U.S. patent application number 12/564963 was filed with the patent office on 2010-12-30 for porous polymer and synthetic method thereof.
Invention is credited to Teng Ben, Shilun QIU, Guangshan Zhu.
Application Number | 20100331436 12/564963 |
Document ID | / |
Family ID | 43381433 |
Filed Date | 2010-12-30 |
United States Patent
Application |
20100331436 |
Kind Code |
A1 |
QIU; Shilun ; et
al. |
December 30, 2010 |
Porous Polymer and Synthetic Method Thereof
Abstract
The present invention relates to a porous polymer and a
synthetic method thereof. The porous polymer has the following
general formula: ##STR00001## wherein, the positions marked with
the numeral 1-10 are C, CH, N, or CH with its H being substituted
by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester
group; the positions marked with letter a or b are C, N+, or
B-.
Inventors: |
QIU; Shilun; (Changchun
City, CN) ; Zhu; Guangshan; (Changchun City, CN)
; Ben; Teng; (Changchun City, CN) |
Correspondence
Address: |
Jackson Intellectual Property Group PLLC
106 Starvale Lane
Shipman
VA
22971
US
|
Family ID: |
43381433 |
Appl. No.: |
12/564963 |
Filed: |
September 23, 2009 |
Current U.S.
Class: |
521/124 ;
521/146 |
Current CPC
Class: |
C08G 61/12 20130101;
C08G 2261/3162 20130101; B01J 20/28042 20130101; B01J 20/267
20130101; B01J 20/3085 20130101; B01J 20/28083 20130101; C08G
2261/135 20130101; B01J 20/2808 20130101; C08G 61/10 20130101; C08G
2261/312 20130101 |
Class at
Publication: |
521/124 ;
521/146 |
International
Class: |
C08J 9/28 20060101
C08J009/28 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 29, 2009 |
CN |
200910108154.1 |
Jul 20, 2009 |
CN |
200910108821.6 |
Claims
1. A porous polymer having the following general formula:
##STR00041## wherein, the positions marked with the numeral 1-10
being C, CH, N, or CH with its H being substituted by methyl,
ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the
positions marked with letter a or b being C, N.sup.+, or
B.sup.-.
2. A synthetic method of the porous polymer of claim 1 comprising
the following steps: Step 1, adding
bis(1,5-cycloocta-1,5-diene)nickel(0), 2, 2'-bipyridyl, and
1,5-cycloocta-1,5-diene with the molar ratio thereof being
1:(0-15):(0-15) to a solution of DMF (N,N-dimethyl-Formamide) or
toluene, and heating the mixture at 20-140.degree. C. for 0-10
hours; Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M, and at the same time, making the
initial molar ratio of bis(1,5-cycloocta-1,5-diene)nickel(0) to the
monomer to be (2-18):1; Step 3, stirring the above mentioned
mixture at 20-140.degree. C. for 10 minutes to 10 days; Step 4,
cooling the mixture to room temperature, and then adding conc. HCl
to the mixture; Step 5, filtrating the mixture to obtain the
residue, then washing the residue with hot water. THF and CHCl3
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
3. The synthetic method of claim 2, wherein the reaction is
Yamamoto type Ullmann reaction.
4. The synthetic method of claim 2, wherein Step 5 comprises the
following steps: Step 5.1, treating the above mentioned crude
polymer by 10-100 ml water at 50-100.degree. C. for 3-5 times and
then isolating the above mentioned crude polymer by filtration;
Step 5.2, treating the above mentioned crude polymer by 10-100 ml
THF at 20-70.degree. C. for 3-5 times and then isolating the above
mentioned crude polymer by filtration; Step 5.3, treating the above
mentioned crude polymer by 10-100 ml CHCl3 at 20-60.degree. C. for
3-5 times and then isolating the above mentioned crude polymer by
filtration; Step 5.4, drying the polymer in vacuum at 3-10 mmHg for
4-40 hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
5. The synthetic method of claim 2, wherein the general formula of
the monomer is: ##STR00042## wherein, the positions marked with the
numeral 1-10 being C, CH, N, or CH with its H being substituted by
methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group;
the positions marked with letter a or b being C, N.sup.+, or
B.sup.-.
6. A synthetic method of the porous polymer of claim 1 comprising
the following steps: Step 1, adding NiCl2, NaBr, Zn powder, and
PPh3 with the molar ratio thereof being 1:(0-15):(1-15):(0-15) to a
solution of DMF or toluene, and heating the mixture at
20-140.degree. C. for 0-10 hours; Step 2, adding corresponding
quantity of reactive monomer to the resultant solution, keeping the
initial concentration of the monomer between 0.001M and 5M; Step 3,
stirring the above mentioned mixture at 20-140.degree. C. for 10
minutes to 10 days; Step 4, cooling the mixture to room
temperature, and then adding conc. HCl to the mixture; Step 5,
filtrating the mixture to obtain the residue, then washing the
residue with hot water, THF and CHCl3, respectively, and then
drying the residue in vacuum for 4-40 hours at 80-200.degree. C. to
obtain the porous polymer.
7. The synthetic method of claim 6, wherein the reaction is Ullmann
coupling reaction.
8. The synthetic method of claim 6, wherein Step 5 comprises the
following steps: Step 5.1, treating the above mentioned crude
polymer by 10-100 ml water at 50-100.degree. C. for 3-5 times and
then isolating the above mentioned crude polymer by filtration;
Step 5.2, treating the above mentioned crude polymer by 10-100 ml
THF at 20-70.degree. C. for 3-5 times and then isolating the above
mentioned crude polymer by filtration; Step 5.3, treating the above
mentioned crude polymer by 10-100 ml CHCl3 at 20-60.degree. C. for
3-5 times and then isolating the above mentioned crude polymer by
filtration; Step 5.4, drying the polymer in vacuum at 3-10 mmHg for
4-40 hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
9. The synthetic method of claim 6, wherein the general formula of
the monomer is: ##STR00043## wherein, the positions marked with the
numeral 1-10 being C, CH, N, or CH with its H being substituted by
methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group;
the positions marked with letter a or b being C, N.sup.+, or
B.sup.-.
10. A synthetic method of the porous polymer of claim 1 comprising
the following steps: Step 1, adding monomer with its initial
concentration being 0.001M-5M, and Pd(PPh3)4 with its initial molar
concentration being 0.05%-50% of the molar concentration of the
monomer to a solution of DMF or toluene, and stirring the mixture
for 0-10 hours under nitrogen atmosphere; Step 2, adding aqueous
alkaline solution with its initial molar concentration being 4-200
times of the molar concentration of the monomer to the resultant
solution; Step 3, heating the above mentioned solution at
20-140.degree. C. for 10 minutes to 10 days; Step 4, cooling the
mixture to room temperature, and then adding conc. HCl to the
mixture; Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl3, respectively,
and then drying the residue in vacuum for 4-40 hours at
80-200.degree. C. to obtain the porous polymer.
11. The synthetic method of claim 10, wherein the reaction is
Suzuki coupling reaction.
12. The synthetic method of claim 10, wherein Step 5 comprises the
following steps: Step 5.1, treating the above mentioned crude
polymer by 10-100 ml water at 50-100.degree. C. for 3-5 times and
then isolating the above mentioned crude polymer by filtration;
Step 5.2, treating the above mentioned crude polymer by 10-100 ml
THF at 20-70.degree. C. for 3-5 times and then isolating the above
mentioned crude polymer by filtration; Step 5.3, treating the above
mentioned crude polymer by 10-100 ml CHCl3 at 20-60.degree. C. for
3-5 times and then isolating the above mentioned crude polymer by
filtration; Step 5.4, drying the polymer in vacuum at 3-10 mmHg for
4-40 hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
13. The synthetic method of claim 10, wherein the general formula
of the monomer is: ##STR00044## wherein, the positions marked with
the numeral 1-10 being C, CH, N, or CH with its H being substituted
by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester
group; the positions marked with letter a or b being C, N.sup.+, or
B.sup.-.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to functional materials,
particularly relates to a series of porous polymer and a synthetic
method thereof.
BACKGROUND OF THE INVENTION
[0002] One of the most serious problems today is that the natural
disasters caused by the warming climate become increasingly severe,
of which the major cause is that, the greenhouse gases increase day
by day for using fossil fuels. Now, all the governments and
enterprises in the world pay great attention to develop techniques
about new clean energy source. At the same time, the Kyoto Protocol
about energy utilization and limiting the emission of greenhouse
gases is approved by more and more countries. How to increase the
energy utilization efficiency and reduce the environmental
pollution has become a problem that the countries in the world pay
great attention to,
[0003] The fuel cell technology is currently one of the
acknowledged core technologies in the energy technology field of
the 21st century. The working principle of a fuel cell is to
directly isothermally transform the chemical energy stored in fuels
and oxidants into electrical energy. Comparing with a normal fuel
engine, the fuel cell has the advantages of high efficiency, low
noise, high reliability, and especially very low emission, which is
considered as the currently preferred power generation technology
that is clean and highly efficient. The fuel cell can be widely
used in power plants, the automobile industry, or portable devices.
For more detailed presentations about fuel cells, please refer to
Int. J. Hydrogen Energy (22, No. 6, 601-610 (1997)) compiled by
Hynek, et al., the thesis of J. A. Kerres, et al. in Journal of
Membrane Science (185, 2001, 3-27), and the survey article of G.
March in Materials Today (4, No. 2 (2001), 20-24).
[0004] Porous materials have a comparatively large specific surface
area, and can adsorb more gas or small organic molecules that can
be used as fuels. So, the development of porous materials is the
most important thing in the field of key materials research of a
fuel cell. Porous materials comprise microporous materials having
pore size less than 2 nm, mesoporous materials having pore size
between 2 nm and 50 nm, and macroporous materials having pore size
bigger than 50 nm. In 1995, Omar Yaghi synthesized the MOF
(metal-organic-framework) (referring to Nature, 1995, (378), 703),
a metal-organic coordination polymer that is really close to
practical application. As a new functional molecular material, the
MOF not only has a crystal structure similar to the zeolite
molecular sieve, but also its structure is capable of being
designed. The MOF can obtain nano-size pore channels and cavities
by directionally designing the topological structure and expanding
the organic functional groups. So, it has great potential in
applications of storing gas or organic molecules. However, the MOF
has a comparative poor chemical stability. In 2005, Omar Yaghi
disclosed the COF (covalent organic framework) (referring to
Science, 2005, (310), 1166), an organic porous framework material,
which is composed of light elements (C, H, O, B) being connected
via covalent bonds. However, the chemical stability problem is not
really solved.
[0005] Therefore, the performance of porous polymers is still to be
improved further.
SUMMARY OF THE INVENTION
[0006] The first object of the present invention is to provide a
porous polymer, which has good thermal stability, good hydrothermal
stability, and super high BET specific surface area.
[0007] The second object of the present invention is to provide a
synthetic method of a porous polymer, which has high yield.
[0008] To achieve the above mentioned objects, the present
invention provides a porous polymer, which has the general formula
of:
##STR00002##
[0009] wherein, the positions marked with the numeral 1-10 are C,
CH, N, or CH with its H being substituted by methyl, ethyl, amido,
carboxyl, methoxyl, hydroxyl, or ester group; the positions marked
with letter a or b are C, N.sup.+, or B.sup.-.
[0010] The present invention also provides a synthetic method of a
porous polymer, which comprises the following steps:
[0011] Step 1, adding bis(1,5-cycloocta-1,5-diene)nickel(0), 2,
2'-bipyridyl, and 1,5-cycloocta-1,5-diene with the molar ratio
thereof being 1:(0-15):(0-15) to a solution of DMF
(N,N-dimethyl-Formamide) or toluene, and heating the mixture at
20-140.degree. C. for 0-10 hours;
[0012] Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M, and at the same time, making the
initial molar ratio of bis(1,5-cycloocta-1,5-diene)nickel(0) to the
monomer to be (2-18) 1;
[0013] Step 3, stirring the above mentioned mixture at
20-140.degree. C. for 10 minutes to 10 days;
[0014] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0015] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
[0016] Wherein, the reaction is Yamamoto type Ullmann reaction.
[0017] The present invention also provides a synthetic method of a
porous polymer, which comprises the following steps:
[0018] Step 1, adding NiCl.sub.2, NaBr, Zn powder, and PPh.sub.3
with the molar ratio thereof being 1:(0-15):(1-15) :(0-15) to a
solution of DMF or toluene, and heating the mixture at
20-140.degree. C. for 0-10 hours;
[0019] Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M;
[0020] Step 3, stirring the above mentioned mixture at
20-140.degree. C. for 10 minutes to 10 days;
[0021] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0022] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3,
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
[0023] Wherein, the reaction is Ullmann coupling reaction.
[0024] The present invention also provides a synthetic method of a
porous polymer, which comprises the following steps:
[0025] Step 1, adding monomer with its initial concentration being
0.001M-5M, and Pd(PPh.sub.3).sub.4 with its initial molar
concentration being 0.05%-50% of the molar concentration of the
monomer to a solution of DMF or toluene, and stirring the mixture
for 0-10 hours under nitrogen atmosphere;
[0026] Step 2, adding aqueous alkaline solution with its initial
molar concentration being 4-200 times of the molar concentration of
the monomer to the resultant solution;
[0027] Step 3, heating the above mentioned solution at
20-140.degree. C. for 10 minutes to 10 days;
[0028] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0029] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3,
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
[0030] Wherein, the reaction is Suzuki coupling reaction.
[0031] Wherein, Step 5 comprises the following steps:
[0032] Step 5.1, treating the above mentioned crude polymer by
10-100 ml water at 50-100.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0033] Step 5.2, treating the above mentioned crude polymer by
10-100 ml THF at 20-70.degree. C. for 3-5 times and then isolating
the above mentioned crude polymer by filtration.
[0034] Step 5.3, treating the above mentioned crude polymer by
10-100 ml CHCl.sub.3 at 20-60.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0035] Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40
hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
[0036] Wherein, the general formula of the monomer that is used in
the Yamamoto type Ullmann reaction and Ullmann coupling reaction
is:
##STR00003##
[0037] wherein, the positions marked with the numeral 1-10 are C,
CH, N, or CH with its H being substituted by methyl, ethyl, amido,
carboxyl, methoxyl, hydroxyl, or ester group; the positions marked
with letter a or b are C, N.sup.+, or B.sup.-.
[0038] Wherein, the general formula of the monomer that is used in
the Suzuki coupling reaction is:
##STR00004##
[0039] wherein, the positions marked with the numeral 1-10 are C,
CH, N, or CH with its H being substituted by methyl, ethyl, amido,
carboxyl, methoxyl, hydroxyl, or ester group; the positions marked
with letter a or b are C, N.sup.+, or B.sup.-.
[0040] In summary, the porous polymer of the present invention has
excellent thermal stability and good hydrothermal stability, which
can be widely used in fields of energy source, or electric
appliance, and so on, such as a power plant, an automobile, a
wireless electric equipment, a mobile phone, or a portable device.
Particularly, the present invention can be used as the carrier of
fuel in a fuel cell using fuels such as hydrogen, with big specific
surface area, high stability, and high efficiency in recycling use.
The synthetic method of the porous polymer of the present invention
has high yield.
[0041] The characteristic and the technical solution of the present
invention are best understood from the following detailed
description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] FIGS. 1A and 1B provide the topology structures of
polymerization products from the monomer in accordance with an
embodiment of the present invention;
[0043] FIG. 2A provides the FT-IR spectra of the polymerization
products from the monomer in accordance with an embodiment of the
present invention from 400-4000 cm.sup.-1;
[0044] FIG. 2B provides the characterization absorption bands for
Carbon-Bromine highlighted, clearly showing the lack of bromine in
the final product and indicating the formation of the porous
polymer;
[0045] FIG. 3 provides the TGA plot of polymerization products from
the monomer in accordance with an embodiment of the present
invention at air condition;
[0046] FIG. 4 provides TEM of polymerization products from the
monomer in accordance with an embodiment of the present invention
via Yamamoto Type Ullmann coupling reaction;
[0047] FIG. 5 provides N.sub.2 absorption-desorption isotherm of
polymerization products from the monomer in accordance with an
embodiment of the present invention via Yamamoto Type Ullmann
coupling reaction;
[0048] FIG. 6 provides pore size distribution of polymerization
products from the monomer in accordance with an embodiment of the
present invention via Yamamoto Type Ullmann coupling reaction;
[0049] FIG. 7 provides the N.sub.2 absorption-desorption isotherm
of polymerization products from the monomer in accordance with an
embodiment of the present invention after treated by boiling water
for 7 days, which is synthesized via Yamamoto Type Ullmann coupling
reaction;
[0050] FIG. 8 provides the pore size distribution of polymerization
products from the monomer in accordance with an embodiment of the
present invention after treated by boiling water for 7days, which
is synthesized via Yamamoto Type Ullmann coupling reaction;
[0051] FIGS. 9A and 9B provide absorption isotherms of
polymerization products from the monomer in accordance with an
embodiment of the present invention storing H.sub.2 at high
pressure;
[0052] FIG. 10 provides absorption isotherm of polymerization
products from the monomer in accordance with an embodiment of the
present invention storing CO.sub.2 at high pressure, which is
synthesized via Yamamoto Type Ullmann coupling reaction;
[0053] FIG. 11 provides toluene vapor adsorption isotherms at
298K;
[0054] FIG. 12 provides benzene vapor adsorption isotherms at
298K.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0055] The following embodiments and examples of this invention are
meant as an illustration of the microporous materials that are
obtained using the synthetic strategy defined by this invention,
and are not meant to limit in any way the scope of the
invention.
[0056] The present invention provides a porous polymer, which has
the general formula of:
##STR00005##
[0057] wherein, the positions marked with the numeral 1-10 are C,
CH, N, or CH with its H being substituted by methyl, ethyl, amido,
carboxyl, methoxyl, hydroxyl, or ester group; the positions marked
with letter a or b are C, N.sup.+, or B.sup.-.
[0058] The present invention provides three synthetic methods of
the above mentioned porous polymer: Yamamoto type Ullmann reaction,
Ullmann reaction, and Suzuki coupling reaction. The porous polymer
of the present invention can be obtained by all the three methods.
Some performance of the porous polymers obtained via the three
synthetic methods may be different, but these different synthetic
methods will not lead to any limitation to the practical
application of these porous polymers.
[0059] To clearly describe the three synthetic methods of the
porous polymer of the present invention, poly (tetra
p-phenylsilane) is cited as an example to detailedly describe the
present invention.
[0060] Poly (tetra p-phenylsilane) is synthesized by Yamamoto type
Ullmann reaction, which can be shown as the following reaction
equation:
##STR00006##
[0061] The reaction type is Yamamoto type Ullmann coupling
reaction, and the catalyst used in the reaction is the mixture of
bis(1,5-cycloocta-1,5-diene)nickel(0), 2, 2'-bipyridyl, and
1,5-cycloocta-1,5-diene.
[0062] The synthetic method comprises the following steps:
[0063] Step 1, adding bis(1,5-cycloocta-1,5-diene)nickel(0), 2,
2'-bipyridyl, and 1,5-cycloocta-1,5-diene with the molar ratio
thereof being 1:(0-15):(0-15) to a solution of DMF
(N,N-dimethyl-Formamide) or toluene, and heating the mixture at
20-140.degree. C. for 0-10 hours;
[0064] Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M, and at the same time, making the
initial molar ratio of bis(1,5-cycloocta-1,5-diene)nickel(0) to the
monomer to be (2-18):1;
[0065] Step 3, stirring the above mentioned mixture at
20-140.degree. C. for 10 minutes to 10 days;
[0066] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0067] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3
respectively, and then drying the residue, in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
[0068] Step 5 comprises the following steps:
[0069] Step 5.1, treating the above mentioned crude polymer by
10-100 ml water at 50-100.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0070] Step 5.2, treating the above mentioned crude polymer by
10-100 ml THF at 20-70.degree. C. for 3-5 times and then isolating
the above mentioned crude polymer by filtration;
[0071] Step 5.3, treating the above mentioned crude polymer by
10-100 ml CHCl.sub.3 at 20-60.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0072] Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40
hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
[0073] Poly (tetra p-phenylsilane) is synthesized by Ullmann
reaction, which can be shown as the following reaction
equation:
##STR00007##
[0074] The reaction type is Ullmann reaction, and the catalyst used
in the reaction is the system of Zn powder, NiCl.sub.2, NaBr, and
PPh.sub.3.
[0075] The synthetic method comprises the following steps:
[0076] Step 1, adding NiCl.sub.2, NaBr, Zn powder, and PPh.sub.3
with the molar ratio thereof being 1:(0-15):(1-15):(0-15) to a
solution of DMF or toluene, and heating the mixture at
20-140.degree. C. for 0-10 hours;
[0077] Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M;
[0078] Step 3, stirring the above mentioned mixture at
20-140.degree. C. for 10 minutes to 10 days;
[0079] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0080] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3,
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the porous polymer.
[0081] Step 5 comprises the following steps:
[0082] Step 5.1, treating the above mentioned crude polymer by
10-100 ml water at 50-100.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0083] Step 5.2, treating the above mentioned crude polymer by
10-100 ml THF at 20-70.degree. C. for 3-5 times and then isolating
the above mentioned crude polymer by filtration;
[0084] Step 5.3, treating the above mentioned crude polymer by
10-100 ml CHCl.sub.3 at 20-60.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0085] Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40
hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
[0086] Poly (tetra p-phenylsilane) is synthesized by Suzuki
coupling reaction, which can be shown as the following reaction
equation:
##STR00008##
[0087] The reaction type is Suzuki coupling reaction, and the
catalyst used in the reaction is the system of Pd(PPh.sub.3).sub.4
and alkaline solution.
[0088] The synthetic method comprises the following steps:
[0089] Step 1, adding monomer with its initial concentration being
0.001M-5M, and Pd(PPh.sub.3).sub.4 with its initial molar
concentration being 0.05%-50% of the molar concentration of the
monomer to a solution of DMF or toluene, and stirring the mixture
for 0-10 hours under nitrogen atmosphere;
[0090] Step 2, adding aqueous alkaline solution with its initial
molar concentration being 4-200 times of the molar concentration of
the monomer to the resultant solution;
[0091] Step 3, heating the above mentioned solution at
20-140.degree. C. for 10 minutes to 10 days;
[0092] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0093] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3,
respectively, and then drying the is residue in vacuum for 4-40
hours at 80-200.degree. C. to obtain the porous polymer.
[0094] Step 5 comprises the following steps:
[0095] Step 5.1, treating the above mentioned crude polymer by
10-100 ml water at 50-100.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0096] Step 5.2, treating the above mentioned crude polymer by
10-100 ml THF at 20-70.degree. C. for 3-5 times and then isolating
the above mentioned crude polymer by filtration;
[0097] Step 5.3, treating the above mentioned crude polymer by
10-100 ml CHCl.sub.3 at 20-60.degree. C. for 3-5 times and then
isolating the above mentioned crude polymer by filtration;
[0098] Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40
hours at 80-200.degree. C., and then obtaining the pure porous
polymer.
[0099] To further describe the three synthetic methods of the
porous polymer of the present invention, the following will further
describe typical compounds that are synthesized by five different
types of monomers, and the corresponding three synthetic methods
thereof. In the general formulas of the following five monomers,
the substituent R1, R2, R3, or R4 is phenyl, naphthyl, biphenylyl,
pyridyl, pyridazinyl, triazinyl, tetrazinyl, pentazinyl, Hexazinyl,
or 1-phenylpyridinyl. Any position of the substituent R1, R2, R3,
or R4 can be provided with one or more substituents, such as
methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group.
The connection mode of the substituents may be connecting the
substituents at any position. Ionic polymer involved in the present
invention is all provided with corresponding counterion, so as to
make the final material to be electrically neutral.
[0100] 1. Poly tetra aryl methane monomer has the general formula
of
##STR00009##
[0101] and a typical compound that can be synthesized with it is
poly tetrabiphenyl-4-ylmethane with the structural formula of
##STR00010##
[0102] In the first two methods(Yamamoto type Ullmann reaction,
Ullmann reaction), the reactive monomer is:
##STR00011##
[0103] (tetrakis(4'-bromobiphenyl-4-yl)methane) or
##STR00012##
[0104] (tetrakis(4'-iodobiphenyl-4-yl)methane).
[0105] In the third method (Suzuki coupling reaction), the reactive
monomer is:
##STR00013##
[0106]
(4',4'',4''',4''''-methanetetrayltetrakis(biphenyl-4',4-diyl)tetrab-
oronic acid) and
##STR00014##
[0107] (tetrakis(4'-iodobiphenyl-4-yl)methane).
[0108] 2. Poly tetra aryl silane monomer has the general formula
of
##STR00015##
[0109] and a typical compound that can be synthesized with it is
poly tetra p-phenylsilane with the structural formula of
##STR00016##
[0110] In the first two methods(Yamamoto type Ullmann reaction,
Ullmann reaction), the reactive monomer is:
##STR00017##
[0111] (tetrakis(4-bromophenyl)silane) or
##STR00018##
[0112] (tetrakis(4-iodophenyl)silane).
[0113] In the third method (Suzuki coupling reaction), the reactive
monomer is:
##STR00019##
[0114] (tetrakis(4-iodophenyl)silane) and
##STR00020##
[0115]
(4,4',4'',4'''-silanetetrayltetrakis(benzene-4,1-diyl)tetraboronic
acid).
[0116] 3. Poly tetra aryl ammonium salt monomer has the general
formula of
##STR00021##
[0117] and a typical compound that can be synthesized with it is
poly tetra p-phenylammonium salt with the structural formula of
##STR00022##
[0118] In the first two methods (Yamamoto type Ullmann reaction,
Ullmann reaction), the reactive monomer is:
##STR00023##
[0119] (tetrakis(4-bromophenyl)ammonium salt) or
##STR00024##
[0120] (tetrakis(4-iodophenyl)ammonium salt),
[0121] In the third method (Suzuki coupling reaction), the reactive
monomer is:
##STR00025##
[0122] (tetrakis(4-iodophenyl)ammonium salt) and
##STR00026##
[0123] (tetrakis(4-boronophenyl)ammonium salt).
[0124] 4. Poly tetra aryl phosphonium salt monomer has the general
formula of
##STR00027##
[0125] and a typical compound that can be synthesized with it is
poly tetra p-phenylphosphonium salt with the structural formula
of
##STR00028##
[0126] In the first two methods(Yamamoto type Ullmann reaction,
Ullmann reaction), the reactive monomer is:
##STR00029##
[0127] (tetrakis(4-bromophenyl)phosphonium salt) or
##STR00030##
[0128] (tetrakis(4-iodophenyl)phosphonium salt).
[0129] In the third method (Suzuki coupling reaction), the reactive
monomer is:
##STR00031##
[0130] (tetrakis(4-iodophenyl)phosphonium salt) and
##STR00032##
[0131] (tetrakis(4-boronophenyl)phosphonium salt).
[0132] 5. Poly tetra aryl borate salt monomer has the general
formula of
##STR00033##
[0133] and a typical compound that can be synthesized with it is
poly tetra p-phenylborate salt with the structural formula of
##STR00034##
[0134] In the first two methods(Yamamoto type Ullmann reaction,
Ullmann reaction), the reactive monomer is:
##STR00035##
[0135] (tetrakis(4-bromophenyl)borate salt) or
##STR00036##
[0136] (tetrakis(4-iodophenyl)borate salt).
[0137] In the third method (Suzuki coupling reaction), the reactive
monomer is:
##STR00037##
[0138] (tetrakis(4-iodophenyl)borate salt) and
##STR00038##
[0139] (tetrakis(4-boronophenyl)borate salt).
[0140] As an example, the following will detailedly describe
synthesizing poly tetra p-phenylmethane by Yamamoto Type Ullmann
coupling reaction,
[0141] Referring to FIGS. 1A and 1B, the topology structures of
polymerization products from the monomer in accordance with an
embodiment of the present invention are shown. The polymer that is
synthesized can be regarded as a porous polymer that has super high
specific surface area and is formed by connecting the carbon atoms
of diamond via biphenylyl. The molecular formula of poly tetra
p-phenylmethane is (C(Ph).sub.4).sub.n, and its structural formula
is
##STR00039##
[0142] The reaction process can be shown as the following reaction
equation:
##STR00040##
[0143] The synthetic method of poly tetra p-phenylmethane in the
present invention comprises the following steps:
[0144] Step 1, adding bis(1,5-cycloocta-1,5-diene)nickel(0), 2,
2'-bipyridyl, and 1,5-cycloocta-1,5-diene with same molar ratio to
a solution of DMF (N,N-dimethyl-Formamide) or toluene, and heating
the mixture at 20-140.degree. C. for 0.5-3 hours;
[0145] Step 2, adding corresponding quantity of reactive monomer to
the resultant solution, keeping the initial concentration of the
monomer between 0.001M and 5M, and at the same time, making the
initial molar ratio of bis(1,5-cycloocta-1,5-diene)nickel(0) to the
halogen to be 0.6 to 1.5;
[0146] Step 3, stirring the above mentioned mixture at
20-140.degree. C. for 10 minutes to 5 days;
[0147] Step 4, cooling the mixture to room temperature, and then
adding conc. HCl to the mixture;
[0148] Step 5, filtrating the mixture to obtain the residue, then
washing the residue with hot water, THF and CHCl.sub.3
respectively, and then drying the residue in vacuum for 4-40 hours
at 80-200.degree. C. to obtain the poly tetra p-phenylmethane.
[0149] The following steps are adopted to concretely synthesize
poly tetra p-phenylmethane.
[0150] (1) To a 1 mL of DMF solution was added 1 g of
bis(1,5-cycloocta-1,5-diene)nickel(0), 0.568 g of 2, 2'-bipyridyl,
and 0.4 mL of 1,5-cycloocta-1,5-diene, and the mixture was heated
at 60.degree. C. for 0.5-3 hours;
[0151] (2) To the resultant solution was added 3 mL of 0.2M
tetrakis(4-bromophenyl)methane DMF solution, and stirred at that
temperature for 60 hours;
[0152] (3) After cooling to room temperature, conc. HCl was added
to the mixture;
[0153] (4) After filtration the residue was washed with 100 mL hot
water, THF, and CHCl.sub.3, respectively;
[0154] (5) After dried in vacuum at 3-10 mmHg for 4-40 hours at
80-200.degree. C., the pure porous polymer was obtained with 76%
yield.
[0155] FIG. 1A shows the topology structure of diamond and FIG. 2A
shows the topology structure of poly tetra p-phenylmethane that is
synthesized with tetrakis(4-bromophenyl)methane via Yamamoto Type
Ullmann coupling reaction.
[0156] Referring to FIG. 2A and FIG. 2B, FT-IR of poly tetra
p-phenylmethane that is synthesized with
tetrakis(4-bromophenyl)methane via Yamamoto Type Ullmann coupling
reaction, and the reactive monomer are shown. The solid line shows
IR absorption of the monomer, and the dashed line shows IR
absorption of the porous polymer. Characterization absorption bands
for Carbon-Bromine highlighted, clearly shows the lack of bromine
in the final product and indicates the completely formation of the
porous polymer.
[0157] Referring to FIG. 3, a thermogravimetric diagram of a porous
polymer that is synthesized with tetrakis(4-bromophenyl)methane via
Yamamoto Type Ullmann coupling reaction is shown. According to the
result, the temperature of 5% mass loss of this porous polymer is
420.degree. C., which means that the porous polymer has a very good
thermal stability.
[0158] FIG. 4 shows a TEM photography of a porous polymer that is
synthesized with tetrakis(4-bromophenyl)methane via Yamamoto Type
Ullmann coupling reaction. According to the TEM results, wormlike
porestructures can clearly be observed.
[0159] FIG. 5 shows a N.sub.2 absorption-desorption isotherm of a
porous polymer that is synthesized with
tetrakis(4-bromophenyl)methane via Yamamoto Type Ullmann coupling
reaction at 77K. The solid dot shows the absorption curve, and the
hollow dot shows the desorption curve. According to the N.sub.2
absorption-desorption isotherm, the BET specific surface area of
the porous polymer is 5600 m.sup.2/g.
[0160] FIG. 6 provides a pore size distribution of a porous polymer
that is synthesized with tetrakis(4-bromophenyl)methane via
Yamamoto Type Ullmann coupling reaction. The pore size distribution
is calculated according to H-K method. Indicated in FIG. 7, the
average pore diameter of the porous polymer is about 1 nm.
[0161] FIG. 7 shows a N.sub.2 absorption-desorption isotherm of a
porous polymer after treated by boiling water for 7 days, which is
synthesized with tetrakis(4-bromophenyl)methane via Yamamoto Type
Ullmann coupling reaction. The solid dot shows the absorption
curve, and the hollow dot shows the desorption curve. After treated
in boiling water for even 7 days, the surface area of the porous
polymer has almost no change, which indicates the excellent
hydrothermal stability.
[0162] FIG. 8 shows the pore size distribution of a porous polymer
after treated by boiling water for 7 days, which is synthesized
with tetrakis(4-bromophenyl)methane via Yamamoto Type Ullmann
coupling reaction. The pore size distribution is calculated
according to H-K method. After treated by boiling waters the pore
size has almost no change.
[0163] FIG. 9A and FIG. 9B show absorption isotherms of a porous
polymer storing H.sub.2 with different temperature at high
pressure, which is synthesized with tetrakis(4-bromophenyl)methane
via Yamamoto Type Ullmann coupling reaction. As shown in FIGS. 9A
and 9B, the excess hydrogen uptake capacity of PPB-1 at 48 bar, 77
K can reach 7.0 wt %, which corresponds to an absolute uptake of
10.7 wt %. These values are comparable to the best performances of
conventional high-surface area porous MOFs and COFs, and represent
the highest among porous organic polymers.
[0164] High-pressure CO2 adsorption isotherm at 298 K was also
collected to assess the potential of PPB-1 for carbon dioxide
capture application. As indicated in FIG. 10, porous polymer which
is synthesized with tetrakis(4-bromophenyl)methane can adsorb 1300
mg/g CO.sub.2 at 40 bar and at room temperature, which is also
among the highest for conventional porous materials. Given the
hydrophobicity of porous polymer together with its exceptional
surface area, we also explored its capability for adsorption of
organic vapors such as benzene and toluene, chemicals which are of
environmental concern. As indicated in FIGS. 11 and 12, porous
polymer can adsorb large amounts of benzene and toluene vapors at
room temperature with values of 1306 mg/g (16.74 mmol/g) and 1357
mg/g (14.73 mmol/g) respectively at their saturated vapor
pressures. The excellent sorption performances of this porous
polymer, widely surpassing that of all conventional porous
materials, promises great potential for further environmental
application of this material.
[0165] The porous polymer poly tetra p-phenylmethane of the present
invention has super high specific surface area for storing gas,
which can be used to store hydrogen. Using the porous polymer to
store hydrogen comprises the following steps:
[0166] (1) after activation, using an ordinary oil bump to dry he
activated porous polymer in vacuum for 4-40 hours at 80-200.degree.
C.;
[0167] (2) at 290K-30K, at the pressure of 1-50 bar, testing the
hydrogen storage capacity of the above mentioned material.
[0168] The porous polymer of the present invention has super high
specific surface area for storing gas, which can also be used to
store carbon dioxide. Using the porous polymer to store carbon
dioxide comprises the following steps:
[0169] (1) after activation, using an ordinary oil bump to dry the
activated porous polymer in vacuum for 4-40 hours at 80-200.degree.
C.;
[0170] (2) at 25.degree. C., at the pressure of 1-42 bar, testing
the carbon dioxide storage capacity of the above mentioned
material.
[0171] The porous polymer poly tetra p-phenylmethane of the present
invention has super high specific surface area for adsorbing
liquid, which can be used to adsorb toluene. Using the porous
polymer to adsorb toluene comprises the following steps:
[0172] (1) after activation, using an ordinary oil bump to dry the
activated porous polymer in vacuum for 4-40 hours at 80-200.degree.
C.;
[0173] (2) at 25.degree. C., at the pressure of 0-1 bar, testing
the toluene adsorbing capacity of the above mentioned material.
[0174] The porous polymer poly tetra p-phenylmethane of the present
invention has super high specific surface area for adsorbing
liquid, which can also be used to adsorb benzene. Using the porous
polymer to adsorb benzene comprises the following steps:
[0175] (1) after activation, using an ordinary oil bump to dry he
activated porous polymer in vacuum for 4-24 hours at 80-200.degree.
C.;
[0176] (2) at 25.degree. C., at the pressure of 0-1 bar, testing
the benzene adsorbing capacity of the above mentioned material.
[0177] Herein, we present a strategy that has enabled us to achieve
a structure possessing by far the highest surface area as well as
exceptional thermal and hydrothermal stabilities. For example, poly
tetra p-phenylmethane synthesized by present invention has rigid
aromatic open framework which has a Langmuir surface area of 7100
m.sup.2/g. Besides its exceptional surface area, poly tetra
p-phenylmethane outperforms highly porous MOFs in thermal and
hydrothermal stabilities, as well as demonstrates high uptake
capacities of hydrogen (10.7% wt % at 77 K, 48 bar) and carbon
dioxide (1300 mg/g at 298 K, 40 bar). Moreover, the aromatic
backbone and high surface area enable poly tetra p-phenylmethane to
possess unprecedented uptake capacities of benzene and toluene
vapors at room temperature with values of 1306 mg/g (16.74 mmol/g)
and 1357 mg/g (14.73 mmol/g) respectively at their saturated vapor
pressures. The excellent sorption performances of poly tetra
p-phenylmethane, widely surpassing that of all other porous
materials, promises great potential for further environmental and
energy application of this material.
[0178] The following non-limiting examples illustrate the various
embodiments of the present invention. Those skilled in the art will
recognize many variations that are within the spirit of the present
invention and scope of the claims.
Example 1
[0179] (1) To 1 mL of DMF solution was added
bis(1,5-cycloocta-1,5-diene)nickel(0) (1 g), 2, 2'-bipyridyl (0.568
g) and 1,5-cycloocta-1,5-diene (0.4 mL) and the mixture was heated
at 50.degree. C. for 0.5 hour;
[0180] (2) To the resultant mixture was added 3 mL
tetrakis(4-bromophenyl)silane (DMF solution, 0.2M), and stirred at
that temperature for 60 hours;
[0181] (3) After cooling to room temperature, conc. HCl was added
to the reaction mixture;
[0182] (4) After filtration the residue was washed with 100 mL hot
water, THF, and CHCl.sub.3, respectively;
[0183] (5) After dried in vacuum at 3-10 mmHg for 10-40 hours at
80-200.degree. C., the pure porous polymer was obtained with 76%
yield.
Example 2
[0184] The procedure is repeated in a manner similar to that of
step (1) of example 1. The reaction mixture was injected into a
stainless steel autoclave at 90.degree. C., which yields a polymer
with properties very similar to those of the polymer made in
example 1.
Example 3
[0185] The procedure is repeated in a manner similar to that of
example 1. The monomer was changed to
tetrakis(4-iodophenyl)methane, which yields a polymer (84% yield)
with properties very similar to those of the polymer made in
example 1.
Example 4
[0186] The procedure is repeated in a manner similar to that of
step (1) of example 1. 2, 2'-bipyridyl and 0.4 mL of
1,5-cycloocta-1,5-diene are absent, which yields a polymer with
properties very similar to those of the polymer made in example
1.
Example 5
[0187] The procedure is repeated in a manner similar to that of
step (1) of example 1. The solvent changes to toluene, which yields
a polymer with properties very similar to those of the polymer made
in example 1.
Example 6
[0188] The procedure is repeated in a manner similar to that of
step (1) of example 1. The solvent changes to DMAc, which yields a
polymer with properties very similar to those of the polymer made
in example 1.
Example 7
[0189] The procedure is repeated in a manner similar to that of
step (1) of example 1. The solvent changes to NMP, which yields a
polymer with properties very similar to those of the polymer made
in example 1.
Example 8
[0190] The procedure is repeated in a manner similar to that of
step (1) of example 1. The solvent changes to benzene, which yields
a polymer with properties very similar to those of the polymer made
in example 1.
Example 9
[0191] The procedure is repeated in a manner similar to that of
step (1) of example 1. The aging time extend to 10 hours and yields
a polymer with properties very similar to those of the polymer made
in example 1.
Example 10
[0192] (1) To a 1L DMF solution was added
tetrakis(4-bromophenyl)silane (6.52 g),
4,4',4'',4'''-silanetetrayltetrakis(benzene-4,1-diyl)tetraboron- ic
acid (5.1 g), and Pd(PPh.sub.3).sub.4 (0.1 g), and stirred the
mixture under N.sub.2 for 1 hour;
[0193] (2) To the above mentioned mixture was added 100 mL of 1M
K.sub.2CO.sub.3 aqueous solution;
[0194] (3) Keep the above mentioned mixture reflux for 3 days;
[0195] (4) After cooling to room temperature, dilute hydrochloric
acid is added to the reaction system;
[0196] (5) After filtration, the mixture is washed by hot water,
THF and CHCl.sub.3, respectively;
[0197] (6) After dried in vacuum for 10-40 hours at 80-200.degree.
C., the pure porous polymer was obtained with 58% yield,
Example 11
[0198] The procedure is repeated in a manner similar to that of
step (3) of example 10. The reaction mixture was injected into a
stainless steel autoclave at 90.degree. C., which yields a polymer
with properties very similar to those of the polymer made in
example 10.
Example 12
[0199] The procedure is repeated in a manner similar to that of
example 10. The tetrakis(4-bromophenyl)silane was changed to
tetrakis(4-iodophenyl)silane, which yields a polymer (76% yield)
with properties very similar to those of the polymer made in
example 1.
Example 13
[0200] The procedure is repeated in a manner similar to that of
step (1) of example 10. The solvent changes to toluene, which
yields a polymer with properties very similar to those of the
polymer made in example 10.
Example 14
[0201] The procedure is repeated in a manner similar to that of
step (1) of example 10. The solvent changes to DMAc, which yields a
polymer with properties very similar to those of the polymer made
in example 10.
Example 15
[0202] The procedure is repeated in a manner similar to that of
step (1) of example 10. The solvent changes to NMP, which yields a
polymer with properties very similar to those of the polymer made
in example 10.
Example 16
[0203] The procedure is repeated in a manner similar to that of
step (1) of example 10. The solvent changes to benzene, which
yields a polymer with properties very similar to those of the
polymer made in example 10.
Example 17
[0204] (1) To DMF is added NiCl.sub.2 (0.09 g), NaBr (0.1 g), Zn
powder (6.5 g), and PPh.sub.3 (1.05 g), and the mixture was heated
at 60.degree. C. for 3 hours;
[0205] (2) To the resultant mixture was added
tetrakis(4-bromophenyl)silane (6.5 g);
[0206] (3) keep the above mentioned solution stirred at 140.degree.
C. for 3 days;
[0207] (4) After cooling to room temperature, dilute hydrochloric
acid was added to the reaction mixture;
[0208] (5) After filtration the residue was washed with hot water,
of THF, and of CHCl.sub.3, respectively;
[0209] (6) After dried in vacuum at 3-10 mmHg for 10-40 hours at
80-200.degree. C., the pure porous polymer was obtained with 62%
yield.
Example 18
[0210] The procedure is repeated in a manner similar to that of
step (3) of example 17. The reaction mixture was injected into a
stainless steel autoclave at 90.degree. C., which yields a polymer
with properties very similar to those of the polymer made in
example 1.
Example 19
[0211] The procedure is repeated in a manner similar to that of
step (2) of example 17. The tetrakis(4-bromophenyl)silane was
changed to tetrakis(4-iodophenyl)silane, which yields a polymer
(81% yield) with properties very similar to those of the polymer
made in example 1.
Example 20
[0212] The procedure is repeated in a manner similar to that of
step (1) of example 17. The solvent changes to toluene, which
yields a polymer with properties very similar to those of the
polymer made in example 17.
Example 21
[0213] The procedure is repeated in a manner similar to that of
step (1) of example 17. The solvent changes to DMAc, which yields a
polymer with properties very similar to those of the polymer made
in example 17.
Example 22
[0214] The procedure is repeated in a manner similar to that of
step (1) of example 17. The solvent changes to NMP, which yields a
polymer with properties very similar to those of the polymer made
in example 17.
Example 23
[0215] The procedure is repeated in a manner similar to that of
step (1) of example 17. The solvent changes to benzene, which
yields a polymer with properties very similar to those of the
polymer made in example 17.
[0216] In summary, the porous polymer of the present invention has
excellent thermal stability and good hydrothermal stability, which
can be widely used in fields of energy source, or electric
appliance, such as a power plant, an automobile, a wireless
electric equipment, a mobile phone, or a portable device.
Particularly, the porous polymer of the present invention can be
used as the carrier of fuel in a fuel cell using fuels such as
hydrogen with large specific surface area, high stability, and high
efficiency in recycling use. Comparing with conventional materials,
the material of the present invention can make a hydrogen fuel cell
to have practical significance. The synthetic method of the porous
polymer of the present invention has high yield.
[0217] Although the present invention has been described in detail
with above said embodiments, but it is not to limit the scope of
the invention. So, all the modifications and changes according to
the characteristic and spirit of the present invention are involved
in the protected scope of the invention.
* * * * *