U.S. patent application number 14/828628 was filed with the patent office on 2017-02-23 for method of forming polyaryl polymers and polymers formed thereby.
The applicant listed for this patent is DOW Global Technologies LLC. Invention is credited to Patrick Hanley, Arkady Krasovskiy, Matthias S. Ober.
Application Number | 20170051102 14/828628 |
Document ID | / |
Family ID | 58017408 |
Filed Date | 2017-02-23 |
United States Patent
Application |
20170051102 |
Kind Code |
A1 |
Ober; Matthias S. ; et
al. |
February 23, 2017 |
METHOD OF FORMING POLYARYL POLYMERS AND POLYMERS FORMED THEREBY
Abstract
In a method of forming a polyaryl polymer, a
fluorosulfonate-containing monomer is coupled with itself or a
boron-containing comonomer in the presence of a catalyst and a
base. The resulting polymers can be used as precursors to
electrically conducting polymers, and as components of resist or
underlayer compositions for photolithography, among other
applications.
Inventors: |
Ober; Matthias S.; (Midland,
MI) ; Krasovskiy; Arkady; (Midland, MI) ;
Hanley; Patrick; (Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW Global Technologies LLC |
Midland |
MI |
US |
|
|
Family ID: |
58017408 |
Appl. No.: |
14/828628 |
Filed: |
August 18, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 61/10 20130101;
C08G 2261/312 20130101; C08G 2261/314 20130101; C08G 2261/344
20130101; C08G 61/12 20130101; C08G 2261/41 20130101; C08G
2261/3142 20130101; C08G 61/128 20130101 |
International
Class: |
C08G 61/12 20060101
C08G061/12; C08G 61/10 20060101 C08G061/10 |
Claims
1. A method of forming a polyaryl polymer, the method comprising:
reacting a monomer in the presence of a catalyst and a base to form
a polymer; wherein the monomer comprises (a) a first monomer having
structure (1) ##STR00040## wherein Ar.sup.x is unsubstituted or
substituted C.sub.6-43 arylene, or unsubstituted or substituted
C.sub.3-43 heteroarylene; and B.sup.x is a boron-containing
functional group bonded to Ar.sup.x via a boron atom; or (b) a
first comonomer having structure (2) and a second comonomer having
structure (3) ##STR00041## wherein Ar.sup.x is independently at
each occurrence unsubstituted or substituted C.sub.6-24 arylene, or
unsubstituted or substituted C.sub.3-24 heteroarylene; Y.sup.1 is
chloro, bromo, iodo, mesylate, tosylate, triflate, sulfonyl
fluoride, sulfonyl chloride, sulfonyl bromide, or sulfonyl iodide;
and B.sup.x is independently at each occurrence a boron-containing
functional group bonded to Ar.sup.x via a boron atom.
2. The method of claim 1, wherein the monomer comprises the first
monomer having structure (1).
3. The method of claim 1, wherein the monomer comprises the first
comonomer having structure (2) and the second comonomer having
structure (3).
4. The method of claim 1, further comprising forming in situ the
first monomer having structure (1) by reacting sulfuryl fluoride
(S(O).sub.2F.sub.2) with a first monomer precursor having structure
(4) HO--Ar.sup.x--B.sup.x (4) wherein Ar.sup.x and B.sup.x are
defined as in claim 1; or further comprising forming in situ the
first comonomer having structure (2) by reacting sulfuryl fluoride
with a first comonomer precursor having structure (5) or structure
(6) HO--Ar.sup.x--Y.sup.2 (5) HO--Ar.sup.x--OH (6) wherein Ar.sup.x
is defined as in claim 1; and Y.sup.2 is chloro, bromo, iodo,
mesylate, tosylate, or triflate.
5. The method of claim 1, wherein in structure (1) and structure
(3) each occurrence of B.sup.x is selected from the group
consisting of --BF.sub.3.sup.-M.sup.+, wherein each occurrence of
M.sup.+ is independently an alkali metal cation, or an
unsubstituted or substituted ammonium ion; --B(OH).sub.2;
##STR00042## wherein R.sup.3 and R.sup.4 are each independently
C.sub.1-18 alkyl, C.sub.3-18 cycloalkyl, or C.sub.6-18 aryl; and
R.sup.3 and R.sup.4 are optionally covalently linked to each other
to form a ring that includes --R.sup.3--O--B--O--R.sup.4--; and
##STR00043## wherein R.sup.5 and R.sup.6 are each independently
hydrogen, unsubstituted or substituted C.sub.1-12 linear or
branched alkyl, unsubstituted or substituted C.sub.3-12 cycloalkyl,
unsubstituted or substituted C.sub.6-12 aryl, unsubstituted or
substituted C.sub.3-12 heteroaryl, or ##STR00044## wherein Ar.sup.x
is defined as in claim 1; and wherein Z is chloro, bromo, iodo,
mesylate, tosylate, triflate, or sulfonyl fluoride, or B.sup.z
wherein B.sup.z is selected from the group consisting of
--BF.sub.3.sup.-M.sup.+, wherein each occurrence of M.sup.+ is
independently an alkali metal cation, or an unsubstituted or
substituted ammonium ion; --B(OH).sub.2; ##STR00045## wherein
R.sup.3 and R.sup.4 are each independently C.sub.1-18 alkyl,
C.sub.3-18 cycloalkyl, or C.sub.6-18 aryl; and R.sup.3 and R.sup.4
are optionally covalently linked to each other to form a ring that
includes --R.sup.3--O--B--O--R.sup.4--.
6. The method of claim 1, wherein in structure (1) Ar.sup.x is
substituted with at least one functional group selected from the
group consisting of hydroxyl, acetals, ketals, esters, and
lactones; and wherein in structure (2) or structure (3) or both
structure (2) and structure (3), Ar.sup.x is substituted with at
least one functional group selected from the group consisting of
hydroxyl, acetals, ketals, esters, and lactones.
7. The method of claim 1, wherein in structure (1) Ar.sup.x has
structure (7) ##STR00046## wherein Ar.sup.1 and Ar.sup.2 are each
independently unsubstituted or substituted C.sub.6-18 arylene, or
unsubstituted or substituted C.sub.3-18 heteroarylene, provided
that the sum of carbon atoms in Ar.sup.1 and Ar.sup.2 is 9 to 24;
and R.sup.3 and R.sup.4 are each independently hydrogen,
unsubstituted or substituted C.sub.1-18 linear or branched alkyl,
unsubstituted or substituted C.sub.3-18 cycloalkyl; unsubstituted
or substituted C.sub.6-18 aryl, or unsubstituted or substituted
C.sub.3-18 heteroaryl; and R.sup.1 and R.sup.2 are optionally
covalently linked to each other to form a ring that includes
--R.sup.1--C--R.sup.2--; and wherein in structure (2) or structure
(3) or both structure (2) and structure (3), Ar.sup.x has structure
(7) as defined above.
8. The method of claim 1, wherein the monomer comprises the first
monomer having structure (1), and wherein the first monomer having
structure (1) is selected from the group consisting of ##STR00047##
##STR00048## and combinations thereof; or wherein the monomer
comprises the first comonomer having structure (2) and the second
comonomer having structure (3), and wherein the first comonomer
having structure (2) is selected from the group consisting of
##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053##
##STR00054## and combinations thereof.
9. The method of claim 1, wherein the monomer comprises the first
monomer having structure (1), and wherein the first monomer having
structure (1) is selected from the group consisting of ##STR00055##
##STR00056## ##STR00057## ##STR00058## and combinations thereof; or
wherein the monomer comprises the first comonomer having structure
(2) and the second comonomer having structure (3), and wherein the
first comonomer having structure (2) is selected from the group
consisting of ##STR00059## ##STR00060## ##STR00061## ##STR00062##
and combinations thereof.
10. The method of claim 1, wherein the catalyst comprises a group
10 atom; and wherein the base is selected from the group consisting
of lithium carbonate, sodium carbonate, potassium carbonate,
rubidium carbonate, cesium carbonate, ammonium carbonate,
substituted ammonium carbonates, hydrogen carbonates, lithium
phosphate, sodium phosphate, potassium phosphate, rubidium
phosphate, cesium phosphate, ammonium phosphate, substituted
ammonium phosphates, hydrogen phosphates, lithium acetate, sodium
acetate, potassium acetate, rubidium acetate, cesium acetate,
ammonium acetate, substituted ammonium acetates, formate salts,
fluoroacetate salts, propionate anions with lithium, sodium,
potassium, rubidium, cesium, ammonium, and substituted ammonium
cations, lithium hydroxide, sodium hydroxide, potassium hydroxide,
magnesium dihydroxide, calcium dihydroxide, strontium dihydroxide,
and barium dihydroxide, aluminum trihydroxide, gallium
trihydroxide, indium trihydroxide, thallium trihydroxide,
triethylamine, N,N-diisopropylethylamine,
1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene,
1,8-diazabicyclo[5.4.0]undec-7-ene, lithium, sodium, and potassium
salts of bis(trimethylsilyl)amide, lithium, sodium, and potassium
salts of t-butoxide, 1,8-bis(dimethylamino)naphthalene, pyridine,
morpholine, 2,6-lutidine, triethylamine,
N,N-dicyclohexylmethylamine, diisopropylamine, sodium fluoride,
potassium fluoride, cesium fluoride, silver fluoride, tetra butyl
ammonium fluoride, ammonium fluoride, triethyl ammonium fluoride,
and combinations thereof.
Description
FIELD
[0001] The present invention relates to a method of synthesizing
polyaryl polymers using fluorosulfonyl-substituted monomers.
INTRODUCTION
[0002] Polyaryl polymers in which aryl groups are directly bonded
to each other are useful in a variety of applications, including as
precursors to conductive and semiconductive polymers for use in
Organic Light Emitting Diodes (OLED) and Polymeric Light Emitting
Diodes (PLED), as acid-sensitive polymers and highly etch-resistant
polymers for photolithography, and as pH-sensitive drug delivery
encapsulants.
[0003] Ober U.S. Pat. No. 8,962,779 B2 describes forming polyacetal
and polyketal polymers by coupling an acetal- or ketal-containing
monomer with itself or a comonomer in the presence of a catalyst
and a base. The aryl-aryl coupling reaction involves the reaction
of a first functional group directly bound to an aryl group and
selected from chloro, bromo, iodo, mesylate, tosylate, or triflate
with a second functional group that is a boron-containing
functional group in which the boron atom is directly bound to an
aryl group. While the Ober polymerization method works well, it is
known to be sensitive to impurities in the aryl halide. Also, the
synthesis and handling of aryl mesylates, tosylates, and triflates
adds cost and complexity to the polymerization process.
[0004] There is therefore a desire for a simpler polymerization
method that does not require a monomer substituted with a chloro,
bromo, iodo, mesylate, tosylate, or triflate group.
SUMMARY
[0005] One embodiment is a method of forming a polyaryl polymer,
the method comprising: reacting a monomer in the presence of a
catalyst and a base to form a polymer; wherein the monomer
comprises (a) a first monomer having structure (1)
##STR00001##
[0006] wherein Ar.sup.x is unsubstituted or substituted C.sub.6-43
arylene, or unsubstituted or substituted C.sub.3-43 heteroarylene;
and B.sup.x is a boron-containing functional group bonded to
Ar.sup.x via a boron atom; or (b) a first comonomer having
structure (2) and a second comonomer having structure (3)
##STR00002##
wherein Ar.sup.x is independently at each occurrence unsubstituted
or substituted C.sub.6-24 arylene, or unsubstituted or substituted
C.sub.3-24 heteroarylene; Y.sup.1 is chloro, bromo, iodo, mesylate,
tosylate, triflate, sulfonyl fluoride, sulfonyl chloride, sulfonyl
bromide, or sulfonyl iodide; and B.sup.x is independently at each
occurrence a boron-containing functional group bonded to Ar.sup.x
via a boron atom.
[0007] This and other embodiments are described in detail
below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a chemical scheme for polymerization of a monomer
comprising a fluorosulfonyl groups and a dioxaborolanyl group.
[0009] FIG. 2 is a chemical scheme for copolymerization of a first
comonomer with two fluorosulfonyl groups and a second comonomer
with two dioxaborolanyl groups.
[0010] FIG. 3 is a chemical scheme for another copolymerization of
a first comonomer with two fluorosulfonyl groups and a second
comonomer with two dioxaborolanyl groups.
[0011] FIG. 4 is a chemical scheme for copolymerization of a two
monomers, each having a fluorosulfonyl group and a dioxaborolanyl
group.
[0012] FIG. 5 is a chemical scheme for copolymerization of a first
comonomer with two fluorosulfonyl groups and a second comonomer
with two dioxaborolanyl groups, wherein neither monomer comprises a
ketal or other acid-sensitive group.
DETAILED DESCRIPTION
[0013] The present inventors have determined that polyaryl polymers
can be produced by the catalyzed reaction of an aryl fluorosulfonyl
group with a boron-functionafized aryl group. The two functional
group types can reside on the same monomer, which can be
polymerized with itself, or on different monomers, which can be
copolymerized. The fluorosulfonyl-substituted aryl monomer can be
prepared in situ by reaction of the corresponding phenol with
sulfuryl fluoride (FS(O).sub.2F), and used without purification
other than degassing. The fluorosulfonyl-substituted aryl monomer
thus provides a more convenient and less expensive alternative to
the chloro-, bromo-, iodo-, mesylate-, tosylate-, or
triflate-substituted monomers used in prior art methods.
[0014] As used herein, "substituted" means including at least one
substituent such as a halogen (i.e., F, Cl, Br, I), hydroxyl,
amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide,
disulfide, nitro, C.sub.1-18 alkyl, C.sub.1-18 alkoxyl, C.sub.6-18
aryl, C.sub.6-18 aryloxyl, C.sub.7-18 alkylaryl, or C.sub.7-18
alkylaryloxyl. It will be understood that any group or structure
disclosed with respect to the formulas herein may be so substituted
unless otherwise specified, or where such substitution would
significantly adversely affect the desired properties of the
resulting structure. Also, "fluorinated" means having one or more
fluorine atoms incorporated into the group. For example, where a
C.sub.1-18 fluoroalkyl group is indicated, the fluoroalkyl group
can include one or more fluorine atoms, for example, a single
fluorine atom, two fluorine atoms (e.g., as a 1,1-difluoroethyl
group), three fluorine atoms (e.g., as a 2,2,2-trifluoroethyl
group), or fluorine atoms at each free valence of carbon (e.g., as
a perfluorinated group such as --CF.sub.3, --C.sub.2F.sub.5,
--C.sub.3F.sub.7, or --C.sub.4F.sub.9).
[0015] As used herein, "alkyl", whether alone or as part of another
group (e.g., in dialkylamino), encompasses straight and branched
chain aliphatic groups having the indicated number of carbon atoms.
If no number is indicated (e.g., aryl-alkyl-), then 1-6 alkyl
carbons are contemplated. Preferred alkyl groups include, without
limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, and hexyl.
[0016] As used herein, "cycloalkyl", whether alone as part of
another group, encompasses fully saturated aliphatic cyclic groups
having the indicated number of carbon atoms. In no number of carbon
atoms is indicated, then 3 to 12 atoms are contemplated. Preferred
cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopropyl,
1-methylcyclopropyl, cyclohexyl, cyclooctyl, cyclodecyl, and
cyclododecyl.
[0017] As used herein, "aryl" is an aromatic moiety comprising one
to three aromatic rings. In one instance, the aryl group is a
C.sub.6-18 aryl group. In some embodiments, the aryl group is a
C.sub.6-10 aryl group. In some embodiments, the aryl group is a
C.sub.10-18 aryl group. Aryl groups contain 4n+2 pi electrons,
where n is an integer. Preferred aryls include, without limitation,
phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl,
and fluorenyl. Unless otherwise indicated, the aryl group is
optionally substituted with 1 or more substituents that are
compatible with the syntheses described herein. Such substituents
include, but are not limited to, sulfonate groups, boron-containing
groups, C.sub.1-6 alkyl, nitro, halogen, cyano, carboxylic acids
(e.g., C.sub.0-6--COOH), esters, amides, and C.sub.2-C.sub.6
alkenyl. Other substituents are known in the art. Unless otherwise
indicated, the foregoing substituent groups are not themselves
further substituted.
[0018] As used herein, "heteroaryl" refers to an aromatic ring
system containing at least one heteroatom selected from nitrogen,
oxygen, and sulfur. Preferably, the heteroaryl group is a five or
six-membered ring. The heteroaryl ring may be fused or otherwise
attached to one or more heteroaryl rings, aromatic or non-aromatic
hydrocarbon rings or heterocycloalkyl rings. Examples of heteroaryl
groups include, without limitation, pyridine, pyrimidine,
pyridazine, pyrazine and furan. The heteroaryl group may be
optionally substituted with 1 or more substituents that are
compatible with the syntheses described herein. Such substituents
include, but are not limited to, fluorosulfonate groups,
boron-containing groups, C.sub.1-6 alkyl, nitro, halogen, cyano,
carboxylic acids (e.g., C.sub.0-6--COOH), esters, amides and
C.sub.2-6 alkene. Other substituents are known in the art. Unless
otherwise indicated, the foregoing substituent groups are not
themselves further substituted.
[0019] One embodiment is a method of forming a polyaryl polymer,
the method comprising: reacting a monomer in the presence of a
catalyst and a base to form a polymer; wherein the monomer
comprises (a) a first monomer having structure (1)
##STR00003##
wherein Ar.sup.x is unsubstituted or substituted C.sub.6-43
arylene, or unsubstituted or substituted C.sub.3-43 heteroarylene;
and B.sup.x is a boron-containing functional group bonded to
Ar.sup.x via a boron atom; or (b) a first comonomer having
structure (2) and a second comonomer having structure (3)
##STR00004##
wherein Ar.sup.x is independently at each occurrence unsubstituted
or substituted C.sub.6-24 arylene, or unsubstituted or substituted
C.sub.3-24 heteroarylene; Y.sup.1 is chloro, bromo, iodo, mesylate,
tosylate, triflate, or sulfonyl fluoride; and B.sup.x is
independently at each occurrence a boron-containing functional
group bonded to Ar.sup.x via a boron atom.
[0020] In structures (1), (2), and (3), each occurrence of Ar.sup.x
is independently unsubstituted or substituted C.sub.6-43 arylene,
or unsubstituted or substituted C.sub.3-43 heteroarylene. Examples
of Ar.sup.x groups include
##STR00005## ##STR00006##
[0021] In some embodiments of structures (1), (2), and (3),
Ar.sup.x includes an acetal or ketal groups that becomes
incorporated into the main chain of the resulting polymer. In these
embodiment, Ar.sup.x can have structure (7)
##STR00007##
wherein Ar.sup.1 and Ar.sup.2 are each independently unsubstituted
or substituted C.sub.6-18 arylene, or unsubstituted or substituted
C.sub.3-18 heteroarylene, provided that the sum of carbon atoms in
Ar.sup.1 and Ar.sup.2 is 9 to 24; and R.sup.3 and R.sup.4 are each
independently hydrogen, unsubstituted or substituted C.sub.1-18
linear or branched alkyl, unsubstituted or substituted C.sub.3-18
cycloalkyl; unsubstituted or substituted C.sub.6-18 aryl, or
unsubstituted or substituted C.sub.3-18 heteroaryl; and R.sup.1 and
R.sup.2 are optionally covalently linked to each other to form a
ring that includes --R.sup.1--C--R.sup.2--. Examples of Ar.sup.x
having structure (7) include
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
##STR00013## ##STR00014## ##STR00015##
[0022] In structures (1) and (3), each occurrence of B.sup.x is
independently a boron-containing functional group bonded to
Ar.sup.x via a boron atom. Examples of B.sup.x include
--BF.sub.3.sup.-M.sup.+, wherein each occurrence of M.sup.+ is
independently an alkali metal cation, or an unsubstituted or
substituted ammonium ion; --B(OH).sub.2;
##STR00016##
wherein R.sup.3 and R.sup.4 are each independently C.sub.1-18
alkyl, C.sub.3-18 cycloalkyl, or C.sub.6-18 aryl; and R.sup.3 and
R.sup.4 are optionally covalently linked to each other to form a
ring that includes --R.sup.3--O--B--O--R.sup.4--; and
##STR00017##
wherein R.sup.5 and R.sup.6 are each independently hydrogen,
unsubstituted or substituted C.sub.1-12 linear or branched alkyl,
unsubstituted or substituted C.sub.3-12 cycloalkyl, unsubstituted
or substituted C.sub.6-12 aryl, unsubstituted or substituted
C.sub.3-12 heteroaryl, or
##STR00018##
wherein Ar.sup.x is defined as in structure (1); and wherein Z is
chloro, bromo, iodo, mesylate, tosylate, triflate, sulfonyl
fluoride, or B.sup.z wherein B.sup.z is selected from the group
consisting of --BF.sub.3.sup.-M.sup.+, wherein each occurrence of
M.sup.+ is independently an alkali metal cation, or an
unsubstituted or substituted ammonium ion; --B(OH).sub.2;
##STR00019##
wherein R.sup.3 and R.sup.4 are each independently C.sub.1-18
alkyl, C.sub.3-18 cycloalkyl, or C.sub.6-18 aryl; and R.sup.3 and
R.sup.4 are optionally covalently linked to each other to form a
ring that includes --R.sup.3--O--B--O--R.sup.4--.
[0023] Specific examples of B.sup.x include
##STR00020## ##STR00021##
[0024] In some embodiments, the monomer comprises two comonomers,
the first comonomer having at least one fluorosulfonyl group, and
the second comonomer having two boron-containing functional groups.
In these embodiments, the first comonomer can have structure (2),
and the second comonomer can have structure (3)
##STR00022##
In structures (2) and (3), Ar.sup.x is defined as it is for
structure (1). It will be understood that Ar.sup.x groups in
structures (2) and (3) are defined independently. In structure (3),
B.sup.x is defined as for structure (1). B.sup.x groups in
structures (1) and (3) are defined independently. In structure (2),
Y.sup.1 is chloro, bromo, iodo, mesylate, tosylate, triflate, or
sulfonyl fluoride. Among these, sulfonyl fluoride is preferred.
[0025] In some embodiments, the monomer comprises the first monomer
having structure (1). In other embodiments, the monomer comprises
the first comonomer having structure (2) and the second comonomer
having structure (3). It is also possible that the monomer
comprises the first monomer having structure (1), the first
comonomer having structure (2), and the second comonomer having
structure (3).
[0026] One of the advantages of the invention is that monomers with
fluorosulfonyl groups can be formed in situ from the corresponding
phenols. Thus, in some embodiments the method further comprises
forming in situ the first monomer having structure (1) by reacting
sulfuryl fluoride (S(O).sub.2F.sub.2) with a first monomer
precursor having structure (4)
HO--Ar.sup.x--B.sup.x (4)
wherein Ar.sup.x and B.sup.x are defined for structure (1). The
comonomer having structure (2) can be formed in situ instead of or
in addition to the monomer having structure (1). Thus, in some
embodiments, the method further comprises forming in situ the first
comonomer having structure (2) by reacting sulfuryl fluoride with a
first comonomer precursor having structure (5) or structure (6)
HO--Ar.sup.x--Y.sup.2 (5)
HO--Ar.sup.x--OH (6)
wherein Ar.sup.x is defined as for structure (2); and Y.sup.2 is
chloro, bromo, iodo, mesylate, tosylate, or triflate.
[0027] In some embodiments, in structure (1) Ar.sup.x is
substituted with at least one functional group selected from the
group consisting of hydroxyl, acetals, ketals, esters, and
lactones; and in structure (2) or structure (3) or both structure
(2) and structure (3), Ar.sup.x is substituted with at least one
functional group selected from the group consisting of hydroxyl,
acetals, ketals, esters, and lactones. In this context, acetals,
ketals, esters, and lactones can be monovalent or divalent
substituents.
[0028] In very specific embodiments, the monomer comprises the
first monomer having structure (1), and the first monomer having
structure (1) is selected from the group consisting of
##STR00023## ##STR00024##
and combinations thereof; or the monomer comprises the first
comonomer having structure (2) and the second comonomer having
structure (3), and the first comonomer having structure (2) is
selected from the group consisting of
##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
##STR00030##
and combinations thereof.
[0029] In other very specific embodiments, the monomer comprises
the first monomer having structure (1), and the first monomer
having structure (1) is selected from the group consisting of
##STR00031## ##STR00032## ##STR00033## ##STR00034##
and combinations thereof; or the monomer comprises the first
comonomer having structure (2) and the second comonomer having
structure (3), and the first comonomer having structure (2) is
selected from the group consisting of
##STR00035## ##STR00036## ##STR00037## ##STR00038##
and combinations thereof.
[0030] Monomer synthesis is described in co-filed U.S. patent
application Ser. No. ______ [attorney docket number 78156-US-NP
(DOW0047US)].
[0031] In the method, the monomer is reacted in the presence of a
catalyst and a base to form the polymer. The catalyst comprises a
group 10 atom. In some instances, the reaction mixture also
includes a ligand, and a base. The group 10 atoms include nickel,
palladium and platinum. The catalyst having at least one group 10
atom is preferably generated in situ from one or more precatalysts
and one or more ligands. Examples of palladium precatalysts include
palladium(II) acetate, palladium(II) chloride,
dichlorobis(acetonitrile)palladium(II),
dichlorobis(benzonitrile)palladium(II), allylpalladium chloride
dimer, palladium(II) acetylacetonate, palladium(II) bromide,
bis(dibenzylideneacetone)palladium(0), bis(2-methylallyl)palladium
chloride dimer, crotylpalladium chloride dimer,
dichloro(1,5-cyclooctadiene)palladium(II),
dichloro(norbornadiene)palladium(II), palladium(II)
trifluoroacetate, palladium(II) benzoate, palladium(II)
trimethylacetate, palladium(II) oxide, palladium(II) cyanide,
tris(dibenzylideneacetone)dipalladium(0), palladium(II)
hexafluoroacetylacetonate,
cis-dichloro(N,N,N',N'-tetramethylethylenediamine)palladium(II),
and cyclopentadienyl[(1,2,3-n)-1-phenyl-2-propenyl]palladium(II).
In other embodiments, nickel-based and catalysts are used. In still
other embodiments, platinum-based catalysts and precatalysts are
used.
[0032] In some embodiments, pyridine-enhanced precatalyst
preparation stabilization and initiation (PEPPSI) type catalysts
are used, for example,
[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyrid-
yl)palladium(II) dichloride, and
(1,3-Bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl)palladium(I-
I) dichloride.
[0033] The ligand used in the reaction mixture is preferably
selected to generate the catalyst from the selected precatalyst.
For example, the ligand may be a phosphine ligand, a carbene
ligand, an amine-based ligand, an aminophosphine-based ligand, or
an N-heterocyclic carbene-based ligand.
[0034] Suitable phosphine ligands include mono- and bi-dentate
phosphines containing functionalized aryl or alkyl substituents.
For example, suitable phosphine ligands include triphenylphosphine;
tri(o-tolyl)phosphine; tris(4-methoxyphenyl)phosphine;
tris(pentafluorophenyl)phosphine; tri(p-tolyl)phosphine;
tri(2-furyl)phosphine; tris(4-chlorophenyl)phosphine;
di(1-adamantyl)(1-naphthoyl)phosphine; benzyldiphenylphosphine;
1,1'-bis(di-t-butylphosphino)ferrocene;
(-)-1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene;
(-)-2,3-bis[(2R,5R)-2,5-dimethylphospholanyl]-1-[3,5-bis(trifluoromethyl)-
phenyl]-1H-pyrrole-2,5-dione; 1,2-bis(diphenylphosphino)benzene;
2,2'-bis(diphenylphosphino)-1,1'-binaphthyl;
2,2'-bis(diphenylphosphino)-1,1'-biphenyl,
1,4-bis(diphenylphosphino)butane; 1,2-bis(diphenylphosphino)ethane;
2-[bis(diphenylphosphino)methyl]pyridine;
1,5-bis(diphenylphosphino)pentane;
1,3-bis(diphenylphosphino)propane;
1,1'-bis(di-i-propylphosphino)ferrocene;
(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole;
tricyclohexylphosphine;
N-[2-(di-1-adamantylphosphino)phenyl]morpholine;
2-(di-t-butylphosphino)biphenyl;
2-(di-t-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-i-propyl-1,1'-biphenyl-
; 2-di-t-butylphosphino-2'-(N,N-dimethylamino)biphenyl;
2-di-t-butylphosphino-2'-methylbiphenyl;
dicyclohexylphenylphosphine;
2-(dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-tri-i-propyl-1,1'-biphen-
yl; 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl;
2-dicyclohexylphosphino-2',6'-dimethylamino-1,1'-biphenyl;
2-dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl;
2-dicyclohexylphosphino-2'-methylbiphenyl;
2-[2-(dicyclohexylphosphino)phenyl]-1-methyl-1H-indole;
2-(dicyclohexylphosphino)-2',4',6'-tri-i-propyl-1,1'-biphenyl;
[4-(N,N-dimethylamino)phenyl]di-t-butylphosphine;
9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene;
(R)-(-)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine-
; tribenzylphosphine; tri-t-butylphosphine; tri-n-butylphosphine;
and 1,1'-bis(diphenylphosphino)ferrocene.
[0035] Suitable amine and aminophosphine-based ligands include any
combination of monodentate or bidentate alkyl and aromatic amines
including pyridine, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-dipyridyl,
1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline,
4,7-dimethoxy-1,10-phenanthroline,
N,N,N'N'-tetramethylethylenediamine, 1,3-diaminopropane, ammonia,
4-(aminomethyl)pyridine,
(1R,2S,9S)-(+)-11-methyl-7,11-diazatricyclo[7.3.1.0.sup.2,7]tridecane,
2,6-di-tert-butylpyridine, 2,2'-bis[(4S)-4-benzyl-2-oxazoline],
2,2-bis((4S)-(-)-4-isopropyloxazoline)propane,
2,2'-methylenebis[(4S)-4-phenyl-2-oxazoline], and
4,4'-di-tert-butyl-2,2'bipyridyl. In addition, aminophosphine
ligands such as 2-(diphenylphosphino)ethylamine,
2-(2-(diphenylphosphino)ethyl)pyridine,
(1R,2R)-2-(diphenylphosphino)cyclohexanamine, and
2-(di-tert-butylphosphino)ethylamine can be used.
[0036] Suitable carbene ligands include N-heterocyclic carbene
(NHC) based ligands, including
1,3-bis(2,4,6-trimethylphenyl)imidazolinium chloride,
1,3-bis(2,6-diisopropylphenyl)imidazolium chloride,
1,3-bis-(2,6-diisopropylphenyl)imidazolinium chloride,
1,3-diisopropylimidazolium chloride, and
1,3-dicyclohexylbenzimidazolium chloride.
[0037] In some embodiments, the catalyst or a pre-catalyst thereof
has structure (8)
##STR00039##
wherein each occurrence of R.sup.5 is independently unsubstituted
or substituted C.sub.1-12 linear or branched alkyl, unsubstituted
or substituted C.sub.3-12 cycloalkyl, unsubstituted or substituted
C.sub.6-12 aryl, or unsubstituted or substituted ferrocenyl;
R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10, are each
independently hydrogen, C.sub.1-6 linear or branched alkyl,
C.sub.3-6 cycloalkyl, or phenyl; and Z is selected from the group
consisting of fluoro, chloro, bromo, iodo, cyano (--CN), cyanato
(--OCN), isocyanato (--NCO), thiocyanato (--SCN), isothiocyanato
(--NCS), nitro (--NO.sub.2), nitrito (--ON.dbd.O), azido
(--N.dbd.N.dbd.N--), and hydroxyl.
[0038] The base used in the reaction mixture is selected to be
compatible with the catalyst, the boron-containing group, and the
halosulfonate. Suitable bases include, but are not limited to,
carbonate salts, phosphate salts, acetate salts and carboxylic acid
salts.
[0039] Examples of carbonate salts include lithium carbonate,
sodium carbonate, potassium carbonate, rubidium carbonate, cesium
carbonate, ammonium carbonate, substituted ammonium carbonates, the
corresponding hydrogen carbonate salts, and combinations of the
foregoing salts.
[0040] Examples of phosphate salts include, but are not limited to,
lithium phosphate, sodium phosphate, potassium phosphate, rubidium
phosphate, cesium phosphate, ammonium phosphate, substituted
ammonium phosphates, corresponding hydrogen phosphate salts, and
combinations of the foregoing salts.
[0041] Examples of acetate salts include lithium acetate, sodium
acetate, potassium acetate, rubidium acetate, cesium acetate,
ammonium acetate, substituted ammonium acetates, and combinations
of the foregoing salts.
[0042] Other bases include salts of formate, fluoroacetate, and
propionate anions with lithium, sodium, potassium, rubidium,
cesium, ammonium, and substituted ammonium cations; metal
hydroxides, such as lithium hydroxide, sodium hydroxide, potassium
hydroxide; metal dihydroxides such as magnesium dihydroxide,
calcium dihydroxide, strontium dihydroxide, and barium dihydroxide;
metal trihydroxides such as aluminum trihydroxide, gallium
trihydroxide, indium trihydroxide, thallium trihydroxide;
non-nucleophilic organic amines such as triethylamine,
N,N-diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO),
1,5-Diazabicyclo[4.3.0]non-5-ene (DBN),
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU); bis(silyl)amide salts
such as the lithium, sodium, and potassium salts of
bis(trimethylsilyl)amide; alkoxide salts such as the lithium,
sodium, and potassium salts oft butoxide; and
1,8-bis(dimethylamino)naphthalene; metal fluorides, such as sodium
fluoride, potassium fluoride, cesium fluoride, silver fluoride,
tetra butyl ammonium fluoride, ammonium fluoride, triethyl ammonium
fluoride; and combinations of the foregoing.
[0043] Examples of amine bases, such as alkylamines and
heteroarenes include triethylamine, pyridine, morpholine,
2,6-lutidine, triethylamine, N,N-dicyclohexylmethylamine,
diisopropylamine, and combinations thereof.
[0044] In some embodiments, the base is used in the presence of a
phase-transfer catalyst. In some embodiments, the base is used in
the presence of water. In some embodiments, the base is used in the
presence of an organic solvent. In some embodiments, the base is
used in the presence of two or more of a phase-transfer catalyst,
water, and an organic solvent.
[0045] In some embodiments, the base is selected from the group
consisting of lithium carbonate, sodium carbonate, potassium
carbonate, rubidium carbonate, cesium carbonate, ammonium
carbonate, substituted ammonium carbonates, hydrogen carbonates,
lithium phosphate, sodium phosphate, potassium phosphate, rubidium
phosphate, cesium phosphate, ammonium phosphate, substituted
ammonium phosphates, hydrogen phosphates, lithium acetate, sodium
acetate, potassium acetate, rubidium acetate, cesium acetate,
ammonium acetate, substituted ammonium acetates, formate salts,
fluoroacetate salts, propionate anions with lithium, sodium,
potassium, rubidium, cesium, ammonium, and substituted ammonium
cations, lithium hydroxide, sodium hydroxide, potassium hydroxide,
magnesium dihydroxide, calcium dihydroxide, strontium dihydroxide,
and barium dihydroxide, aluminum trihydroxide, gallium
trihydroxide, indium trihydroxide, thallium trihydroxide,
triethylamine, N,N-diisopropylethylamine,
1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene,
1,8-diazabicyclo[5.4.0]undec-7-ene, lithium, sodium, and potassium
salts of bis(trimethylsilyl)amide, lithium, sodium, and potassium
salts of t-butoxide, 1,8-bis(dimethylamino)naphthalene, pyridine,
morpholine, 2,6-lutidine, triethylamine,
N,N-dicyclohexylmethylamine, diisopropylamine, sodium fluoride,
potassium fluoride, cesium fluoride, silver fluoride, tetra butyl
ammonium fluoride, ammonium fluoride, triethyl ammonium fluoride,
and combinations thereof
[0046] Preferably, at least one equivalent of base is present for
each equivalent of halosulfonate. In some embodiments, no more than
10 equivalents of base are present for each equivalent of
halosulfonate. In some embodiments, at least 2 equivalents of base
are present for each equivalent of halosulfonate. In some
embodiments, no more than 6 equivalents of base are present for
each equivalent of halosulfonate.
[0047] The solvent in the reaction mixture is selected such that it
is suitable for use with the reactants, the catalyst, the ligand,
and the base. For example, suitable solvents include toluene,
xylenes (ortho-xylene, meta-xylene, para-xylene or mixtures
thereof), benzene, water, methanol, ethanol, 1-propanol,
2-propanol, n-butanol, 2-butanol, pentanol, hexanol, tert-butyl
alcohol, tert-amyl alcohol, ethylene glycol, 1,2-propanedioal,
1,3-propanediol, glycerol, N-methyl-2-pyrrolidone, acetonitrile,
N,N-dimethylformamide, methyl acetate, ethyl acetate, propyl
acetate, isopropyl acetate, triacetin, acetone, methyl ethyl
ketone, and ethereal solvents, such as 1,4-dioxane,
tetrahydrofuran, 2-methyltetrahydrofuran, diethylether, cyclopenyl
methyl ether, 2-butyl ethyl ether, dimethoxyethane,
polyethyleneglycol and combinations thereof. In some embodiments in
which the halosulfonate is fluorosulfonate, sulfuryl fluoride is
used neat at a sufficiently low temperature that the sulfuryl
fluoride is a liquid.
[0048] In some embodiments, water is included in the reaction
mixture. One benefit of using fluorosulfonates as compared to
triflates, is that the reaction can be carried out without a
subsequent separation step, or with a simple separation step. In
Suzuki couplings involving triflates, a dedicated purification step
is required to remove byproducts since the products and the
byproducts typically occupy the same phase. In the reaction schemes
described herein, the byproducts are either in the gas phase, and
will bubble out spontaneously or with a simple degassing step, or
will partition into the aqueous phase, which is easily separable.
As such, the reaction scheme described herein provides additional
benefits as compared to Suzuki couplings involving triflates.
EXAMPLES
Synthesis of Polymer 1
[0049] This example illustrates homopolymerization of a single
monomer. FIG. 1 is a chemical scheme for the synthesis of Polymer
1. Polymer 1, shown in FIG. 1, is synthesized by the following
prophetic procedure. Inside a nitrogen-purged glovebox, to a 30
millilter vial is added
4-((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)methoxy)phenyl
sulfurofluoridate (500 milligrams, 1 millimole, 1 equivalent) and
1,4-dioxane (3 milliliters). Potassium phosphate (637 milligrams, 3
millimoles, 3 equivalents) is dissolved in water (637 microliters)
and added to the vial. The mixture is vigorously stirred until both
phases are well-blended after which a catalyst solution of
Pd(crotyl)(P(tBu).sub.3) (0.4 milligram, 1 micromole, 0.001
equivalent) dissolved in 1,4-dioxane (100 microliters) is added.
The reaction is vigorously stirred overnight, optionally with mild
heating. The obtained polymer is optionally end-capped by adding
phenyl boronic acid (18 milligrams, 0.15 millimole, 0.15
equivalent), followed by stirring for another 18-24 hours, addition
of bromobenzene (47 milligrams, 0.3 millimoles, 0.3 equivalents)
and another period of stirring for 18-24 hours.
[0050] The reaction mixture is worked up by adding 5 milliliters of
brine and 15-30 milliliters of ethyl acetate followed by shaking in
an extraction funnel. The aqueous layer is removed and the
remaining organic phase is further washed with brine (1.times.5
milliliters). In order to remove trace palladium and salts, the
organic phase is optionally further transferred into a round bottom
flask equipped with reflux condenser. A saturated aqueous solution
of diethyldithiocarbamate (0.5-1.0 milliliter) is added and the
mixture is vigorously stirred and heated to reflux. The organic
phase is phase separated, dried over magnesium sulfate and filtered
through a two-layered plug of neutral alumina and silica gel. The
crude product is fully eluted with 20-30 mL of additional ethyl
acetate and the combined organic phases are washed with deionized
water (5.times.5 milliliters) and concentrated on the rotary
evaporator. The residue is redissolved in ethyl acetate (.about.5
milliliters) and toluene (0.5-1 milliliters). The polymer is
precipitated by drop-wise addition to stirred methanol. Once the
addition is completed, the suspension is stirred for 30 minutes and
then allowed to settle. The precipitate is collected by filtration.
Optionally, the precipitate can be redissolved in ethyl
acetate/toluene and the precipitation from methanol repeated twice
more. After the final precipitation, the filter cake is dried under
high vacuum at approximately 65.degree. C.
Synthesis of Polymer 2
[0051] This example illustrates copolymerization of a first
comonomer with two fluorosulfonyl groups and a second comonomer
with two dioxaborolanyl groups. FIG. 2 is a chemical scheme for the
synthesis of Polymer 2. Polymer 2, shown in FIG. 2, is synthesized
by the following prophetic procedure. Inside a nitrogen-purged
glovebox, to a 30 milliliter vial is added
((phenylmethylene)bis(oxy))bis(4,1-phenylene)bis(sulfurofluoridate)
(472 milligrams, 1 millimole, 1 equivalent),
3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl acetate
(388 milligrams, 1 millimole, 1 equivalent) and 1,4-dioxane (3
milliliters). Potassium phosphate (637 milligrams, 3 millimoles, 3
equivalents) is dissolved in water (637 microliters) and added to
the vial. The mixture is vigorously stirred until both phases are
well-blended after which catalyst solution of
Pd(crotyl)(P(tBu).sub.3) (0.4 milligram, 1 micromole, 0.001
equivalent) dissolved in 1,4-dioxane (100 microliters) is added.
The reaction is vigorously stirred overnight, optionally with mild
heating. The obtained polymer is optionally end-capped by adding
phenyl boronic acid (18 milligrams, 0.15 millimole, 0.15
equivalent), followed by stirring for another 18-24 hours, addition
of bromobenzene (47 milligrams, 0.3 millimole, 0.3 equivalent) and
another period of stirring for 18-24 hours. Workup is performed as
outlined for Polymer 1.
Synthesis of Polymer 3
[0052] This example provides another illustration of
copolymerization of a first comonomer with two fluorosulfonyl
groups and a second comonomer with two dioxaborolanyl groups. FIG.
3 is a chemical scheme for the synthesis of Polymer 3. Polymer 3,
shown in FIG. 3, is synthesized by the following prophetic
procedure. Inside a nitrogen-purged glovebox, to a 30 milliliter
vial is added
2,2'-(((phenylmethylene)bis(oxy))bis(4,1-phenylene))bis(4,4,5,5-tetrameth-
yl-1,3,2-dioxaborolane) (528 milligrams, 1 millimole, 1
equivalent), 1,3-phenylene bis(sulfurofluoridate) (274 milligrams,
1 millimole, 1 equivalent) and 1,4-dioxane (3 milliliters).
Potassium phosphate (637 milligrams, 3 millimoles, 3 equivalents)
is dissolved in water (637 microliters) and added to the vial. The
mixture is vigorously stirred until both phases are well-blended
after which catalyst solution of Pd(crotyl)(P(tBu).sub.3) (0.4
milligram, 1 micromole, 0.001 equivalent) dissolved in 1,4-dioxane
(100 microliters) is added. The reaction is vigorously stirred
overnight, optionally with mild heating. The obtained polymer is
optionally end-capped by adding phenyl boronic acid (18 milligrams,
0.15 millimole, 0.15 equivalent), followed by stirring for another
18-24 hours, addition of bromobenzene (47 milligrams, 0.3
millimole, 0.3 equivalent) and another period of stirring for 18-24
hours. Workup is performed as outlined for Polymer 1.
Synthesis of Polymer 4
[0053] This example illustrates copolymerization of a two monomers,
each having a fluorosulfonyl group and a dioxaborolanyl group. FIG.
4 is a chemical scheme for the synthesis of Polymer 4. Polymer 4,
shown in FIG. 4, is synthesized by the following prophetic
procedure. Inside a nitrogen-purged glovebox, to a 30 milliliter
vial is added
4-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)ethoxy)pheny-
l sulfurofluoridate (428 milligrams, 1 millimole, 1 equivalent),
3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl
sulfurofluoridate (302 milligrams, 1 millimole, 1 equivalent) and
1,4-dioxane (3 milliliters). Potassium phosphate (637 milligrams, 3
millimoles, 3 equivalents) is dissolved in water (637 microliters)
and added to the vial. The mixture is vigorously stirred until both
phases are well-blended after which catalyst solution of
Pd(crotyl)(P(tBu).sub.3) (0.4 milligram, 1 micromole, 0.001
equivalent) dissolved in 1,4-dioxane (100 microliters) is added.
The reaction is vigorously stirred overnight, optionally with mild
heating. The obtained polymer is optionally end-capped by adding
phenyl boronic acid (18 milligrams, 0.15 millimole, 0.15
equivalent), followed by stirring for another 18-24 hours, addition
of bromobenzene (47 milligrams, 0.3 millimole, 0.3 equivalent) and
another period of stirring for 18-24 hours. Workup is performed as
outlined for Polymer 1.
Synthesis of Polymer 5
[0054] This example illustrates copolymerization of a first
comonomer with two fluorosulfonyl groups and a second comonomer
with two dioxaborolanyl groups. In this example, neither monomer
comprises a ketal or other acid-sensitive group. FIG. 5 is a
chemical scheme for the synthesis of Polymer 5. Polymer 5, shown in
FIG. 5, is synthesized by the following prophetic procedure. Inside
a nitrogen-purged glovebox, to a 30 milliliter vial is added
propane-2,2-diylbis(4,1-phenylene)bis(sulfurofluoridate) (392
milligrams, 1 millimole, 1 equivalent),
1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (330
milligrams, 1 millimole, 1 equivalent) and 1,4-dioxane (3
milliliter). Potassium phosphate (637 milligrams, 3 millimoles, 3
equivalents) is dissolved in water (637 microliters) and added to
the vial. The mixture is vigorously stirred until both phases are
well-blended, after which catalyst solution of
Pd(crotyl)(P(tBu).sub.3) (0.4 milligram, 1 micromole, 0.001
equivalent) dissolved in 1,4-dioxane (100 microliters) is added.
The reaction is vigorously stirred overnight, optionally with mild
heating. The obtained polymer is optionally end-capped by adding
phenyl boronic acid (18 milligrams, 0.15 millimole, 0.15
equivalent), followed by stirring for another 18-24 hours, addition
of bromobenzene (47 milligrams, 0.3 millimole, 0.3 equivalent) and
another period of stirring for 18-24 hours. Workup is performed as
outlined for Polymer 1.
* * * * *