U.S. patent application number 16/679859 was filed with the patent office on 2020-03-05 for pbi modification and cross-linking methods.
This patent application is currently assigned to WHITEFOX TECHNOLOGIES LIMITED. The applicant listed for this patent is WHITEFOX TECHNOLOGIES LIMITED. Invention is credited to Stephan Rudiger BLUM, Wolfgang BREMSER, Katharina KLEINE.
Application Number | 20200071465 16/679859 |
Document ID | / |
Family ID | 45418274 |
Filed Date | 2020-03-05 |
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United States Patent
Application |
20200071465 |
Kind Code |
A1 |
BLUM; Stephan Rudiger ; et
al. |
March 5, 2020 |
PBI MODIFICATION AND CROSS-LINKING METHODS
Abstract
The present disclosure provides methods for modifying and
cross-linking polybenzimidazoles, PBI. In one embodiment, the
polybenzimidazole reacts with a compound, which has a halogen and a
double bond functionality and which comprises a halogen and an
organic group to form modified polymers by means of a nucleophilic
substitution of the amine proton of the benzimidazole functionality
in a solution, and a functional group is connected via each
resulting free double bond and/or the polymers that are thus
modified are cross-linked.
Inventors: |
BLUM; Stephan Rudiger;
(Calgary, CA) ; KLEINE; Katharina; (Paderborn,
DE) ; BREMSER; Wolfgang; (Dahl, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
WHITEFOX TECHNOLOGIES LIMITED |
London |
|
GB |
|
|
Assignee: |
WHITEFOX TECHNOLOGIES
LIMITED
London
GB
|
Family ID: |
45418274 |
Appl. No.: |
16/679859 |
Filed: |
November 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15876350 |
Jan 22, 2018 |
10472468 |
|
|
16679859 |
|
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|
14979039 |
Dec 22, 2015 |
9873768 |
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15876350 |
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13821390 |
May 28, 2013 |
9221951 |
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PCT/DE2011/001690 |
Sep 7, 2011 |
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14979039 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/0677 20130101;
C08G 73/18 20130101 |
International
Class: |
C08G 73/18 20060101
C08G073/18; C08G 73/06 20060101 C08G073/06 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 7, 2010 |
DE |
10 2010 044 579.7 |
Claims
1. A method for modification and cross-linking of polybenzimidazole
(PBI) having the structure ##STR00008## wherein the
polybenzimidazole reacts in a solution with a compound having a
halogen and a double bond functionality of the type ##STR00009##
where X is a halogen and R an organic group through a nucleophilic
substitution of the amine protons of the benzimidazole
functionality to obtain the modified polymers ##STR00010## where
the resulting free double bonds are connected in each case to a
functional group and/or cross-linking of the modified polymers
occurs.
2. Method according to claim 1, wherein the cross-linking between
two modified polymers occurs.
3. Method according to claim 1, wherein in that the cross-linking
between two modified polymers occurs by means of a cross-linking
molecule having at least two double bonds.
4. Method according to claim 1, characterized in wherein the
cross-linking of two modified polymers is via two double bonds.
5. A method according to claim 1, wherein at least one functional
group having a double bond is connected to a modified polymer.
6. A method according to claim 5, wherein the functional group has
high proton conductivity.
7. A method according to claim 5, wherein the functional group is
an amine group.
8. A method according to claim 5, wherein the functional group is
based on an ionic liquid.
9. A method according to claim 5, wherein the functional group
reduces the degree of crystallinity of the polybenzimidazole.
10. A method according to claim 1, wherein a monomer having a
double bond is connected to the double bond of a modified
polymer.
11. A modified polybenzimidazole polymer comprising repeat units of
formula ##STR00011## wherein at least one of the nitrogen atoms of
the repeat units is covalently bound to a compound of formula
##STR00012## wherein R' is an organic group.
12. The modified polybenzimidazole polymer of claim 11, wherein R'
is alkyl.
13. The modified polybenzimidazole polymer of claim 11, wherein R'
is --CH.sub.2--.
14. A crosslinked polybenzimidazole polymer produced from the
modified polybenzimidazole polymer of claim 11.
15. A modified polybenzimidazole polymer having the structure
##STR00013##
16. A crosslinked polybenzimidazole polymer produced from the
modified polybenzimidazole polymer of claim 15.
17. A crosslinked polybenzimidazole polymer having the structure
##STR00014## wherein C-L includes a crosslinker produced by
coupling any one or two of: an allyl group, vinylphosphonic acid,
1-allyl-3-methylimidazolium chloride, an amine group, allyl
benzene, allyl p-toluol sulfate, and triallyl isocyanurate.
18. The crosslinked polybenzimidazole polymer of claim 17, wherein
the crosslinker includes triallyl isocyanurate.
19. The crosslinked polybenzimidazole polymer of claim 17, wherein
the polymer has a failure temperature of about 528.degree. C.
20. The crosslinked polybenzimidazole polymer of claim 17, wherein
the polymer has a significantly higher modulus of elasticity at
high temperatures, compared to an unmodified polybenzimidazole
polymer.
Description
PRIORITY CLAIM
[0001] The present application is a continuation of U.S. patent
application Ser. No. 15/876,350, filed Jan. 22, 2018, which is a
divisional application of U.S. patent application Ser. No.
14/979,039, filed Dec. 22, 2015, issued as U.S. Pat. No. 9,873,768
on Jan. 23, 2018, which is a divisional application of U.S. patent
application Ser. No. 13/821,390, filed May 28, 2013 (371 (c) date),
issued as U.S. Pat. No. 9,221,951 on Dec. 29, 2015, which is a
national stage entry of International Application No.
PCT/DE2011/001690, filed on Sep. 7, 2011, which claims priority to
German Patent Application Number DE 10 2010 044 579.7, filed on
Sep. 7, 2010. The entire disclosure of each of these applications
is incorporated by reference herein.
SUMMARY
[0002] The present disclosure provides methods for the modification
and cross-linking of polybenzimidazole ("PBI").
[0003] PBI fibers, a product of space exploration in the 1980s,
originally served as the upper material of fire protective
clothing.
[0004] Because of its extraordinary thermal and chemical
resistance, PBI has now found its way into the production of fuel
cells as a membrane material and is used especially as a material
for high-temperature membranes in polymer electrolyte fuel cells
("PEFC"). PBI often serves as a matrix for proton-conducting
phosphoric acid because PBI withstands the high temperatures of
such fuel cells without problem but is itself a very poor proton
conductor, and therefore regularly needs corresponding doping.
[0005] Such doping has the advantage that by the choice of a
suitable dopant, membranes can be produced for fuel cells for both
acidic and alkaline fuels, for example with KOH as a dopant in the
case of alkaline fuels.
[0006] However, a disadvantage of such doping is the migration of
the dopant during operation of the fuel cell, so that the initial
high proton conductivity then decreases significantly over the
lifetime of the fuel cell.
[0007] Another disadvantage is the low mechanical stability of
highly doped PBI membranes. This can be encountered, for example,
in the case of cross-linking of polymers with difunctional halogen
compounds according to U.S. Patent Publication No. 2004/0261616 or
difunctional epoxides and isocyanates according to published German
Patent Application No. DE 101 10 752 A1. However, in the case of
the methods described there, the cross-linking reaction and the
competing doping process both take place because of the imidazole
functionality, especially in the case of the amine proton.
[0008] Against this technical background, the present disclosure
provides methods for preparing a modified PBI polymer that is easy
to manufacture, and, in particular when used as a starting material
for the membrane, can be largely freely functionalized and/or
cross-linked.
DETAILED DESCRIPTION
[0009] This technical problem is solved by the procedure as
disclosed herein. In one embodiment, a PBI with the structure
##STR00001##
[0010] is reacted in a solution, with a compound of a halogen and a
double bond functionality of the type
##STR00002##
[0011] where X is a halogen and R an organic group, for example an
alkyl halide, in particular 3-bromo-propene, which by a
nucleophilic substitution of the amine proton of the benzimidazole
functionality enables the modified polymers
##STR00003##
[0012] to be obtained. The free double bonds are now available for
cross-linking or functionalization of the thus modified polymer in
a simple manner.
[0013] The modified polymers in the form of precipitated powder or
granules can be mixed later with a cross-linking agent also in
powder form under suitable reaction conditions in order to form a
molded part.
[0014] If a molded part such as a membrane or a film is produced
from the solution, then the modified polymers, in particular
allyl-functionalized polymers, can be cross-linked directly or
indirectly to one another with or without an initiator, whereby a
non-soluble molded part is obtained.
[0015] The cross-linking between two modified polymers can be
obtained indirectly via a cross-linking molecule having at least
two double bonds. After the successful reaction of the original
PBI, a compound having a halogen and a double bond functionality is
added to the solution, which then has the modified polymers or,
after production of a molded part, this may be introduced into a
solution together with a component not dissolving the molded part
along with the cross-linking agent, and the cross-linking agent
diffuses into the molded part. Cross-linking is then obtained again
through associated heat treatment.
[0016] A particularly stable cross-linking is the direct
crosslinking of two modified polymers via two double bonds, which
is described below in the explanation of an embodiment.
[0017] In one embodiment, a polymer solution with polybenzimidazole
having the structure
##STR00004##
[0018] is obtained by the addition of LiCl to improve the
solubility and by the addition of a catalyst, preferably a bicyclic
tertiary amine, such as triethylenediamine or
1,4-diazabicyclo[2.2.2]octane or TEDA or DABCO in
dimethylacetamide, DMAc, is used as the solvent.
[0019] 4n 3-bromopropene (allyl bromide) is added as a compound
having a halogen and a double bond functionality:
##STR00005##
[0020] Following a reaction time of about 8 to 24 hours, 4n HBr can
be desorbed by heating the solution to about 40.degree. C., and a
modified polymer is obtained having the structure
##STR00006##
[0021] Films can be drawn from the solution and the LiCl washed
out.
[0022] The subsequent cross-linking is effected in an oven under
the influence of temperature to form:
##STR00007##
[0023] where C-L stands for cross-linking and can represent one of
the above-mentioned bonding functions.
[0024] Surprisingly, the failure temperature of the modified
cross-linked polymers at around 528.degree. C. when tested by
thermogravimetric analysis is only slightly lower than that of the
original polymers at around 536.degree. C., but this was expected
due to the linking of an aliphatic chain.
[0025] On the other hand, the behavior of the modified cross-linked
polymers when subjected to dynamic mechanical analysis, denotes a
significantly higher modulus of elasticity of the modified
cross-linked polymers at high temperatures, which indicates very
good cross-linking.
[0026] Accordingly, in one embodiment, cross-linking can be
provided that connects a functional group with at least two double
bonds to a double bond of a modified polymer.
[0027] Thus from the point of view of acidic membranes for fuel
cells, it is considered in particular that the functional group
would have a high proton conductivity, such as vinylphosphonic
acid, or 1-allyl-3-methylimidazolium chloride.
[0028] Thus one obtains an acidic PBI when a stoichiometric amount
of vinylphosphonic acid to the allyl units and an initiator such as
tert-butyl perbenzoate is added to a 3% aqueous solution of an
allyl-functionalized PBI in DMAc as described above.
[0029] The reaction solution is heated under nitrogen at
140.degree. C. for 4 hours to reflux.
[0030] The functional group may also be an amine group, through
which, in particular, the existing alkaline properties of the PBI
can be further emphasized. This may be beneficial in the production
of H.sub.2/CO.sub.2-selective, alkaline then anion-conducting
gas-separation membranes.
[0031] For such membranes, it may also be advantageous when the
functional group is based on an ionic liquid, for example,
connected to the allyl-bonding imidazolium. In the case of
membranes based on known ionic liquids, it is known that loss of
conduction may occur due to migration of the ionic liquid. By using
1-allyl-3-methylimidazolium chloride, one can connect the ionic
liquid covalently to the modified polymer, and thus prevent the
migration.
[0032] In another embodiment, the functional group decreases the
degree of crystallization of the polybenzimdazole, for example by
the connection of a bulky group such as allylbenzene or allyl
p-toluol sulfate.
[0033] In addition, the formation of copolymers is not a problem
when a monomer having a double bond is connected to the double bond
of a modified polymer, which can, for example, take place by means
of a radical polymerization.
[0034] As an example of functionalization and cross-linking of the
modified polymers, reference is also made to the possibility of
producing a film or a membrane made from an allyl-functionalized
PBI and then soaking it in an appropriate solution, for example,
vinylphosphonic acid, if necessary with the addition of a
cross-linking agent, in order to obtain a reaction between the
allyl function and the vinyl phosphonic acid in an oven and achieve
the cross-linking.
[0035] Another example of functionalization and linking of the
modified polymer is the addition of triallyl isocyanurate,
tradename TAIC, known as a co-activator for peroxide cross-linking,
which enables a variety of three double bond cross-linking
possibilities. Furthermore, triallyl isocyanurate, as a
polyfunctional allylic monomer, can itself polymerize or effect a
connection of a functional group to one of the double bonds.
* * * * *