free-standing film. The
color of the SOF was green.
Example 17
Type 2 SOF
[0193] (Action A) Same as EXAMPLE 13. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was rapidly transferred to an actively vented
oven preheated to 120.degree. C. and left to heat for 20 min. These
actions provided a uniformly coated multilayer device wherein the
SOF had a thickness ranging from about 9-10 microns.
Example 18
Type 2 SOF
[0194] (Action A) The following were combined: the building block
4,4'-(cyclohexane-1,1-diyl)diphenol
[segment=4,4'-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (--OH);
(0.8 g, 3.0 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (0.8 g, 1.5 mmol)], 1,4-dioxane,
and 1.57 g of methyl isobutyl ketone. The mixture was shaken and
heated to 60.degree. C. until a homogenous solution resulted. Upon
cooling to room temperature, the solution was filtered through a
0.45 micron PTFE membrane. To the filtered solution was added an
acid catalyst delivered as 0.22 g of a 10 wt % solution of
p-toluenesulfonic acid in 1,4-dioxane to yield the liquid
containing reaction mixture. (Action B) The reaction mixture was
applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having a 10 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer was rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 40 min. These actions provided SOF having a thickness of about
12 microns that could be delaminated from the substrate as a single
free-standing film. The color of the SOF was green.
Example 19
Type 2 SOF
[0195] (Action A) Same as EXAMPLE 7. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was allowed to dry at ambient temperature in an
actively vented fume hood for 5 min and was then transferred to an
actively vented oven preheated to 120.degree. C. and left to heat
for 15 min. These actions provided a uniformly coated multilayer
device wherein the SOF had a thickness ranging from about 9-10
microns.
Example 20
Type 2 SOF
[0196] (Action A) Same as EXAMPLE 10. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was allowed to dry at ambient temperature in an
actively vented fume hood for 5 min and was then transferred to an
actively vented oven preheated to 120.degree. C. and left to heat
for 15 min. These actions provided a uniformly coated multilayer
device wherein the SOF had a thickness ranging from about 9-10
microns.
Example 21
Type 2 SOF
[0197] (Action A) Same as EXAMPLE 13. (Action B) The reaction
mixture was applied to a photoconductive layer, containing a
pigment and polymeric binder, supported on metalized (TiZr)
MYLAR.TM. substrate using a constant velocity draw down coater
outfitted with a bird bar having a 10 mil gap. (Action C) The
supported wet layer was allowed to dry at ambient temperature in an
actively vented fume hood for 5 min and was then transferred to an
actively vented oven preheated to 120.degree. C. and left to heat
for 15 min. These actions provided a uniformly coated multilayer
device wherein the SOF had a thickness ranging from about 9-10
microns and could not be delaminated.
Example 22
Type 2 SOF
[0198] (Action A) Same as EXAMPLE 7. (Action B) The reaction
mixture was applied to a layered photosensitive member comprising a
generator layer and a transport layer containing a diamine type
molecule dispersed in a polymeric binder using a constant velocity
draw down coater outfitted with a bird bar having a 10 mil gap.
(Action C) The supported wet layer was allowed to dry at ambient
temperature in an actively vented fume hood for 5 min and was then
transferred to an actively vented oven preheated to 120.degree. C.
and left to heat for 15 min. These actions provided a uniformly
coated multilayer device wherein the SOF had a thickness ranging
from about 9-10 microns.
Example 23
Type 2 SOF
[0199] (Action A) Same as EXAMPLE 10. (Action B) The reaction
mixture was applied to layered photosensitive member comprising a
generator layer and a transport layer containing a diamine type
molecule dispersed in a polymeric binder using a constant velocity
draw down coater outfitted with a bird bar having a 10 mil gap.
(Action C) The supported wet layer was allowed to dry at ambient
temperature in an actively vented fume hood for 5 min and was then
transferred to an actively vented oven preheated to 120.degree. C.
and left to heat for 15 min. These actions provided a uniformly
coated multilayer device wherein the SOF had a thickness ranging
from about 9-10 microns.
Example 24
Type 2 SOF
[0200] (Action A) Same as EXAMPLE 13. (Action B) The reaction
mixture was applied to layered photosensitive member comprising a
generator layer and a transport layer containing a diamine type
molecule dispersed in a polymeric binder using a constant velocity
draw down coater outfitted with a bird bar having a 10 mil gap.
(Action C) The supported wet layer was allowed to dry at ambient
temperature in an actively vented fume hood for 5 min and was then
transferred to an actively vented oven preheated to 120.degree. C.
and left to heat for 15 min. These actions provided a uniformly
coated multilayer device wherein the SOF had a thickness ranging
from about 9-10 microns.
Example 25
Type 1 SOF
[0201] (Action A) The following were combined: the building block
(4,4',4'',4'''-(biphenyl-4,4'-diylbis(azanetriyl))tetrakis(benzene-4,1-di-
yl))tetramethanol
[segment=(4,4',4'',4'''-(biphenyl-4,4'-diylbis(azanetriyl))tetrakis(benze-
ne-4,1-diyl); Fg=alcohol (--OH); (1.48 g, 2.4 mmol)], and 8.3 g of
1,4-dioxane. The mixture was shaken and heated to 60.degree. C.
until a homogenous solution resulted. Upon cooling to room
temperature, the solution was filtered through a 0.45 micron PTFE
membrane. To the filtered solution was added an acid catalyst
delivered as 0.15 g of a 10 wt % solution of p-toluenesulfonic acid
in 1,4-dioxane to yield the liquid containing reaction mixture.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having a 25 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 130.degree. C. and left to heat for 40 min. These actions
provided SOF having a thickness ranging from about 8-24 microns.
The color of the SOF was green.
Example 26
Type 1 SOF
[0202] (Action A) The following were combined: the building
4,4',4''-nitrilotris(benzene-4,1-diyl)trimethanol
[segment=(4,4',4''-nitrilotris(benzene-4,1-diyl)trimethyl);
Fg=alcohol (--OH); (1.48 g, 4.4 mmol)], and 8.3 g of 1,4-dioxane.
The mixture was shaken and heated to 60.degree. C. until a
homogenous solution resulted. Upon cooling to room temperature, the
solution was filtered through a 0.45 micron PTFE membrane. To the
filtered solution was added an acid catalyst delivered as 0.15 g of
a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to
yield the liquid containing reaction mixture. (Action B) The
reaction mixture was applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having a 15 mil gap. (Action C)
The metalized MYLAR.TM. substrate supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
130.degree. C. and left to heat for 40 min. These actions provided
SOF having a thickness ranging from about 6-15 microns that could
be delaminated from substrate as a single free-standing film. The
color of the SOF was green. The Fourier-transform infrared spectrum
of this film is provided in FIG. 5. Two-dimensional X-ray
scattering data is provided in FIG. 8. As seen in FIG. 8, no signal
above the background is present, indicating the absence of
molecular order having any detectable periodicity.
Example 27
Type 2 SOF
[0203] (Action A) The following were combined: the building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH.sub.3); (0.26 g, 0.40 mmol)] and a second
building block
3,3'-(4,4'-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol
[segment=3,3'-(4,4'-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;
Fg=hydroxy (--OH); (0.34 g, 0.78 mmol)], and 1.29 mL of
1-methoxy-2-propanol. The mixture was shaken and heated to
60.degree. C. until a homogenous solution resulted. Upon cooling to
room temperature, the solution was filtered through a 0.45 micron
PTFE membrane. To the filtered solution was added an acid catalyst
delivered as 0.2 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture. (Action B) The reaction mixture was applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
an 8 mil gap. (Action C) The metalized MYLAR.TM. substrate
supporting the wet layer was rapidly transferred to an actively
vented oven preheated to 150.degree. C. and left to heat for 40
min. These actions provided SOF having a thickness ranging from
about 15-20 microns that could be delaminated from substrate as a
single free-standing film. The color of the SOF was green.
Example 28
Type 2 SOF
[0204] (Action A) Same as EXAMPLE 24. (Action B) The reaction
mixture was applied to layered photosensitive member comprising a
generator layer and a transport layer containing a diamine type
molecule dispersed in a polymeric binder using a constant velocity
draw down coater outfitted with a bird bar having a 5 mil gap.
(Action C) The supported wet layer was rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 40 min. These actions provided a uniformly coated multilayer
device wherein the SOF had a thickness of about 5 microns.
Example 29
Type 2 SOF
[0205] (Action A) Same as EXAMPLE 24. (Action B) The reaction
mixture was applied to layered photosensitive member comprising a
generator layer and a transport layer containing a diamine type
molecule dispersed in a polymeric binder affixed to a spin coating
device rotating at 750 rpm. The liquid reaction mixture was dropped
at the centre rotating substrate to deposit the wet layer. (Action
C) The supported wet layer was rapidly transferred to an actively
vented oven preheated to 140.degree. C. and left to heat for 40
min. These actions provided a uniformly coated multilayer device
wherein the SOF had a thickness of about 0.2 microns.
Example 30
Type 2 SOF
[0206] (Action A) The following were combined: the building block
terephthalaldehyde [segment=benzene; Fg=aldehyde (--CHO); (0.18 g,
1.3 mmol)] and a second building block tris(4-aminophenyl)amine
[segment=triphenylamine; Fg=amine (--NH.sub.2); (0.26 g, 0.89
mmol)], and 2.5 g of tetrahydrofuran. The mixture was shaken until
a homogenous solution resulted. Upon cooling to room temperature,
the solution was filtered through a 0.45 micron PTFE membrane. To
the filtered solution was added an acid catalyst delivered as 0.045
g of a 10 wt % solution of p-toluenesulfonic acid in
1-tetrahydrofuran to yield the liquid containing reaction mixture.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having an 5 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 120.degree. C. and left to heat for 40 min. These actions
provided a SOF having a thickness of about 6 microns that could be
delaminated from substrate as a single free-standing film. The
color of the SOF was red-orange. The Fourier-transform infrared
spectrum of this film is provided in FIG. 6.
Example 31
Type 1 SOF
[0207] (Action A) The following were combined: the building block
4,4',4''-nitrilotribenzaldehyde [segment=triphenylamine;
Fg=aldehyde (--CHO); (0.16 g, 0.4 mmol)] and a second building
block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine
(--NH.sub.2); (0.14 g, 0.4 mmol)], and 1.9 g of tetrahydrofuran.
The mixture was stirred until a homogenous solution resulted. Upon
cooling to room temperature, the solution was filtered through a
0.45 micron PTFE membrane. (Action B) The reaction mixture was
applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having an 5 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer was rapidly transferred to an
actively vented oven preheated to 120.degree. C. and left to heat
for 40 min. These actions provided a SOF having a thickness of
about 6 microns that could be delaminated from substrate as a
single free-standing film. The color of the SOF was red. The
Fourier-transform infrared spectrum of this film is provided in
FIG. 7.
Example 32
Type 2 SOF
[0208] (Action A) The following were combined: the building block
glyoxal [segment=single covalent bond; Fg=aldehyde (--CHO); (0.31
g, 5.8 mmol--added as 40 wt % solution in water i.e. 0.77 g aqueous
glyoxal)] and a second building block tris(4-aminophenyl)amine
[segment=triphenylamine; Fg=amine (--NH.sub.2); (1.14 g, (3.9
mmol)], and 8.27 g of tetrahydrofuran. The mixture was shaken until
a homogenous solution resulted. Upon cooling to room temperature,
the solution was filtered through a 0.45 micron PTFE membrane.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having a 10 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 120.degree. C. and left to heat for 40 min. These actions
provided a SOF having a thickness ranging from about 6-12 microns
that could be delaminated from substrate as a single free-standing
film. The color of the SOF was red.
Example 33
Type 2 SOF
[0209] (Action A) The following were combined: the building block
terephthalaldehyde [segment=benzene; Fg=aldehyde (--CHO); (0.18 g,
1.3 mmol)] and a second building block tris(4-aminophenyl)amine
[segment=triphenylamine; Fg=amine (--NH.sub.2); (0.26 g, 0.89
mmol)], 2.5 g of tetrahydrofuran, and 0.4 g water. The mixture was
shaken until a homogenous solution resulted. Upon cooling to room
temperature, the solution was filtered through a 0.45 micron PTFE
membrane. (Action B) The reaction mixture was applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 5 mil gap. (Action C) The metalized MYLAR.TM. substrate
supporting the wet layer was rapidly transferred to an actively
vented oven preheated to 120.degree. C. and left to heat for 40
min. These actions provided a SOF having a thickness ranging 6
microns that could be delaminated from substrate as a single
free-standing film. The color of the SOF was red-orange.
Example 34
Type 1 SOF
[0210] (Action A) The following were combined: the building block
4,4',4''-nitrilotribenzaldehyde [segment=triphenylamine;
Fg=aldehyde (--CHO); (0.16 g, 0.4 mmol)] and a second building
block tris(4-aminophenyl)amine [segment=triphenylamine; Fg=amine
(--NH.sub.2); (0.14 g, 0.4 mmol)], 1.9 g of tetrahydrofuran, and
0.4 g water. The mixture was stirred until a homogenous solution
resulted. Upon cooling to room temperature, the solution was
filtered through a 0.45 micron PTFE membrane. (Action B) The
reaction mixture was applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having an 5 mil gap. (Action C)
The metalized MYLAR.TM. substrate supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
120.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness of about 6 microns that could be
delaminated from substrate as a single free-standing film. The
color of the SOF was red-orange.
Example 35
Type 2 SOF
[0211] (Action A) Same as EXAMPLE 28. (Action B) The reaction
mixture was dropped from a glass pipette onto a glass slide.
(Action C) The glass slide was heated to 80.degree. C. on a heating
stage yielding a deep red SOF having a thickness of about 200
microns which could be delaminated from the glass slide.
Example 36
Type 1 SOF
[0212] (Action A) The following were combined: the building block
tris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;
Fg=hydroxy (--OH); 5.12 g]; the additives Cymel303 (55 mg) and
Silclean 3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and
1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling
wave rotator for 10 min and then heated at 55.degree. C. for 65 min
until a homogenous solution resulted. The mixture was placed on the
rotator and cooled to room temperature. The solution was filtered
through a 1 micron PTFE membrane. (Action B) The reaction mixture
was applied to a commercially available, 30 mm drum photoreceptor
using a cup coater (Tsukiage coating) at a pull-rate of 240 mm/min.
(Action C) The photoreceptor drum supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
140.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness of about 6.9 microns.
Example 37
Type 1 SOF with Additives
[0213] (Action A) The following were combined: the building block
tris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;
Fg=hydroxy (--OH); 4.65 g]; the additives Cymel303 (49 mg) and
Silclean 3700 (205 mg), and the catalyst Nacure XP-357 (254 mg) and
1-methoxy-2-propanol (12.25 g). The mixture was mixed on a rolling
wave rotator for 10 min and then heated at 55.degree. C. for 65 min
until a homogenous solution resulted. The mixture was placed on the
rotator and cooled to room temperature. The solution was filtered
through a 1 micron PTFE membrane. A polyethylene wax dispersion
(average particle size=5.5 microns, 40% solids in i-propyl alcohol,
613 mg) was added to the reaction mixture which was sonicated for
10 min and mixed on the rotator for 30 min. (Action B) The reaction
mixture was applied to a commercially available, 30 mm drum
photoreceptor using a cup coater (Tsukiage coating) at a pull-rate
of 240 mm/min. (Action C) The photoreceptor drum supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 140.degree. C. and left to heat for 40 min. These actions
provided a film having a thickness of 6.9 microns with even
incorporation of the wax particles in the SOF.
Example 38
Type 2 SOF
[0214] (Action A) The following were combined: the building block
N,N,N',N'-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetra-(p-tolyl)biphenyl-4,4'-diamine; Fg=hydroxy
(--OH); 3.36 g] and the building block
N,N'-diphenyl-N,N'-bis-(3-hydroxyphenyl)-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetraphenyl-biphenyl-4,4'-diamine; Fg--hydroxyl
(--OH); 5.56 g]; the additives Cymel303 (480 mg) and Silclean 3700
(383 mg), and the catalyst Nacure XP-357 (480 mg) and
1-methoxy-2-propanol (33.24 g). The mixture was mixed on a rolling
wave rotator for 10 min and then heated at 55.degree. C. for 65 min
until a homogenous solution resulted. The mixture was placed on the
rotator and cooled to room temperature. The solution was filtered
through a 1 micron PTFE membrane. (Action B) The reaction mixture
was applied to a commercially available, 30 mm drum photoreceptor
using a cup coater (Tsukiage coating) at a pull-rate of 485 mm/min.
(Action C) The photoreceptor drum supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
140.degree. C. and left to heat for 40 min. These actions provided
a film having a thickness ranging from 6.0 to 6.2 microns.
Example 39
Type 2 SOF
[0215] (Action A) The following can be combined: the building block
dipropylcarbonate [segment=carbonyl [--C(.dbd.O)--]; Fg=propoxy
(CH.sub.3CH.sub.2CH.sub.2O--); 4.38 g, 30 mmol] and the building
block 1,3,5-trihydroxycyclohexane [segment=cyclohexane;
Fg--hydroxyl (--OH); 3.24 g, 20 mmol] and catalyst sodium methoxide
(38 mg) and N-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed
on a rolling wave rotator for 10 min and filtered through a 1
micron PTFE membrane. (Action B) The reaction mixture is applied to
the reflective side of a metalized (TiZr) MYLAR.TM. substrate using
a constant velocity draw down coater outfitted with a bird bar
having a 5 mil gap. (Action C) The substrate supporting the wet
layer is rapidly transferred to an actively vented oven preheated
to 200.degree. C. and heated for 40 min.
Example 40
Type 2 SOF
[0216] (Action A) The following can be combined: the building block
dipropylcarbonate [segment=carbonyl [--C(.dbd.O)--]; Fg=propoxy
(CH.sub.3CH.sub.2CH.sub.2O--); 4.38 g, 30 mmol] and the building
block 1,3,5-trihydroxycyclohexane [segment=cyclohexane;
Fg--hydroxyl (--OH); 3.24 g, 20 mmol]; phosphoric acid (2 M aq, 100
mg); and N-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on
a rolling wave rotator for 10 min and filtered through a 1 micron
PTFE membrane. (Action B) The reaction mixture is applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 5 mil gap. (Action C) The substrate supporting the wet layer is
rapidly transferred to an actively vented oven preheated to
200.degree. C. and left to heat for 40 min.
Example 41
Type 2 SOF
[0217] (Action A) The following can be combined: the building block
1,1'-carbonyldiimidazole [segment=carbonyl [--C(.dbd.O)--];
Fg=imidazole; 4.86 g, 30 mmol] and the building block
1,3,5-trihydroxycyclohexane [segment=cyclohexane; Fg--hydroxyl
(--OH); 3.24 g, 20 mmol] and catalyst sodium methoxide (38 mg) and
N-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a
rolling wave rotator for 10 min and filtered through a 1 micron
PTFE membrane. (Action B) The reaction mixture is applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 5 mil gap. (Action C) The substrate supporting the wet layer is
rapidly transferred to an actively vented oven preheated to
200.degree. C. and left to heat for 40 min.
Example 42
Type 2 SOF
[0218] (Action A) The following can be combined: the building block
carbonyldiimidazole [segment=carbonyl [--C(.dbd.O)--];
Fg=imidazole; 4.86 g, 30 mmol] and the building block
1,3,5-trihydroxycyclohexane [segment=cyclohexane; Fg--hydroxyl
(--OH); 3.24 g, 20 mmol]; phosphoric acid (2 M aq, 100 mg); and
N-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a
rolling wave rotator for 10 min and filtered through a 1 micron
PTFE membrane. (Action B) The reaction mixture is applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 5 mil gap. (Action C) The substrate supporting the wet layer is
rapidly transferred to an actively vented oven preheated to
200.degree. C. and left to heat for 40 min.
Example 43
Type 2 SOF
[0219] (Action A) The following can be combined: the building block
trimesic acid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g,
20 mmol] and the building block 1,6-hexanediol [segment=hexane;
Fg--hydroxyl (--OH); 3.55 g, 30 mmol]; phosphoric acid (2 M aq, 100
mg); and N-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on
a rolling wave rotator for 10 min and filtered through a 1 micron
PTFE membrane. (Action B) The reaction mixture is applied to the
reflective side of a metalized (TiZr) MYLAR.TM. substrate using a
constant velocity draw down coater outfitted with a bird bar having
a 5 mil gap. (Action C) The substrate supporting the wet layer is
rapidly transferred to an actively vented oven preheated to
200.degree. C. and left to heat for 40 min.
Example 44
Type 2 SOF
[0220] (Action A) The following can be combined: the building block
trimesic acid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g,
20 mmol] and the building block 1,6-hexanediol [segment=hexane;
Fg--hydroxyl (--OH); 3.55 g, 30 mmol]; N,N-dimethyl-4-aminopyridine
(50 mg); and N-methyl-2-pyrrolidinone (25.5 g). The mixture is
mixed on a rolling wave rotator for 10 min and filtered through a 1
micron PTFE membrane. (Action B) The reaction mixture is applied to
the reflective side of a metalized (TiZr) MYLAR.TM. substrate using
a constant velocity draw down coater outfitted with a bird bar
having a 5 mil gap. (Action C) The substrate supporting the wet
layer is rapidly transferred to an actively vented oven preheated
to 200.degree. C. and left to heat for 40 min.
Example 45
Type 2 SOF
[0221] (Action A) The following can be combined: the building block
trimesic acid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g,
20 mmol] and the building block hexamethylenediamine
[segment=hexane; Fg--amine (--NH.sub.2); 3.49 g, 30 mmol];
phosphoric acid (2 M aq, 100 mg); and N-methyl-2-pyrrolidinone
(25.5 g). The mixture is mixed on a rolling wave rotator for 10 min
and filtered through a 1 micron PTFE membrane. (Action B) The
reaction mixture is applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having a 5 mil gap. (Action C) The
substrate supporting the wet layer is rapidly transferred to an
actively vented oven preheated to 200.degree. C. and left to heat
for 40 min.
Example 46
Type 2 SOF
[0222] (Action A) The following can be combined: the building block
trimesic acid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g,
20 mmol] and the building block hexamethylenediamine
[segment=hexane; Fg--amine (--NH.sub.2); 3.49 g, 30 mmol];
N,N-dimethyl-4-aminopyridine (50 mg); and N-methyl-2-pyrrolidinone
(25.5 g). The mixture is mixed on a rolling wave rotator for 10 min
and filtered through a 1 micron PTFE membrane. (Action B) The
reaction mixture is applied to the reflective side of a metalized
(TiZr) MYLAR.TM. substrate using a constant velocity draw down
coater outfitted with a bird bar having a 5 mil gap. (Action C) The
substrate supporting the wet layer is rapidly transferred to an
actively vented oven preheated to 200.degree. C. and left to heat
for 40 min.
Example 47
Type 2 SOF
[0223] (Action A) Preparation of liquid containing reaction
mixture. The following can be combined: the building block
1,4-diisocyanatobenzene [segment=phenyl; Fg=isocyanate
(--N.dbd.C.dbd.O); (0.5 g, 3.1 mmol)] and a second building block
4,4',4''-nitrilotris(benzene-4,1-diyl)trimethanol
[segment=(4,4',4''-nitrilotris(benzene-4,1-diyl)trimethyl); (0.69,
2.1 mmol)] 10.1 g of dimethylformamide, and 1.0 g of triethylamine.
The mixture is stirred until a homogenous solution is obtained.
Upon cooling to room temperature, the solution is filtered through
a 0.45 micron PTFE membrane. (Action B) The reaction mixture is to
be applied to the reflective side of a metalized (TiZr) MYLAR.TM.
substrate using a constant velocity draw down coater outfitted with
a bird bar having a 8 mil gap. (Action C) The metalized MYLAR.TM.
substrate supporting the wet layer is rapidly transferred to an
actively vented oven preheated to 130.degree. C. and left to heat
for 120 min.
Example 48
Type 2 SOF
[0224] (Action A) Preparation of liquid containing reaction
mixture. The following can be combined: the building block
1,4-diisocyanatohexane [segment=hexyl; Fg=isocyanate
(--N.dbd.C.dbd.O); (0.38 g, 3.6 mmol)] and a second building block
triethanolamine [segment=triethylamine; (0.81, 5.6 mmol)] 10.1 g of
dimethylformamide, and 1.0 g of triethylamine. The mixture is
stirred until a homogenous solution is obtained. Upon cooling to
room temperature, the solution is filtered through a 0.45 micron
PTFE membrane. (Action B) The reaction mixture is to be applied to
the reflective side of a metalized (TiZr) MYLAR.TM. substrate using
a constant velocity draw down coater outfitted with a bird bar
having a 8 mil gap. (Action C) The metalized MYLAR.TM. substrate
supporting the wet layer is rapidly transferred to an actively
vented oven preheated to 130.degree. C. and left to heat for 120
min.
Example 49
Type 2 SOF
[0225] (Action A) The following were combined: the building block
N,N,N',N'-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetra-(p-tolyl)biphenyl-4,4'-diamine; Fg=hydroxy
(--OH); 4.24 g] and the building block
N,N'-diphenyl-N,N'-bis-(3-hydroxyphenyl)-terphenyl-4,4'-diamine
[segment=N,N,N',N'-tetraphenyl-terphenyl-4,4'-diamine; Fg--hydroxyl
(--OH); 5.62 g]; the additives Cymel303 (530 mg) and Silclean 3700
(420 mg), and the catalyst Nacure XP-357 (530 mg) and
1-methoxy-2-propanol (41.62 g). The mixture was mixed on a rolling
wave rotator for 10 min and then heated at 55.degree. C. for 65 min
until a homogenous solution resulted. The mixture was placed on the
rotator and cooled to room temperature. The solution was filtered
through a 1 micron PTFE membrane. (Action B) The reaction mixture
was applied to a commercially available, 30 mm drum photoreceptor
using a cup coater (Tsukiage coating) at a pull-rate of 485 mm/min.
(Action C) The photoreceptor drum supporting the wet layer was
rapidly transferred to an actively vented oven preheated to
140.degree. C. and left to heat for 40 min. These actions provided
a SOF having a thickness of 6.2 microns.
Example 49
Type 2 SOF Attempt
[0226] (Action A) Attempted preparation of the liquid containing
reaction mixture. The following were combined: the building block
tris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;
Fg=hydroxy (--OH); 5.12 g]; the additives Cymel303 (55 mg),
Silclean 3700 (210 mg), and 1-methoxy-2-propanol (13.27 g). The
mixture was heated to 55.degree. C. for 65 min in an attempt to
fully dissolve the molecular building block. However it did not
fully dissolve. A catalyst Nacure XP-357 (267 mg) was added and the
heterogeneous mixture was further mixed on a rolling wave rotator
for 10 min. In this Example, the catalyst was added after the
heating step. The solution was not filtered prior to coating due to
the amount of undissolved molecular building block. (Action B)
Deposition of reaction mixture as a wet film. The reaction mixture
was applied to a commercially available, 30 mm drum photoreceptor
using a cup coater (Tsukiage coating) at a pull-rate of 240 mm/min.
(Action C) Promotion of the change of the wet film to a dry film.
The photoreceptor drum supporting the wet layer was rapidly
transferred to an actively vented oven preheated to 140.degree. C.
and left to heat for 40 min. These actions did not provide a
uniform film. There were some regions where a non-uniform film
formed that contained particles and other regions where no film was
formed at all.
Example 50
Type 2 SOF
[0227] (Action A) The following were combined: the building block
tris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;
Fg=hydroxy (--OH); 5.12 g]; the additives Cymel303 (55 mg) and
Silclean 3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and
1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling
wave rotator for 10 min and then heated at 55.degree. C. for 65 min
until a homogenous solution resulted. The mixture was placed on the
rotator and cooled to room temperature. The solution was filtered
through a 1 micron PTFE membrane. It was noted that the viscosity
of the reaction mixture increased after the heating step (although
the viscosity of the solution before and after heating was not
measured). (Action B) The reaction mixture was applied to a
commercially available, 30 mm drum photoreceptor using a cup coater
(Tsukiage coating) at a pull-rate of 240 mm/min. (Action C) The
photoreceptor drum supporting the wet layer was rapidly transferred
to an actively vented oven preheated to 140.degree. C. and left to
heat for 40 min. These actions provided a SOF having a thickness of
6.9 microns.
Example 51
Type 2 SOF
[0228] (Action A) The following were combined: the building block
N,N,N',N'-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetra-(p-tolyl)biphenyl-4,4'-diamine; Fg=hydroxy
(--OH); 1.84 g] and the building block
3,3'-(4,4'-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol
[segment=3,3'-(4,4'-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;
Fg=hydroxy (--OH); (2.41 g] and a catalyst p-toluenesulphonic acid
(10 wt % solution in dowanol, 460 mg) and 1-methoxy-2-propanol
(16.9 g--containing 50 ppm DC510). The mixture was mixed on a
rolling wave rotator for 5 min and then heated at 70.degree. C. for
30 min until a homogenous solution resulted. The mixture was placed
on the rotator and cooled to room temperature. The solution was
filtered through a 1 micron PTFE membrane. (Action B) The reaction
mixture was applied to a production-coated web photoreceptor with a
Hirano web coater. Syringe pump speed: 4.5 mL/min. (Action C) The
photoreceptor supporting the wet layer was fed at a rate of 1.5
m/min into an actively vented oven preheated to 130.degree. C. for
2 min. These actions provided a SOF overcoat layer having a
thickness of 2.1 microns on a photoreceptor.
Example 52
Type 2 SOF
[0229] (Action A) The following were combined: the building block
N,N,N',N'-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetra-(p-tolyl)biphenyl-4,4'-diamine; Fg=hydroxy
(--OH); 5.0 g] and the building block benzenedimethanol
[segment=p-xylyl; Fg--hydroxyl (--OH); 2.32 g] and a catalyst
p-toluenesulphonic acid (10 wt % solution in dowanol, 720 mg) and
1-methoxy-2-propanol (22.5 g--containing 50 ppm DC510). The mixture
was mixed on a rolling wave rotator for 5 min and then heated at
40.degree. C. for 5 min until a homogenous solution resulted. The
mixture was placed on the rotator and cooled to room temperature.
The solution was filtered through a 1 micron PTFE membrane. (Action
B) The reaction mixture was applied to a production-coated,
production web photoreceptor a Hirano web coater. Syringe pump
speed: 5 mL/min. (Action C) The photoreceptor supporting the wet
layer was fed at a rate of 1.5 m/min into an actively vented oven
preheated to 130.degree. C. for 2 min. These actions provided a SOF
overcoat layer having a thickness of 2.2 microns on a
photoreceptor.
Example 53
Type 2 SOF
[0230] (Action A) The following were combined: the building block
N,N,N',N'-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4'-diamine
[segment=N,N,N',N'-tetra-(p-tolyl)biphenyl-4,4'-diamine; Fg=hydroxy
(--OH); 5.0 g] and the building block benzenedimethanol
[segment=p-xylyl; Fg--hydroxyl (--OH); 2.32 g] and a catalyst
p-toluenesulphonic acid (10 wt % solution in dowanol, 720 mg) and
1-methoxy-2-propanol (22.5 g--containing 50 ppm DC510). The mixture
was mixed on a rolling wave rotator for 5 min and then heated at
40.degree. C. for 5 min until a homogenous solution resulted. The
mixture was placed on the rotator and cooled to room temperature.
The solution was filtered through a 1 micron PTFE membrane. (Action
B) The reaction mixture was applied to a production-coated,
production web photoreceptor with a Hirano web coater. Syringe pump
speed: 10 mL/min. (Action C) The photoreceptor supporting the wet
layer was fed at a rate of 1.5 m/min into an actively vented oven
preheated to 130.degree. C. for 2 min. These actions provided a SOF
overcoat layer having a thickness of 4.3 microns on a
photoreceptor.
Example 54
[0231] (Action A) The following were combined: the building
4,4',4''-nitrilotris(benzene-4,1-diyl)trimethanol
[segment=(4,4',4''-nitrilotris(benzene-4,1-diyl)trimethyl);
Fg=alcohol (--OH); (1.48 g, 4.4 mmol)], 0.5 g water and 7.8 g of
1,4-dioxane. The mixture was shaken and heated to 60.degree. C.
until a homogenous solution resulted. Upon cooling to room
temperature, the solution was filtered through a 0.45 micron PTFE
membrane. To the filtered solution was added an acid catalyst
delivered as 0.15 g of a 10 wt % solution of p-toluenesulfonic acid
in 1,4-dioxane to yield the liquid containing reaction mixture.
(Action B) The reaction mixture was applied to the reflective side
of a metalized (TiZr) MYLAR.TM. substrate using a constant velocity
draw down coater outfitted with a bird bar having a 15 mil gap.
(Action C) The metalized MYLAR.TM. substrate supporting the wet
layer was rapidly transferred to an actively vented oven preheated
to 130.degree. C. and left to heat for 40 min. These actions
provided SOF having a thickness ranging from about 4-10 microns
that could be delaminated from substrate as a single free-standing
film. The color of the SOF was green. Two-dimensional X-ray
scattering data is provided in FIG. 8. As seen in FIG. 8, 2.theta.
is about 17.8 and d is about 4.97 angstroms, indicating that the
SOF possesses molecular order having a periodicity of about 0.5
nm.
Example 55
Type 2 SOF
[0232] (Action A) The following can be combined: the building block
4-hydroxybenzyl alcohol [segment=toluene; Fg=hydroxyl (--OH);
(0.0272 g, 0.22 mmol)] and a second building block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH3); (0.0728 g, 0.11 mmol)], and 0.88 g of
1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean
in 1-methoxy-2-propanol. The mixture is shaken and heated to
55.degree. C. until a homogenous solution is obtained. Upon cooling
to rt, the solution is filtered through a 0.45 micron PTFE
membrane. To the filtered solution is added an acid catalyst
delivered as 0.01 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture. (Action B) The reaction mixture was applied to the
aluminum substrate using a constant velocity draw down coater
outfitted with a bird bar having a 5 mil gap. (Action C) The
aluminum substrate supporting the wet layer is rapidly transferred
to an actively vented oven preheated to 140.degree. C. and left to
heat for 40 min.
Example 56
Type 2 SOF
[0233] (Action A) The following can be combined: the building block
4-(hydroxymethyl)benzoic acid [segment=4-methylbenzaldehyde;
Fg=hydroxyl (--OH); (0.0314 g, 0.206 mmol)] and a second building
block
N4,N4,N4',N4'-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4'-diamine
[segment=N4,N4,N4',N4'-tetra-p-tolylbiphenyl-4,4'-diamine;
Fg=methoxy ether (--OCH3); (0.0686 g, 0.103 mmol)], and 0.88 g of
1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean
in 1-methoxy-2-propanol. The mixture is shaken and heated to
55.degree. C. until a homogenous solution is obtained. Upon cooling
to rt, the solution is filtered through a 0.45 micron PTFE
membrane. To the filtered solution is added an acid catalyst
delivered as 0.01 g of a 10 wt % solution of p-toluenesulfonic acid
in 1-methoxy-2-propanol to yield the liquid containing reaction
mixture. (Action B) The reaction mixture was applied to the
aluminum substrate using a constant velocity draw down coater
outfitted with a bird bar having a 5 mil gap. (Action C) The
aluminum substrate supporting the wet layer is rapidly transferred
to an actively vented oven preheated to 140.degree. C. and left to
heat for 40 min.
Example 57
Type 2 SOF
[0234] (Action A) The following were combined: the building block
1,4 diaminobenzene [segment=benzene; Fg=amine (--NH.sub.2); (0.14
g, 1.3 mmol)] and a second building block 1,3,5-triformylbenzene
[segment=benzene; Fg=aldehyde (--CHO); (0.144 g, 0.89 mmol)], and
2.8 g of NMP. The mixture was shaken until a homogenous solution
resulted. Upon cooling to room temperature, the solution was
filtered through a 0.45 micron PTFE membrane. To the filtered
solution was added an acid catalyst delivered as 0.02 g of a 2.5 wt
% solution of p-toluenesulfonic acid in NMP to yield the liquid
containing reaction mixture. (Action B) The reaction mixture was
applied quartz plate affixed to the rotating unit of a variable
velocity spin coater rotating at 1000 RPM for 30 seconds. (Action
C) The quartz plate supporting the wet layer was rapidly
transferred to an actively vented oven preheated to 180.degree. C.
and left to heat for 120 min. These actions provide a yellow film
having a thickness of 400 nm that can be delaminated from substrate
upon immersion in water.
[0235] It will be appreciated that several of the above-disclosed
and other features and functions, or alternatives thereof, may be
desirably combined into many other different systems or
applications. Various presently unforeseen or unanticipated
alternatives, modifications, variations or improvements therein may
be subsequently made by those skilled in the art which are also
intended to be encompassed by the following claims. Unless
specifically recited in a claim, steps or components of claims
should not be implied or imported from the specification or any
other claims as to any particular order, number, position, size,
shape, angle, color, or material.
* * * * *